Synthesis of new 2-(thiazol-4-yl)thiazolidin-4-one derivatives as potential anti-mycobacterial agents - Abhale, Yogita K.; Shinde, Abhijit; Shelke, Monika; Nawale, Laxman; Sarkar, Dhiman; Mhaske, Pravin C. (Bioorganic Chemistry, 2021)
To search for potent antimycobacterial lead compounds, a new series of 3-substituted phenyl-2-(2-(substituted phenyl)thiazol-4-yl) thiazolidin-4-one (5a-t) derivatives have been synthesized by the condensation of 2 substituted phenyl thiazole-4-carbaldehyde with aromatic amine followed by cyclocondensation with thioglycolic acid. The structure of the newly synthesized 2-(thiazol-4-yl)thiazolidin-4-one derivatives were characterized by the spectroscopic analysis. The synthesized compounds were screened for antimycobacterial activity against Mycobacterium tuberculosis H37Ra (MTB) (ATCC 25177) and Mycobacterium bovis BCG (BCG, ATCC 35743). Most of the 2-(thiazol-4-yl)thiazolidin-4-one derivatives showed good to excellent antimycobacterial activity against both the Mtb strains. Nine derivatives 5c, 5g, 5j, 5m, 5n, 5o, 5p, 5s, and 5t showed excellent activity against M. bovis BCG with MIC 4.43 to 24.04 mu M were further evaluated for the cytotoxicity activity against HeLa A549, and HCT-116 cell lines and showed no significant cytotoxic activity at the maximum concentration evaluated. The potential antimycobacterial activities enforced that the thiazolyl-thiazolidin-4-one derivatives could lead to compounds that could treat tuberculosis.
Keywords: Cytotoxicity; Mycobacterium tuberculosis; Thiazole; Thiazolidin-4-one

Synthetic heparan sulfate ligands for vascular endothelial growth factor to modulate angiogenesis - Jain, Prashant; Shanthamurthy, Chethan D.; Leviatan Ben-Arye, Shani; Yehuda, Sharon; Nandikol, Sharvani S.; Thulasiram, V, Hirekodathakallu; Padler-Karavani, Vered; Kikkeri, Raghavendra (Chemical Communications, 2021)
We report the discovery of a potential heparan sulfate (HS) ligand to target several growth factors using 13 unique HS tetrasaccharide ligands. By employing an HS microarray and SPR, we deciphered the crucial structure-binding relationship of these glycans with the growth factors BMP2, VEGF(165), HB-EGF, and FGF2. Notably, GlcNHAc(6-O-SO3-)-IdoA(2-O-SO3-) (HT-2,6S-NAc) tetrasaccharide showed strong binding with the VEGF(165) growth factor. In vitro vascular endothelial cell proliferation, migration and angiogenesis was inhibited in the presence of VEGF(165) and HT-2,6S-NAc or HT-6S-NAc, revealing the potential therapeutic role of these synthetic HS ligands.

Tuning the selectivity of CO2 hydrogenation using ceramic hollow fiber catalytic modules - Jogdand, Shunottara M.; Bedadur, Prachiti R.; Torris, Arun; Kharul, Ulhas K.; Naidu, V. Satyam; Devi, R. Nandini (Reaction Chemistry & Engineering, 2021)
The unique structural features and advantageous pore distributions of alumina hollow fibers can be exploited to tune the selectivity in heterogeneous catalysis. Formation of a finger-like cavity structure is the unique characteristic of the phase inversion method, which provides a larger surface area to volume ratio desirable for catalytic reactions. This feature, along with a highly porous sandwiched skin layer, makes this architecture superior to conventional powder catalysts or other structured catalyst forms like monoliths. Alumina hollow fibers are prepared by the modified phase inversion method and characterized for their pore size and distribution. Ni metal nanoparticles are uniformly deposited in the Al2O3 hollow fibers to prepare a Ni/Al2O3 catalyst and tested for the CO2 methanation reaction. Suitable reactor and catalyst loading methods are designed and optimized to achieve higher CO2 to methane conversion in a temperature range of 225 to 400 degrees C. The alpha-alumina phase, which is usually reported to be a poor support for Ni in CO2 methanation in the conventional fixed bed configuration, showed high activity when modulated as hollow fibers. Also, the selectivity to CH4 is enhanced and minimal CO formation is observed. The kinetic rate expressions are simulated for the prediction of methane and CO gas evolution at the outlet with temperature. The experimental results for the gas composition are in good agreement with the model predictions. The advantage of such a module reactor is explained based on the mass transfer limitations and consequently the reaction time constants arrived at from the predicted gas compositions.

A universal framework for detecting cis-regulatory diversity in DNA regions - Biswas, Anushua; Narlikar, Leelavati (Genome Research, 2021)
High-throughput sequencing-based assays measure different biochemical activities pertaining to gene regulation, genomewide. These activities include transcription factor (TF)-DNA binding, enhancer activity, open chromatin, and more. A major goal is to understand underlying sequence components, or motifs, that can explain the measured activity. It is usually not one motif but a combination of motifs bound by cooperatively acting proteins that confers activity to such regions. Furthermore, regions can be diverse, governed by different combinations of TFs/ motifs. Current approaches do not take into account this issue of combinatorial diversity. We present a new statistical framework, cisDIVERSITY, which models regions as diverse modules characterized by combinations of motifs while simultaneously learning the motifs themselves. Because cisDIVERSITY does not rely on knowledge of motifs, modules, cell type, or organism, it is general enough to be applied to regions reported by most high-throughput assays. For example, in enhancer predictions resulting from different assays-GRO-cap, STARR-seq, and those measuring chromatin structure-cisDIVERSITY discovers distinct modules and combinations of TF binding sites, some specific to the assay. From protein-DNA binding data, cisDIVERSITY identifies potential cofactors of the profiled TF, whereas from ATAC-seq data, it identifies tissue-specific regulatory modules. Finally, analysis of single-cell ATAC-seq data suggests that regions open in one cell-state encode information about future states, with certain modules staying open and others closing down in the next time point.

Uraria picta: a comprehensive review on evidences of utilization and strategies of conservation - Bhusare, B. P.; Ahire, M. L.; John, C. K.; Nikam, T. D. (Journal of Phytology, 2021)
<em style="color: rgba(0, 0, 0, 0.87); font-family: "Noto Sans", -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, Oxygen-Sans, Ubuntu, Cantarell, "Helvetica Neue", sans-serif; font-size: 14px; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; text-align: justify;">Uraria picta <span style="color: rgba(0, 0, 0, 0.87); font-family: "Noto Sans", -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, Oxygen-Sans, Ubuntu, Cantarell, "Helvetica Neue", sans-serif; font-size: 14px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; text-align: justify;">(Jacq.) DC. (Prishnaparni) is one of the most important medicinal plants used in different traditional systems of medicines including the Ayurveda and Traditional Chinese medicine. The major use of this plant was found in the most popular Ayurvedic formulation “Dashmula” and in several many other important Ayurvedic formulations. IUCN placed this woody herb in the least concern category as per version 3.1. It has extensive therapeutic uses and pharmacological activities. Though this plant is a source of many phytochemicals, the uses are uncertain because the raw plant parts or crude extracts are being used in all formulations. Therefore, extensive investigations are necessary to focus on the identification of these phytochemicals. It is an urgent need to give special attention to collecting various aspects and more efforts are required in all areas for utilization and conservation of this valuable medicinal herb. Herein, a compilation of all information with various aspects has been presented, including the authors published work on <em style="color: rgba(0, 0, 0, 0.87); font-family: "Noto Sans", -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, Oxygen-Sans, Ubuntu, Cantarell, "Helvetica Neue", sans-serif; font-size: 14px; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; text-align: justify;">Uraria picta<span style="color: rgba(0, 0, 0, 0.87); font-family: "Noto Sans", -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, Oxygen-Sans, Ubuntu, Cantarell, "Helvetica Neue", sans-serif; font-size: 14px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; text-align: justify;">. This review pursues attention towards biological activity, phytochemical profile, utilization, propagation and conservation of <em style="color: rgba(0, 0, 0, 0.87); font-family: "Noto Sans", -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, Oxygen-Sans, Ubuntu, Cantarell, "Helvetica Neue", sans-serif; font-size: 14px; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; text-align: justify;">Uraria picta<span style="color: rgba(0, 0, 0, 0.87); font-family: "Noto Sans", -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, Oxygen-Sans, Ubuntu, Cantarell, "Helvetica Neue", sans-serif; font-size: 14px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; text-align: justify;">.

Water mediated allosteric network in beta 2AR T164I variant modulates agonist binding affinity - Nikte, Siddhanta V.; Sonar, Krushna; Tandale, Aditi; Sengupta, Durba; Joshi, Manali (European Biophysics Journal with Biophysics Letters, 2021)

Amide-linked monocarbonyl curcumin analogues: efficient synthesis, antitubercular activity and molecular docking study - Subhedar, Dnyaneshwar D.; Shaikh, Mubarak H.; Nagargoje, Amol A.; Akolkar, V. Satish; Bhansali, Sujit G.; Sarkar, Dhiman; Shingate, Bapurao B. (Polycyclic Aromatic Compounds, 2022)
An approach toward the synthesis of novel conjugates of 3,5-bis (arylidene)-4-piperidones (DAP) pharmacophore with amide-linkage has been developed via one-pot multicomponent reaction of aryl aldehydes, piperidinone and 2-chloro-N-phenylacetamide using [Et3NH][HSO4] as a catalyst/medium. Both substitutions on arylidene rings and piperidinone nitrogen (substituted 2-chloro-N-phenylacetamide) were varied. The synthesized conjugates were evaluated for their in vitro antitubercular activity against M. tuberculosis H37Ra (MTB) and M. bovis BCG strains. Among the series, compounds 4f, 4g, 4i and 4j showed remarkable broad spectrum antitubercular activity with low IC50 values. Furthermore, computer docking simulations, for the most active conjugates were performed with the active site of mycobacterial enoyl-acyl carrier protein reductase (InhA) support the antitubercular activity. Lower cytotoxicity, high potency and promising activity against MTB and M. Bovis BCG suggest that amide linked DAP could serve as good leads for further modifications and development.
Keywords: antimycobacterial activity; Bis (arylidene)-4-piperidones; Cytotoxicity; Ionic liquid; Molecular docking Study

Assembly, annotation, and comparative whole genome sequence of fusarium verticillioides isolated from stored maize grains - Navale, Vishwambar D.; Sawant, Amol M.; Gowda, Varun U.; Vamkudoth, Koteswara Rao (2022)
Fusarium verticillioides is a plant pathogenic fungus affecting a wide range of crops worldwide due to its toxigenic properties. F. verticillioides BIONCL4 strain was isolated from stored maize grain samples in India, and produces high amount of fumonisin B1 (FB1). We report a comparative genomic analysis of F. verticillioides, covering the basic genome information, secretome, and proteins involved in host-pathogen interactions and mycotoxin biosynthesis. Whole-genome sequencing (WGS) was performed using the Illumina platform with an assembly size of 42.91 Mb, GC content of 48.24%, and 98.50% coverage with the reference genome (GCA000149555). It encodes 15,053 proteins, including 2058 secretory proteins, 676 classical secretory proteins, and 569 virulence and pathogenicity-related proteins. There were also 1447 genes linked to carbohydrate active enzymes (CaZymes) and 167 genes related to mycotoxin production. Furthermore, F. verticillioides genome comparison revealed information about the species' evolutionary history. The overall study helps in disease prevention and management of mycotoxins to ensure food safety.
Keywords: comparative genomics; Fusarium verticillioides; mycotoxin biosynthesis; plant-pathogen interaction; Secretome; whole-genome sequencing

Case report: a fatal case of babesiosis in a splenectomized male patient from Western India - Godbole, Ravi; Gaur, Avantika; Nayar, Priyanka; Kiruthiga, Kala; D'Costa, Pradeep; Manchanda, Rumma; Khilari, Ajinkya; Shanmugam, Dhanasekaran; Muglikar, Kalpana D.; Kundu, Krishnendu (American Journal of Tropical Medicine and Hygiene, 2022)
Human babesiosis is a rare disease, caused by Babesia species and commonly transmitted by tick bite. Although human babesiosis is known to be asymptomatic in immunocompetent hosts, clinical cases of severe babesiosis have been reported from splenectomized or immunocompromised individuals. To our knowledge, only one case of human babesiosis in India has been previously reported. Here, we report a case of severe babesiosis with high parasitemia (similar to 70%) in a 30-year-old asplenic farmer. The patient presented with fever, yellowish discoloration of skin, oliguria, and anemia; he eventually developed multiorgan failure syndrome and died. Peripheral blood films were prepared and used to confirm the presence of piroplasms by microscopy. Total DNA isolated from blood was used for 18S ribosomal RNA gene fragment amplification by polymerase chain reaction, which was subjected to Sanger sequencing. Although 18S sequence indicated that the Babesia species infecting the patient was similar to that of other Babesia species originating from wild mammals, species identification could not be done. Phylogenetic analysis revealed that the patientderived pathogen is distinct because it forms a separate clade in the cladogram.

Catalytic activity of CuFe2O4 spinel oxide for liquid-phase oxidation of cinnamyl alcohol - Dange, Rutvija M.; Niphadkar, Prashant S.; Bokade, Vijay V.; Nandanwar, Sachin U. (ChemistrySelect, 2022)
CuFe2O4 spinel oxide catalyst was synthesized by sol-gel and co-precipitation methods for liquid phase oxidation of Cinnamyl alcohol (CnOH) to Cinnamaldehydes (CnHO) using tert-Butyl hydroperoxide (TBHP) as oxidising agent. Spinel oxide catalyst was characterized by different techniques such as X-ray diffraction (XRD), N-2 adsorption-desorption, BET surface area, and X-ray photoelectron spectroscopy (XPS) to understand the structural, physical properties and oxidation state of the catalyst. The result shows that catalyst prepared by sol-gel method was found higher surface area and smaller crystalline size than co-precipitation method. XPS data confirm the formation of Cu2+ in the spinel which helps to improve the catalytic activity of oxidation. This reaction follows radical mechanism, and exhibited 76.7 % of CnOH conversion and 68.4 % of CnHO, and 24.8 % benzaldehyde (benzald) selectivity using TBHP at 60 degrees C. Kinetic data reveal that 41.2 kJ/mol of activation energy for the reaction. The higher activity of spinel oxide catalyst could be due synergetic effect of spinel (88 %) and oxides (12 %) formed in the catalyst, which helps to provide the oxygen during reaction. The contribution of Cu2+ is higher in sol-gel than co-precipitation, which may provide the better reactivity of catalyst. This work helps to select the effective and cost-effective catalyst for the oxidation of CnOH.
Keywords: Catalysts; Cinnamaldehyde; Cinnamyl Alcohol; Cupper; iron; oxide; spinel

Comparison of hydrodynamic characteristics of Tulsion and Siran immobilised beads in a fluidised bed bioreactor - Kashid, Shweta; Joshi, Kalpana; Nene, Sanjay (Biocatalysis and Agricultural Biotechnology, 2022)
<span style="box-sizing: border-box; margin: 0px; padding: 0px; color: rgb(46, 46, 46); font-family: ElsevierGulliver, Georgia, "Times New Roman", STIXGeneral, "Cambria Math", Arial, Helvetica, "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 16px;">The fluidised bed reactors are successfully utilised in various bioprocesses to produce <a class="topic-link" href="https://www.sciencedirect.com/topics/agricultural-and-biological-sciences/high-value-products" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: transparent; word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(46, 46, 46); color: rgb(46, 46, 46); text-underline-offset: 1px;" title="Learn more about high value products from ScienceDirect's AI-generated Topic Pages">high value products using <a class="topic-link" href="https://www.sciencedirect.com/topics/immunology-and-microbiology/immobilized-cell" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: transparent; word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(46, 46, 46); color: rgb(46, 46, 46); text-underline-offset: 1px;" title="Learn more about immobilised cells from ScienceDirect's AI-generated Topic Pages">immobilised cells and enzymes. The present work aims at evaluating hydrodynamic characteristics of a three phase fluidised bed <a class="topic-link" href="https://www.sciencedirect.com/topics/immunology-and-microbiology/bioreactor" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: transparent; word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(46, 46, 46); color: rgb(46, 46, 46); text-underline-offset: 1px;" title="Learn more about bioreactor from ScienceDirect's AI-generated Topic Pages">bioreactor using Tulsion® A-1X MP, Tulsion® ADS-400 and Tulsion® ADS-800, <a class="topic-link" href="https://www.sciencedirect.com/topics/agricultural-and-biological-sciences/polystyrene" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: transparent; word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(46, 46, 46); color: rgb(46, 46, 46); text-underline-offset: 1px;" title="Learn more about polystyrene from ScienceDirect's AI-generated Topic Pages">polystyrene and polyacrylic based three types of free and <a class="topic-link" href="https://www.sciencedirect.com/topics/immunology-and-microbiology/immobilized-cell" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: transparent; word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(46, 46, 46); color: rgb(46, 46, 46); text-underline-offset: 1px;" title="Learn more about immobilised cells from ScienceDirect's AI-generated Topic Pages">immobilised cells solid carriers viz. and comparing their performance with Siran® SIKUG41 glass beads. The hydrodynamic parameters such as particle density (cells and beads), drag coefficient, minimum and maximum <a class="topic-link" href="https://www.sciencedirect.com/topics/immunology-and-microbiology/fluidization" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: transparent; word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(46, 46, 46); color: rgb(46, 46, 46); text-underline-offset: 1px;" title="Learn more about fluidisation from ScienceDirect's AI-generated Topic Pages">fluidisation velocity, particle settling velocity were estimated and compared in water and biological media (E2 and MSM) having varying rheological properties. The relationships between drag coefficient (C<span style="box-sizing: border-box; margin: 0px; padding: 0px; line-height: 0; position: relative; vertical-align: baseline; bottom: -0.25em; color: rgb(46, 46, 46); font-family: ElsevierGulliver, Georgia, "Times New Roman", STIXGeneral, "Cambria Math", Arial, Helvetica, "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif;">D<span style="color: rgb(46, 46, 46); font-family: ElsevierGulliver, Georgia, "Times New Roman", STIXGeneral, "Cambria Math", Arial, Helvetica, "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 16px;">)–Reynolds numbers (N<span style="box-sizing: border-box; margin: 0px; padding: 0px; line-height: 0; position: relative; vertical-align: baseline; bottom: -0.25em; color: rgb(46, 46, 46); font-family: ElsevierGulliver, Georgia, "Times New Roman", STIXGeneral, "Cambria Math", Arial, Helvetica, "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif;">Re<span style="color: rgb(46, 46, 46); font-family: ElsevierGulliver, Georgia, "Times New Roman", STIXGeneral, "Cambria Math", Arial, Helvetica, "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 16px;">), superficial liquid velocity (U<span style="box-sizing: border-box; margin: 0px; padding: 0px; line-height: 0; position: relative; vertical-align: baseline; bottom: -0.25em; color: rgb(46, 46, 46); font-family: ElsevierGulliver, Georgia, "Times New Roman", STIXGeneral, "Cambria Math", Arial, Helvetica, "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif;">f<span style="color: rgb(46, 46, 46); font-family: ElsevierGulliver, Georgia, "Times New Roman", STIXGeneral, "Cambria Math", Arial, Helvetica, "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 16px;">)–void fraction(ε), expansion index(n)–N<span style="box-sizing: border-box; margin: 0px; padding: 0px; line-height: 0; position: relative; vertical-align: baseline; bottom: -0.25em; color: rgb(46, 46, 46); font-family: ElsevierGulliver, Georgia, "Times New Roman", STIXGeneral, "Cambria Math", Arial, Helvetica, "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif;">Re<span style="color: rgb(46, 46, 46); font-family: ElsevierGulliver, Georgia, "Times New Roman", STIXGeneral, "Cambria Math", Arial, Helvetica, "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 16px;"> were obtained.

Coordination flexibility aided CO2-specific gating in an iron isonicotinate MOF - Singh, Himan Dev; Nandi, Shyamapada; Chakraborty, Debanjan; Singh, Kirandeep; Vinod, Chathakudath P.; Vaidhyanathan, Ramanathan (Chemistry-an Asian Journal, 2022)
Coordination flexibility assisted porosity has been introduced into an Iron-isonicotinate metal-organic framework (MOF), (Fe(4-PyC)(2) . (OH). The framework showed CO2-specific gate opening behavior, which gets tuned as a function of temperature and pressure. The MOF ` s physisorptive porosity towards CO2, CH4, and N-2 was investigated; it adsorbed only CO2 via a gate opening phenomenon. The isonicotinate, representing a borderline soft base, is bound to the hard Fe3+ centre through monodentate carboxylate and pyridyl nitrogen. This moderately weak binding enables isonicotinate to spin like a spindle under the CO2 pressure opening the gate for a sharp increase in CO2 uptake at 333 mmHg (At 298 K, the CO2 uptake increases from 0.70 to 1.57 mmol/g). We investigated the MOF ` s potential for CO2/N-2 and CO2/CH4 gas separation aided by this gating. IAST model reveals that the CO2/N-2 selectivity jumps from 325 to 3131 when the gate opens, while the CO2/CH4 selectivity increases three times. Interestingly, this Fe-isonicotinate MOF did not follow the trend set by our earlier reported Hard-Soft Gate Control (established for isostructural M2+-isonicotinate MOFs (M=Mg, Mn)). However, we account for this discrepancy using the different oxidation state of metals confirmed by X-ray photoelectron spectroscopy and magnetism.
Keywords: CO2 capture; flexible MOF; gating; Isonicotinic

[DBUH][OAc]-catalyzed domino synthesis of novel benzimidazole incorporated 3,5-Bis (Arylidene)-4-piperidones as potential antitubercular agents - Subhedar, Dnyaneshwar D.; Shaikh, Mubarak H.; Nagargoje, Amol A.; Sarkar, Dhiman; Khedkar, Vijay M.; Shingate, Bapurao B. (Polycyclic Aromatic Compounds, 2022)
A series of new benzimidazole incorporated 3,5-bis (arylidene)-4-piperidones were synthesized by using aryl aldehydes, piperidinone, 2-(chloromethyl)-benzimidazole and DBU acetate [DBUH][OAc] act as a catalyst under solvent free condition in excellent yields. The synthesized compounds were screened for their in vitro antimycobacterial activity against M. tuberculosis H37Ra (MTB) and M. bovis BCG strains. The compounds 4a, 4b, 4e, 4i, 4k and 4l are highly potent against both the strains. Most of the active compounds are non-cytotoxic against MCF-7, A549, HCT 116 and THP-1 cell lines. Furthermore, a molecular docking study of these compounds was carried out to investigate their binding pattern with the target, active site of mycobacterial enoyl-acyl carrier protein reductase (Inh A). Therefore, these compounds can be subjected for further optimization and drug development which could give promising chemical leads for treatment of TB.
Keywords: Antitubercular activity; curcumin; Cytotoxicity; Ionic liquid; multicomponent reactions

Direct (hetero)arylation (DHAP) polymerization of conjugated polymers - new A-B-A monomer design for P(NDI2OD-T2) & the challenges of adopting DHAP for continuous flow processes - Kakde, Navnath R.; Bharathkumar, H. J.; Wavhal, Bhaiyyasaheb A.; Nikam, Arun; Patil, Suneha; Dash, Soumya Ranjan; Vanka, Kumar; Krishnamoorthy, K.; Kulkarni, Amol; Asha, S. K. (Journal of Materials Chemistry C, 2022)
P(NDI2OD-T2), also known as Polyera ActivInk N2200, was synthesized by the atom-economic direct hetero arylation polymerization (DHAP) route using a newly designed A-B-A monomer. The new monomer design involved flanking naphthalene diimide with bithiophene units in the bay position, which was further polymerized with bay substituted 1,4-dibromo naphthalene diimide, to afford the same polymer structure as P(NDI2OD-T2). The new monomer design resulted in a very high molecular weight (M-n: 99.5 kDa, D-M: 2.8) defect-free polymer in a quantitative yield by the DHAP batch process using 1,2,4-trichlorobenzene (TCB) as the solvent. DFT studies revealed that the abstraction of the alpha-proton from the naphthalene diimide substituted 2,2 `-bithiophene was favorable by 2.6 kcal mol(-1) (Delta Delta G) as compared to that from 2,2 `-bithiophene. The reason for this improved C-H activation at the alpha position can be attributed to the presence of C-HMIDLINE HORIZONTAL ELLIPSIS pi stabilizing interactions in naphthalene diimide substituted 2,2 `-bithiophene, which strengthens upon the extended charge delocalization throughout the ring, thus stabilizing the conjugate base generated after the proton abstraction. Continuous flow polymerization was carried out by pumping the DHAP reaction mixture including the monomers, catalyst, and additive (pivalic acid) solubilized in degassed TCB through a pre-heated glass condenser packed with K2CO3 and Celite under aerobic conditions. Reproducible molecular weights of M-n: 29.5 kDa, D-M: 1.7 were obtained at much lower concentrations of reactant mixture compared to that for batch polymerization. This is the first report of the synthesis of P(NDI2OD-T2) by a Continuous Flow Process adopting the DHAP route to obtain a defect-free polymer with reasonable molecular weights. P(NDI2OD-T2) was also synthesized by Stille polymerization as a reference control sample to compare the thermal and charge carrier transport properties of the DHAP polymers. Organic field-effect (OFET) mobility measurements indicated mobility values in the order of 10(-3) cm(2) V-1 s(-1) for the DHAP batch polymer (using the novel monomer design). The P(NDI2OD-T2) synthesized by DHAP batch using the commonly used starting materials - bisbromo naphthalene diimide and bithiophene, exhibited OFET mobilities which were one order less, similar to 10(-4) cm(2) V-1 s(-1). This observation highlights the importance of structural design in the monomer to enhance reactivity and thereby the bulk properties using the DHAP route.

Direct oxidation of bromo-derived Fischer-Borsche oxo-ring using molecular iodine with combined experimental and computational study - Humne, Vivek T.; Ghom, Monica H.; Naykode, Mahavir S.; Dangat, Yuvraj; Vanka, Kumar; Lokhande, Pradeep (Organic & Biomolecular Chemistry, 2022)
A direct oxidation of the bromo-derived Fischer-Borsche oxo-ring leading to carbazolequinone has been developed by using molecular iodine. This unprecedented transformation has been used for the modular synthesis of the anti-cardiotonic agent murrayaquinone. Furthermore, the present method has been generalized to a broad range of functional groups, with good to excellent yield.

Diversity assessment of Gloriosa superba accessions from Western Ghats of India based on morphological traits, ISSR markers and metabolite content - Mahajan, Yogesh A.; Shinde, Balkrishna A.; Mulani, Fayaj A.; Gade, Akshay B.; Kasodekar, Amol K.; Thulasiram, H. V.; Kadoo, Narendra Y.; Nikam, Tukaram D. (Journal of Applied Research on Medicinal and Aromatic Plants, 2022)
Gloriosa superba L. (glory lily) is a medicinally and horticulturally important plant used as a commercial source of the alkaloid colchicine. The Western Ghats in India is mostly unexplored for the morphological, genetic, and metabolite diversity of the species. In the current study, three methodologies were employed to assess the diversity among 50 established accessions of G. superba collected from several locations in the Western Ghats. The morphological analysis revealed that, among the studied traits, seed yield per vine and dry seed weight per 100 seeds for the established accessions were the most diverse traits. The former exhibited a significantly positive correlation with four vegetative and five yield traits. The first three principal components showed nine traits contributing to the variation. Intra-specific molecular variation based on inter simple sequence repeat markers distributed the accessions in three clusters with high polymorphism and low genetic diversity indices. Liquid chromatography high-resolution mass spectrometry analysis revealed significant variation among the screened accessions for colchicine content in tuber and seed tissue. Interestingly, an unexplored tissue, pod shell, was found to contain significantly high colchicine, which could be explored for commercial colchicine extraction. The morphogenetic and metabolite variation revealed by the study would be useful to develop elite varieties to expand the cultivation of glory lily across the country, fulfilling the increasing demand for colchicine and providing remunerative income to the farmers.
Keywords: Colchicine; Genetic diversity; Gloriosa superba; Metabolite diversity; Morphological diversity; Western Ghats

DNA binding, antitubercular, antibacterial and anticancer studies of newly designed piano-stool ruthenium(ii) complexes - Navale, Govinda; Singh, Sain; Agrawal, Sonia; Ghosh, Chandrachur; Choudhury, Angshuman Roy; Roy, Partha; Sarkar, Dhiman; Ghosh, Kaushik (Dalton Transactions, 2022)
The chemotherapeutic potential of ruthenium(ii) complexes has recently attracted researchers' interest as antibacterial and anticancer agents. In this study, two novel half-sandwich imine-based Ru complexes ([Ru(p-cymene)Cl(L-1)][PF6] (Ru-1) and [Ru(p-cymene)Cl(L-2)][PF6] (Ru-2)) were reported for their deoxyribonucleic acid (DNA) binding and antitubercular, antibacterial, and anticancer activities. The molecular structure of Ru-2 was obtained by single-crystal X-ray crystallography. DNA interaction studies were conducted by UV-Vis absorbance and fluorescence spectral titration which gave rise to DNA binding constants (K-b) of 1.32 x 10(6) and 1.82 x 10(6) for Ru-1 and Ru-2, respectively and the Stern-Volmer binding constant (K-SV) values for Ru-1 and Ru-2 were 1.7763 x 10(4) M-1 and 7.6 x 10(3) M-1, respectively. The in vitro antitubercular activity was evaluated against Mycobacterium tuberculosis H37Ra. The antibacterial potential of both the Ru-complexes was examined against Gram-negative (Escherichia coli and Pseudomonas aeruginosa) and Gram-positive (Staphylococcus aureus and Bacillus subtilis) bacteria. The half-maximal inhibitory concentration (IC50) values for the antitubercular activity of Ru-1 and Ru-2 were 4.87 +/- 1.32 mu M and 5.78 +/- 0.54 mu M, respectively. A cytotoxic study of these complexes was performed against the human breast cancer cell line (MCF-7) and the human embryonic kidney cell line (HEK293) (normal cells). The study revealed meaningful activity of the Ru-1 complex against (cancer) MCF-7 cells, while the viability of HEK293 (normal) cells in the presence of Ru-2 was higher as compared to a reference drug 5FU. We suggest that these kinds of Ru-complexes could have potential for application in metallopharmaceuticals.

Donor-acceptor based solvent-free organic liquid hybrids with exciplex emission and room temperature phosphorescence - Wakchaure, Vivek Chandrakant; Veer, Sairam D.; Nidhankar, Aakash D.; Goudappagouda; Nayak, Rashmi; Asokan, Kiran; Ravindranathan, Sapna; Babu, Sukumaran Santhosh (Chemical Communications, 2022)
Solvent-free organic liquids are well-known for their excellent luminescence features. Hence, the recent developments in this area have marked them as potential emitters with high quantum yield and enhanced processability. The support of an available liquid matrix enables doping to deliver hybrid liquids with intriguing luminescence features. In this direction, we report solvent-free liquid donor-acceptor pairs with exciplex emission and room temperature phosphorescence at very low acceptor loading. The underlying weak intermolecular interactions have been revealed by 2D NMR techniques and theoretical calculations. The formation of large-area thin films by exciplex and phosphorescent liquid hybrids will encourage the development of scalable lighting and display materials.

Effect of oxalic acid and sulphuric acid hydrolysis on the preparation and properties of pineapple pomace derived cellulose nanofibers and nanopapers - Neenu, K. V.; Dominic, C. D. Midhun; Begum, P. M. Sabura; Parameswaranpillai, Jyotishkumar; Kanoth, Bipinbal Parambath; David, Deepthi Anna; Sajadi, S. Mohammad; Dhanyasree, P.; Ajithkumar, T. G.; Badawi, Michael (International Journal of Biological Macromolecules, 2022)
Nanocellulose is the ``green magnet'' which attracts a wide spectrum of industries towards it due to its availability, biodegradability, and possible smart applications. For the first time, pineapple pomace was being explored as an economic precursor for cellulose nanofibers. Nanofiber isolation was accomplished using a chemo-mechanical method and solution casting was adopted for the development of nanopapers. Moreover, the study examines the structural, optical, crystalline, dimensional, and thermal features of nanofibers isolated using different acid hydrolysis (oxalic acid and sulphuric acid) methods. Fourier-transform infra-red spectroscopy, 13C solid-state nuclear magnetic resonance spectroscopy, and X-ray diffraction analysis indicated the presence of type I cellulose. The transmittance, crystallinity index, and thermal stability of PPNFS (sulphuric acid treated fiber) were greater than PPNFO (oxalic acid treated fiber). The transmission electron microscopy and dynamic light scattering analysis confirmed the nanodimension of PPNFO and PPNFS. While comparing the optical and mechanical properties of nanopapers, PPNFS outperforms PPNFO. The tensile strength of the prepared nanopapers (64 MPa (PPNFO) and 68 MPa (PPNFS)) was found to be high compared to similar works reported in the literature. The prepared nanopaper is proposed to be used for food packaging applications.
Keywords: cellulose nanofibers; Cellulosic nanopapers; Pineapple pomace

The effects of cis and trans butenedioic acid on the physicochemical behavior of lumefantrine - Tomar, Devendrasingh; Lodagekar, Anurag; Gunnam, Anilkumar; Allu, Suryanarayana; Chavan, Rahul B.; Tharkar, Minakshi; Ajithkumar, T. G.; Nangia, Ashwini K.; Shastri, Nalini R. (Crystengcomm, 2022)
The present work investigates the effects of cis and trans butenedioic acid isomers (maleic acid and fumaric acid) on the crystallinity and pharmaceutical behavior of lumefantrine. Differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), attenuated total reflectance infrared spectroscopy (ATR-IR), solid-state nuclear magnetic resonance spectroscopy (ss-NMR), and single-crystal X-ray diffraction (SC-XRD) studies were employed. Lumefantrine-fumaric acid crystallized as a salt in the monoclinic space group P2(1)/c. In comparison, DSC and PXRD showed the formation of a co-amorphous solid with maleic acid. Complete proton transfer with a strong ionic interaction led to crystalline salt formation with the trans isomer, whereas weaker/fewer hydrogen bonds with the cis isomer of butenedioic acid led to a co-amorphous salt. The in vitro dissolution of both salts resulted in a similar 2.6-2.7-fold improvement in dissolution rate when compared to that of the crystalline lumefantrine. The crystalline and co-amorphous salts were stable under accelerated stability conditions (40 +/- 2 degrees C and 75 +/- 5% RH) for one month.

Enantioselective Cu(I)-catalyzed borylative cyclization of enone-tethered cyclohexadienones and mechanistic insights - Jadhav, Sandip B.; Dash, Soumya Ranjan; Maurya, Sundaram; Nanubolu, Jagadeesh Babu; Vanka, Kumar; Chegondi, Rambabu (Nature Communications, 2022)
Rapidly building molecular structures with both elements of complexity and flexibility is a key goal of organic synthesis. Here the authors show a tandem copper-catalyzed beta-borylation/Michael addition on prochiral enone-tethered 2,5-cyclohexadienones, to generate bicyclic borylated products in high yield and enantioselectivity. The catalytic asymmetric borylation of conjugated carbonyls followed by stereoselective intramolecular cascade cyclizations with in situ generated chiral enolates are extremely rare. Herein, we report the enantioselective Cu(I)-catalyzed beta-borylation/Michael addition on prochiral enone-tethered 2,5-cyclohexadienones. This asymmetric desymmetrization strategy has a broad range of substrate scope to generate densely functionalized bicyclic enones bearing four contiguous stereocenters with excellent yield, enantioselectivity, and diastereoselectivity. One-pot borylation/cyclization/oxidation via the sequential addition of sodium perborate reagent affords the corresponding alcohols without affecting yield and enantioselectivity. The synthetic potential of this reaction is explored through gram-scale reactions and further chemoselective transformations on products. DFT calculations explain the requirement of the base in an equimolar ratio in the reaction, as it leads to the formation of a lithium-enolate complex to undergo C-C bond formation via a chair-like transition state, with a barrier that is 22.5 kcal/mol more favourable than that of the copper-enolate complex.

Enantioselective separation of amino acids using chiral polystyrene microspheres synthesized by a post-polymer modification approach - Nikam, Shrikant B.; Asha S. K (ACS Polymers Au, 2022)
The enantioselective separation of a racemic mixture of amino acids was achieved by chiral amino acid-modified polystyrene (PS) that was developed by a post-polymer modification approach. Styrene was polymerized using the reversible addition–fragmentation chain-transfer (RAFT) polymerization technique and further post-polymer modification was applied by Friedel–Crafts acylation reaction with chiral N-phthaloyl-<span class="smallcaps smallerCapital" style="box-sizing: border-box; outline: none; font-variant-numeric: normal; font-variant-east-asian: normal; font-variant-caps: small-caps; font-variant-alternates: normal; color: rgb(0, 0, 0); font-family: georgia, serif; font-size: 17.008px; background-color: rgb(244, 244, 244);">l-leucine acid chloride to obtain the protected PS-<span class="smallcaps smallerCapital" style="box-sizing: border-box; outline: none; font-variant-numeric: normal; font-variant-east-asian: normal; font-variant-caps: small-caps; font-variant-alternates: normal; color: rgb(0, 0, 0); font-family: georgia, serif; font-size: 17.008px; background-color: rgb(244, 244, 244);">l-Leu. The chiral PS (protected PS-<span class="smallcaps smallerCapital" style="box-sizing: border-box; outline: none; font-variant-numeric: normal; font-variant-east-asian: normal; font-variant-caps: small-caps; font-variant-alternates: normal; color: rgb(0, 0, 0); font-family: georgia, serif; font-size: 17.008px; background-color: rgb(244, 244, 244);">l-Leu) was assembled into microspheres using a surfactant and was used for carrying out the enantioselective separation of amino acid racemic mixtures by enantioselective adsorption followed by a simple filtration process. Compared to as-precipitated chiral PS (protected PS-<span class="smallcaps smallerCapital" style="box-sizing: border-box; outline: none; font-variant-numeric: normal; font-variant-east-asian: normal; font-variant-caps: small-caps; font-variant-alternates: normal; color: rgb(0, 0, 0); font-family: georgia, serif; font-size: 17.008px; background-color: rgb(244, 244, 244);">l-Leu) powder, the protected PS-<span class="smallcaps smallerCapital" style="box-sizing: border-box; outline: none; font-variant-numeric: normal; font-variant-east-asian: normal; font-variant-caps: small-caps; font-variant-alternates: normal; color: rgb(0, 0, 0); font-family: georgia, serif; font-size: 17.008px; background-color: rgb(244, 244, 244);">l-Leu microspheres exhibited a better enantioselective separation efficiency (ee %). Furthermore, the protected PS-<span class="smallcaps smallerCapital" style="box-sizing: border-box; outline: none; font-variant-numeric: normal; font-variant-east-asian: normal; font-variant-caps: small-caps; font-variant-alternates: normal; color: rgb(0, 0, 0); font-family: georgia, serif; font-size: 17.008px; background-color: rgb(244, 244, 244);">l-Leu was deprotected to obtain the amine-functionalized deprotected PS-<span class="smallcaps smallerCapital" style="box-sizing: border-box; outline: none; font-variant-numeric: normal; font-variant-east-asian: normal; font-variant-caps: small-caps; font-variant-alternates: normal; color: rgb(0, 0, 0); font-family: georgia, serif; font-size: 17.008px; background-color: rgb(244, 244, 244);">l-Leu chiral PS, which was also assembled into microspheres and used for carrying out enantioselective separation. Deprotected PS-<span class="smallcaps smallerCapital" style="box-sizing: border-box; outline: none; font-variant-numeric: normal; font-variant-east-asian: normal; font-variant-caps: small-caps; font-variant-alternates: normal; color: rgb(0, 0, 0); font-family: georgia, serif; font-size: 17.008px; background-color: rgb(244, 244, 244);">l-Leu-functionalized chiral PS microspheres could achieve up to 81.6 ee % for the enantioselective separation of a racemic mixture of leucine. This is one of the first reports of the synthesis of amino acid-modified chiral PS microspheres and their application to the simple filtration-based enantioselective separation of native amino acids from their racemic mixtures.

Enhanced anisole hydroxylation over a hierarchical micro/mesoporous TS-1 catalyst - Patil, Chetana R.; Niphadkar, Prashant; Kamble, Sanjay P.; Rode, V. Chandrashekhar (New Journal of Chemistry, 2022)
Hierarchical TS-1 materials were synthesized using hydrothermal synthesis and a post modification technique through desilication. They were evaluated for hydroxylation of anisole to produce industrially important chemicals, o-methoxyphenol (OMP) and p-methoxyphenol (PMP). The detailed characterization of the prepared catalysts, such as morphology, structure, nature of Ti and surface area were obtained by SEM, HR-TEM, XRD, UV-VIS spectroscopy and the BET technique. The effects of various operational parameters such as substrate/H2O2 molar ratio, reaction temperature, catalyst concentration and solvent effect on the hydroxylation of anisole have been studied in detail. The microporous TS-1 catalyst showed 32% anisole conversion with 34% selectivity to PMP, while the micro/mesoporous DTS-1 catalyst showed enhanced activity for anisole hydroxylation, i.e. 54% conversion with 55% selectivity towards PMP. The increased framework Ti and improved accessibility of the active sites located in the channels of DTS-1, which permit the mass transfer of reactants, transition states and products from the mesopores of DTS-1, were responsible for the enhanced catalytic activity and selectivity towards p-methoxyphenol.

Exploring the core microbiota in scented rice (Oryza sativa L.) rhizosphere through metagenomics approach - Dhondge, V. Harshal; Barvkar, Vitthal T.; Paul, Dhiraj; Dastager, Syed G.; Pable, Anupama A.; Nadaf, Altafhusain B. (Microbiological Research, 2022)
Rice is a major food crop cultivated around the globe. Specially scented rice varieties are of commercial importance but they are low-yielding. The rhizospheric microflora plays a significant role in improving yield and aroma. However, the core microbiome of the scented rice rhizosphere is comparatively less explored. Here, we analyzed the core microbiome associated with the rhizosphere of the scented (Ambemohar-157 and Dehradun basmati) in comparison with non-scented rice (Kolam and Arize 6444 Gold) cultivated at two different geoclimatic zones of India (Maharashtra and Uttarakhand) using the metagenomics approach. The alpha and beta diversity analysis showed that the microbial communities associated with scented and non-scented varieties significantly changes with respect to richness, diversity, and evenness. The taxonomic profiling revealed the variation in composition, diversity, and abundance of the microbiome in terms of phyla and genera associated with scented rice varieties over non-scented. The cluster analysis distinguishes the microbial communities based on their geographical positions. The core microbiome analysis revealed that scented rice rhizosphere shelters distinct and unique microbiota. 28.6 % of genera were exclusively present only in the scented rice rhizosphere. The putative functional gene annotation revealed the high abundance of genes related to the biosynthesis of 2-acetyl-1-pyrroline (2AP) precursors in scented rice. The precursor feeding analysis revealed proline as a preferred substrate by 2AP synthesizing bacteria. The 2AP precursor proline and proline metabolism genes showed a positive correlation. The scented rice-specific rhizobacteria pointed out in this study can be used as bioinoculants for enhancing aroma, yield, and sustainable rice cultivation.
Keywords: Metagenome; Microbial community; Microbiome; Oryza sativa; Rhizosphere; rice

Facile, sustainable and unassisted plain water oxidation on Au/Ce0.9Ti0.1O2 nanorods in direct sunlight - Dubey, Anjani; Mishra, Abhaya Kumar; Negi, Sanjay Singh; Gopinath, Chinnakonda S. (Journal of Chemical Sciences, 2022)
Impressive rate of solar water oxidation to molecular oxygen (O-2) has been demonstrated on nanorods (NRs) of Ce0.9Ti0.1O2 (CT-NR) and Au-deposited CT-NR (Au-CT-NR) photocatalysts with a sacrificial agent (Fe3+) and in plain water in one sun condition, direct sunlight and with lambda >= 455 nm. Probably the highest 0 2 yield of 11 mmol/h.g was observed with Au-CT-NR thin film in plain water in direct sunlight, with no sacrificial agent or applied potential. Photoelectrochemical measurements demonstrate a marked reduction in oxidation onset potential of Au-CT-NR by 150 mV with stable photocurrent (0.75 mA/cm(2)), compared to CT-NR (0.23 mA/cm(2)), indicating the operative of plasmon-induced resonant energy transfer (PIRET) process. Effective electron quenching by nanogold and hence low recombination in the depletion region is a critical step for the observation of a high rate of oxygen evolution. In addition to this, a predominant change in the nature of the valence band from O-2p dominated on CeO2 to Ce-4f dominated with CT-NR (due to Ti4+ introduction in CeO2), the efficient light absorption of photocatalysts in thin-film form, functional and effective PIRET process, and facile E-F alignment, enhances the oxygen evolution with Au-CT-NR in direct sunlight and make it highly sustainable. A possible mechanism of water oxidation is proposed from the observed experimental findings.
Keywords: ceria; Electronic integration; Photocatalysis; thin film; water splitting

Fluorobenzoic acid coformers to improve the solubility and permeability of the BCS class IV drug naftopidil - Mannava, M. K. Chaitanya; Bommaka, Manish K.; Dandela, Rambabu; Solomon, K. Anand; Nangia, Ashwini K. (Chemical Communications, 2022)
Crystalline salts of the low solubility and low permeability drug naftopidil were investigated with mono-, di-, tri-, and tetrafluorobenzoic acids as coformers to show that 245TFBA (2,4,5-trifluorobenzoic acid) is the optimal salt with faster dissolution and high permeability, thereby opening the study of fluorinated coformers in pharmaceutical cocrystals and salts.

Formation of the secondary phase domain by multi-cation substitution for the superior electrochemical performance of spinel cathodes for high-voltage li-ion batteries - Nayaka, Girish Praveen; Shivamurthy, Bogalera Papaiah; Thripuranthaka, Marulasiddappa; Shelke, V. Manjusha. (ACS Applied Energy Materials, 2022)
{Disorder-structured spinel oxides are opening frontiers for high-capacity/high-voltage cathodes to meet the challenges of independ-ence on cobalt-containing cathodes toward cheap and sustainable energy storage sources in Li-ion batteries (LIBs). In the present work, a series of Co-free materials: LiMn2-x-y-zNixFeyAlzO4 (x = 0.8-0.5
Keywords: 5Ni0; cation-doped spinel cathode material; cobalt-free cathode; disorder structured spinel cathode material; high-voltage cathode; li-ion batteries; LiMn1

Green synthesis of highly dispersed Cu metal nanoparticles catalysts - Nagpure, Atul S.; Mohture, Vikas M.; Kayarkar, Ankush (Inorganic Chemistry Communications, 2022)
Bionanotechnology approach for metal nanoparticles (NPs) synthesis is cost-effective and environmentally friendly. Organic molecules present in plant extracts can be efficiently utilized for bio-reduction of metal ions into metal NPs in a one-step green synthesis methodology. The biosynthesis procedure for metal NPs synthesis is quick, easy to scale up and can be perform at ambient conditions. The present investigations propose the biosynthesis of highly dispersed and stable copper NPs (Cu NPs) supported on NaY zeolite using plant extract of Tinospora cordifolia and Andrographis paniculata for the first time. The structural and morphological attributes of Cu NPs were explored by adopting various physico-chemical techniques, for example Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES), X-ray diffraction (XRD), Temperature Programmed Desorption (CO2-TPD and NH3-TPD), Temperature Programmed Reduction (H2-TPR), N2 sorption, Electron Microscopy (SEM, TEM and HR-TEM), X-ray Photoelectron Spectroscopy (XPS), etc. The experimental study (XRD, SEM, TEM, and HR-TEM) recommend that the green synthesis method by using plant extract has promising effect for the synthesis of nano-sized, stable and homogeneously dispersed Cu NPs catalysts (Cu NPs average size of 1.6 and 1.8 nm) as compared to chemical synthesis approach. The present result is better than those of many state-ofthe art techniques reported for green synthesis of Cu NPs using plant extract. According to the current study, it is advantageous to prepare highly dispersed metal NPs with desired size, shape, morphology and the required properties by using plant extract.
Keywords: Biosynthesis of nanomaterials; Cu nanoparticles; Heterogeneous catalysts; Support -Metal interaction; Zeolite supported catalysts

Heterostructure from heteromixture: unusual OER activity of FeP and CoP nanostructures on physical mixing - Bhutani, Divya; Maity, Sisir; Chaturvedi, Shashank; Chalapathi, Divya; Waghmare, V. Umesh; Narayana, Chandrabhas; Prabhakaran, Vinod C.; Muthusamy, Eswaramoorthy (Journal of Materials Chemistry A, 2022)
Heterointerfaces generated by inter-domain interactions on a nanoscale play a critical role in altering the activity of an electrocatalyst towards an electrochemical process. Heterointerfaces affect the surface characteristics, electronic structure, and physicochemical properties of a nanomaterial. Herein, we report an FeP-CoP heterostructure prepared by simple physical mixing of FeP and CoP nanostructures showing a remarkable performance towards water oxidation in comparison to their individual monometallic phosphides. FeP mixed with 20 wt% CoP shows a low overpotential (eta(10)) of 220 mV as compared to FeP (eta(10), 325 mV). Furthermore, a high current density of 1.37 A cm(-2) and mass activity of 18 987 A g(M)(-1) were also achieved at 500 mV overpotential in 1.0 M KOH. The physical mixture shows immense stability for 200 h to achieve a high current density of 200 mA cm(-2). Meanwhile the potentiostatic performance of FeP at 200 mA cm(-2) decreases to an extent of 50% in 40 h. A full cell arrangement employing this catalyst as the anode material requires 1.56 V to attain a current density of 10 mA cm(-2). Various characterization techniques, control experiments and theoretical studies indicate that the formation of heterointerfaces between the nano-domains of FeP and CoP results in charge transfer between Fe and Co metal sites. In addition, an oxygenated surface at the metal phosphide interface favours the sorption kinetics of intermediates involved in the reaction leading to low energy barriers in the potential determining and other steps, thus showing improved performance towards water oxidation.

Hierarchical TS-1 for epoxidation of non-edible Karanja (Millettia pinnata) oil methyl ester to methyl epoxioleate (biodiesel additive) in presence of H2O2 as oxidizing agent - Anil, Reshma; Niphadkar, Prashant; Bokade, Vijay (Environmental Progress & Sustainable Energy, 2022)
Application of non-edible Karanja (Millettia pinnata) oil which is abundantly available in India is not explored so far. The present study is an attempt to convert fatty acid methyl ester (FAME) obtained from Karanja oil to methyl epoxioleate over hierarchical titanosilicate (TS-1) catalyst. Methyl epoxioleate, a biodiesel additive can blend up to 20% with biodiesels to improve oxidative stability and cold flow properties of biodiesel. A series of hierarchical TS-1 were prepared by desilication of parent TS-1 with 0.1 N NaOH at 80 degrees C for 1, 3, 5, and 7 h, respectively. Samples were characterized by powder XRD, low temperature nitrogen adsorption/desorption, and TEM. Eighty percent FAME conversion with 70% yield of methyl epoxioleate was obtained over 5H-TS-1 catalyst. The enhanced catalytic activity of a 5H-TS-1 compared to parent TS-1 mainly attributed to the high mesoporosity coupled with well-preserved crystallinity. 5H-TS-1 catalyst was found to be completely reusable after calcination at 500 degrees C for 12 h. Hierarchical 5H-TS-1 catalyst for effective conversion of non-edible Karanja oil methyl ester to methyl epoxioleate probably not reported so far.
Keywords: H2O2; hierarchical TS-1; Karanja oil methyl ester; methyl epoxioleate; TS-1

Highly efficient and reusable polymer supported palladium catalyst for copper free sonogashira reaction in water - Sruthi, Pambingal Rajan; Nimmi, Puthan Purayil; Babu, Sukumaran Santhosh; Anas, Saithalavi (ChemistrySelect, 2022)
Development of a novel, greener and efficient heterogeneous catalytic system for copper free Sonogashira reaction in water is described. This novel catalyst can be easily prepared by a simple method through synthetic modification of nitrile group in Polyacrylonitrile (PAN) using monoethanolamine (MEA) followed by its complexation with palladium chloride (PdCl2). The resulting polymer Pd complex (mPAN-Pd) was characterized by means of Fourier Transform Infrared Spectroscopy (FTIR), Energy-Dispersive X-ray Spectroscopy (EDAX), Inductively Coupled Mass Spectrometry (ICP-MS) and X-ray Photo Electron Spectroscopy (XPS) analyses. mPAN-Pd was then explored as highly efficient heterogeneous catalyst for Sonogashira coupling reaction under copper and ligand free conditions in water affording the corresponding coupling products up to 97 % isolated yield. Moreover, the catalyst was recovered by simple filtration after the reaction and reused for next 5 cycles with excellent stability and activity. This is the first report on the use of ethanolamine modified PAN Pd (II) complex as an efficient heterogeneous catalyst for a coupling reaction.
Keywords: catalysis; green chemistry; Palladium; Polymer Support; Sonogashira coupling

Identifying structural signature of dynamical heterogeneity via the local softness parameter - Sharma, Mohit; Nandi, Manoj Kumar; Bhattacharyya, Sarika Maitra (Physical Review E, 2022)
In this work we study the relationship between the softness of a mean-field caging potential and dynamics at the local level. We first describe the local softness, which shows a distribution, thus identifying structural heterogeneity. We show that the lifetime of the softness parameter is connected to the lifetime of the well-known cage structure in supercooled liquids. Finally, our theory predicts that the local softness and the local dynamics is causal below the onset temperature where there is a decoupling between the short and long time dynamics, thus allowing a static description of the cage. With the decrease in temperature, the correlation between structure and dynamics increases. The study shows that at lower temperatures, the structural heterogeneity increases, and since the structure becomes a better predictor of the dynamics, it leads to an increase in the dynamical heterogeneity. We also find that the softness of a hard, immobile region evolves with time and becomes soft and eventually mobile due to the rearrangements in the neighborhood, confirming the well-known facilitation effect.

Indoline-based donor-pi-acceptor visible-light responsive organic dyes for dye-sensitized solar cells: co-sensitization with squaraine dye for panchromatic IPCE response - Singh, Ambarish Kumar; Nithyanandhan, Jayaraj (ACS Applied Energy Materials, 2022)
A series of metal-free indoline-based donor-pi-acceptor (D-pi-A) visible-light active organic dyes, where an indoline unit wrapped with alkyl or alkyl and glycolic (TEG) groups is used as a donor, a mono- or bi-thiophene unit is used as a pi-spacer, and cyanoacrylic acid acts as an acceptor unit, have been designed and synthesized for dye-sensitized solar cell (DSSC) application. These dyes showed three absorption bands in a dichloromethane solution: the first and second transitions are observed in the UV (337-385 nm) and visible (477-514 nm) regions and correspond to pi-pi* and intramolecular charge transfer (ICT) transition, respectively, whereas the third absorption band obtained in the near-IR (629-758 nm) region has been observed for the first time for a D-pi-A type dye architecture. Furthermore, the ICT transition band for AKT dyes showed negative solvatochromism with increasing polarity of solvents. Photovoltaic characterizations for AKT dyes have been systematically studied with a cobalt electrolyte to evaluate the effect of thiophene incorporation and alkyl group substitution by the TEG group on the DSSC device performance. Here, AKT2 showed the highest DSSC efficiency of 3.16% with V-OC of 0.680 V and J(SC) of 6.24 mA/cm(2) without chenodeoxycholic acid (CDCA) in the AKT dye series, whereas DSSC efficiencies for AKT dyes were not affected much upon further addition of CDCA. Furthermore, AKT dyes were co-sensitized with a complementary optical responsive indoline-based SQS4 dye and showed enhanced efficiency. The combination of AKT2/SQS4 dyes with a ratio of 1:1 showed a maximum of 5.20% co-sensitized solar cell efficiency compared to other dye combinations with the cobalt electrolyte.
Keywords: Dye-sensitized solar cells; indoline-based donor-pi-acceptor dye; intramolecular charge transfer; metal-free organic dye; panchromatic-light absorption; Solvatochromism

Introduction to the themed collection on digitalization in reaction engineering - Galvanin, Federico; Hartman, Ryan L.; Kulkarni, Amol A.; Nieves-Remacha, Maria Jose (Reaction Chemistry & Engineering, 2022)

Kupyaphores are zinc homeostatic metallophores required for colonization of Mycobacterium tuberculosis - Mehdiratta, Kritee; Singh, Shubham; Sharma, Sachin; Bhosale, Rashmi S.; Choudhury, Rahul; Masal, Dattatraya P.; Manocha, Alzu; Dhamale, Bhushan Dilip; Khan, Naseem; Asokachandran, Vivekanand; Sharma, Pooja; Ikeh, Melanie; et al. (Proceedings of the National Academy of Sciences of the United States of America, 2022)
Mycobacterium tuberculosis (Mtb) endures a combination of metal scarcity and toxicity throughout the human infection cycle, contributing to complex clinical manifestations. Pathogens counteract this paradoxical dysmetallostasis by producing specialized metal trafficking systems. Capture of extracellular metal by siderophores is a widely accepted mode of iron acquisition, and Mtb iron-chelating siderophores, mycobactin, have been known since 1965. Currently, it is not known whether Mtb produces zinc scavenging molecules. Here, we characterize low-molecular-weight zinc-binding compounds secreted and imported by Mtb for zinc acquisition. These molecules, termed kupyaphores, are produced by a 10.8 kbp biosynthetic cluster and consists of a dipeptide core of ornithine and phenylalaninol, where amino groups are acylated with isonitrilecontaining fatty acyl chains. Kupyaphores are stringently regulated and support Mtb survival under both nutritional deprivation and intoxication conditions. A kupyaphore-deficient Mtb strain is unable to mobilize sufficient zinc and shows reduced fitness upon infection. We observed early induction of kupyaphores in Mtb-infected mice lungs after infection, and these metabolites disappeared after 2 wk. Furthermore, we identify an Mtb-encoded isonitrile hydratase, which can possibly mediate intracellular zinc release through covalent modification of the isonitrile group of kupyaphores. Mtb clinical strains also produce kupyaphores during early passages. Our study thus uncovers a previously unknown zinc acquisition strategy of Mtb that could modulate host-pathogen interactions and disease outcome.
Keywords: metallophore; nutritional immunity; tuberculosis; zinc

Machine learning-based approach to determine infection status in recipients of BBV152 (Covaxin) whole-virion inactivated SARS-CoV-2 vaccine for serological surveys - Singh, Prateek; Ujjainiya, Rajat; Prakash, Satyartha; Naushin, Salwa; Sardana, Viren; Bhatheja, Nitin; Singh, Ajay Pratap; Barman, Joydeb; Kumar, Kartik; Gayali, Saurabh; Khan, Raju; Rawat, Birendra Singh; et al. (Computers in Biology and Medicine, 2022)
Data science has been an invaluable part of the COVID-19 pandemic response with multiple applications, ranging from tracking viral evolution to understanding the vaccine effectiveness. Asymptomatic breakthrough infections have been a major problem in assessing vaccine effectiveness in populations globally. Serological discrimination of vaccine response from infection has so far been limited to Spike protein vaccines since whole virion vaccines generate antibodies against all the viral proteins. Here, we show how a statistical and machine learning (ML) based approach can be used to discriminate between SARS-CoV-2 infection and immune response to an inactivated whole virion vaccine (BBV152, Covaxin). For this, we assessed serial data on antibodies against Spike and Nucleocapsid antigens, along with age, sex, number of doses taken, and days since last dose, for 1823 Covaxin recipients. An ensemble ML model, incorporating a consensus clustering approach alongside the support vector machine model, was built on 1063 samples where reliable qualifying data existed, and then applied to the entire dataset. Of 1448 self-reported negative subjects, our ensemble ML model classified 724 to be infected. For method validation, we determined the relative ability of a random subset of samples to neutralize Delta versus wild-type strain using a surrogate neutralization assay. We worked on the premise that antibodies generated by a whole virion vaccine would neutralize wild type more efficiently than delta strain. In 100 of 156 samples, where ML prediction differed from self-reported uninfected status, neutralization against Delta strain was more effective, indicating infection. We found 71.8% subjects predicted to be infected during the surge, which is concordant with the percentage of sequences classified as Delta (75.6%-80.2%) over the same period. Our approach will help in real-world vaccine effectiveness assessments where whole virion vaccines are commonly used.
Keywords: BBV152; Covaxin; COVID-19; Ensemble methods; Infection; machine learning; SARS-CoV-2

Mechanistic insight into differential interactions of iron oxide nanoparticles with native, glycated albumin and their effect on erythrocytes parameters - Nisar, Akib; Ajabia, Devangi K.; Agrawal, Sanskruthi B.; Varma, Sanjana; Chaudhari, Bhushan P.; Tupe, Rashmi S. (International Journal of Biological Macromolecules, 2022)
Nanoparticles and protein bioconjugates have been studied for multiple biomedical applications. We sought to investigate the interaction and structural modifications of bovine serum albumin (BSA) with iron oxide nanoparticles (IONPs). The IONPs were green synthesized using E. crassipes aqueous leaf extract following characterization using transmission electron microscopy, energy dispersive X-ray analysis and X-ray diffraction. Two different concentrations of native/glycated albumin (0.5 and 1.5 mg/ml) with IONPs were allowed to interact for 1 h at 37 degrees C. Glycation markers, protein modification markers, cellular antioxidant, and hemolysis studies showed structural modifications and conformational changes in albumin due to the presence of IONPs. UV-visible absorbance resulted in hyperchromic and bathochromic effects of IONPs-BSA conjugates. Fluorescence measurements of tyrosine, tryptophan, advanced glycated end products, and ANS binding assay were promising and quenching effects proved IONPs-BSA conjugate formation. In FTIR of BSA-IONPs, transmittance was increased in amide A and B bands while decreased in amide I and II bands. In summary, native PAGE, HPLC, and FTIR analysis displayed a differential behaviour of IONPs with native and glycated BSA. These results provided an understanding of the interaction and structural modifications of glycated and native BSA which may provide fundamental repercussions in future studies.
Keywords: Albumin; Glycation; iron oxide nanoparticles

Methanol-to-light olefins reaction using Zn-Ag modified SSZ-13 catalyst - Dange, Rutvija M.; Gawali, Chirag B.; Niphadkar, Prashant S.; Bokade, Vijay V.; Nandanwar, Sachin U. (ChemistrySelect, 2022)
The 2 wt.% of Zn and Ag (Zn1-x-Ag-x; x=0.2, 0.4, 0.6 %) modified SSZ-13 (SZ-13) zeolite was prepared by wet-impregnation method, and its catalytic activity was demonstrated for methanol-to-olefin (MTO). The Zn-0.6-Ag-0.4/SZ-13 catalyst exhibited high catalytic activity due to change in properties of catalyst. The Zn particles were highly dispersed inside the SZ-13; while Ag particles were dispersed on the surface of SZ-13, confirmed by HRTEM and surface area. The small % of Ag over SZ-13 promotes ethylene production via aromatization of reaction, and highly dispersed Zn on SZ-13 help to produce stable ethylene and propylene. The Zn-0.6-Ag-0.4/SZ-13 catalyst showed (similar to 10 %) higher light olefin (87 %) selectivity than parent SZ-13 as well as mono metal incorporated SZ-13. The higher catalytic activity was attributed due to effect of both metals (Zn and Ag), where Ag promotes partial aromatization on the surface, and Zn increases the Lewis acidity in the zeolite pore. This catalyst can help to improve the selectivity of light olefin using MTO reaction.
Keywords: Ethylene; Methanol-to-Olef; Propyl; Silver; SSZ; zinc

Molecular determinants of GPCR pharmacogenetics: deconstructing the population variants in β2-adrenergic receptor - Joshi, Manali; Nikte, Siddhanta; Sengupta, Durba (Advances in Protein Chemistry and Structural Biology, 2022)
G protein-coupled receptors (GPCRs) are membrane proteins that play a central role in cell signaling and constitute one of the largest classes of drug targets. The molecular mechanisms underlying GPCR function have been characterized by several experimental and computational methods and provide an understanding of their role in physiology and disease. Population variants arising from nsSNPs affect the native function of GPCRs and have been implicated in differential drug response. In this chapter, we provide an overview on GPCR structure and activation, with a special focus on the β2-adrenergic receptor (β2-AR). First, we discuss the current understanding of the structural and dynamic features of the wildtype receptor. Subsequently, the population variants identified in this receptor from clinical and large-scale genomic studies are described. We show how computational approaches such as bioinformatics tools and molecular dynamics simulations can be used to characterize the variant receptors in comparison to the wildtype receptor. In particular, we discuss three examples of clinically important variants and discuss how the structure and function of these variants differ from the wildtype receptor at a molecular level. Overall, the chapter provides an overview of structure and function of GPCR variants and is a step towards the study of inter-individual differences and personalized medicine.

Na-montmorillonite to Fe(II)-Mt using ferrous citrate/ascorbate obtained by dissolving iron powder - S. Chikkamath; J. Manjanna; N. Momin; B.G. Hegde; G.P. Nayaka; Aishwarya S. Kar; B.S. Tomar (Applied Clay Science, 2022)
Bentonite containing montmorillonite (Mt) as the major clay mineral is the potential buffer material of engineered barrier system in the deep geological repository for high-level waste management. The corrosion products of canister/or overpack material (carbon steel) may alter the basic characteristics of bentonite through Fe/clay interaction and formation of FeMt to certain extent. A convenient method is required for quantitative preparation of Fe(II)-Mt because the only few direct methods reported have some limitations. For this, weak ferrous complexes having good solubility to facilitate the cation-exchange with bentonite is essential. Therefore, Fe(II)-citrate, Fe(II)-ascorbate and Fe(II)-citrate/ascorbate were obtained here by dissolving the iron powder (Fe0) in citric acid (CA), ascorbic acid (AA) and their equimolar mixtures from 25 mM to 300 mM at 70 °C under N2 atmosphere. The redox potential was measured to monitor the dissolution of Fe0 in these mild organic acids. Higher dissolution of Fe0 occurred in CA + AA mixture. The dissolved iron in the form of ferrous complex was reasonably stable in inert atmosphere, Fe2+/Fetotal ≈ 1. The parent clay mineral (bentonite, NaMt) was treated with Fe(II) − cit/asc to form Fe(II) − Mt. through cation exchange process. The CEC and ferrous to ferric ratio of the Fe(II)-Mt was close to the stoichiometric amount. The XRF, XRD, ac impedance, FT-IR, TGA/DSC, XPS and FE-SEM are used for further characterization. In-situ complexation reaction of interlayer Fe2+ ions in Fe(II)-Mt with o-phenanthroline was also observed.
Keywords: Ascorbic acid; Bentonite; Citric acid; Cr(VI) reduction; Fe(II)-montmorillonite; Iron dissolution

Novel crystal forms of Entresto: a supramolecular complex of trisodium sacubitril/valsartan hemi-pentahydrate - Shaikh, Tabrez R.; George, Christy P.; Bhukya, Priyanka; Shelke, Nikita; Pawar, Komal; Garai, Abhijit; Dandela, Rambabu; Gonnade, Rajesh G.; Nangia, Ashwini K. (Crystengcomm, 2022)
Entresto is a salt-cocrystal supramolecular complex with the chemical name trisodium sacubitril/valsartan hemi-pentahydrate for treating chronic heart failure and was approved by the US FDA in 2015. This multidrug complex was synthesized in our laboratory to investigate its polymorphic behavior. Different crystallization conditions, including various solvent systems, yielded different novel solid forms of Entresto (Form-I to Form-VI), including the reported form. All the novel solids are solvent-dependent and were reproducibly crystallized on a 10 g scale quantity. The 1H NMR spectra confirmed the 1 : 1 stoichiometry of the two drugs, namely, sacubitril and valsartan, in all the solid forms of the crystalline products. Powder X-ray diffraction and DSC analysis of the crystalline solids established that they are distinct crystalline forms. Stability studies under ambient conditions carried out over a one-year period showed higher stability for Form-I and Form-III compared to the other forms, including the innovator crystal form (labelled as Form-II). The novel crystal forms (notably Form-I and Form-III) exhibit higher stability and less hygroscopicity than the reported Form-II.

Pendant propargyloxy-functionalized aromatic (co)polycarbonates: synthesis, thermal crosslinking and chemical modification - Nagane, Samadhan S.; Maher, Deepak M.; Verma, Savita; Talanikar, Aniket A.; Wadgaonkar, Prakash P. (Journal of Macromolecular Science Part A-Pure and Applied Chemistry, 2022)
A bisphenol monomer bearing pendant propargyloxy group viz, 1, 1-bis (4-hydoxyphenyl)-1-(4 `-propargyloxyphenyl) ethane (BPP) was synthesized starting from commercially available 1, 1, 1-tris (4-hydroxyphenyl) ethane (THPE) by mono O-propargylation reaction using propargyl bromide. A new series of pendant propargyloxy-functionalized aromatic (co)polycarbonates was synthesized by low-temperature solution polycondensation of BPP or different molar ratios of BPP and bisphenol-A with triphosgene in dichloromethane in the presence of triethylamine. The formation of reasonably high molecular weight (co)polycarbonates was confirmed by inherent viscosity (0.52-0.83 dL/g) and gel permeation chromatography (M-n 37,000-69,800 g/mol, polystyrene standards) measurements. C-13 NMR spectral studies supported formation of random copolycarbonates in copolymerization of BPP and BPA with triphosgene. The 10% weight loss temperature (T-10) values of (co)polycarbonates, determined by thermogravimetric analysis under nitrogen atmosphere, were in the range 427-438 degrees C indicating their good thermal stability. The glass transition temperature (T-g) values of (co)polycarbonates were observed in the range 147-152 degrees C. The crosslinking ability of (co)polycarbonates involving pendant propargyloxy groups leading to formation of networked structure was evaluated via non-isothermal curing studies by DSC. As a proof-of-concept, the post-modification of a representative polycarbonate bearing pendant propargyloxy groups with 1-octane thiol as a model compound via thiol-yne click reaction was briefly studied.
Keywords: Aromatic polycarbonate; Chemical modification; propargyloxy groups; thermal crosslinking; thiol-yne click reaction

Post-polymerization modifiable aromatic (co)poly(ether sulfone)s possessing pendant norbornenyl groups based upon a new bisphenol - Talanikar, Aniket A.; Nagane, Samadhan S.; Wadgaonkar, Prakash P.; Rashinkar, Gajanan S. (European Polymer Journal, 2022)
A new bisphenol possessing pendant norbornenyl group viz., 4, 4 `-(bicyclo (2.2.1) hept-5-en-2 yl methylene) bis (2-methoxyphenol) (BPA-NB) was synthesized by a single-step base-catalyzed condensation reaction of 5-norbor-nene-2-carboxaldehyde with guaiacol. NMR spectral data indicated formation of BPA-NB comprising of isomeric components. A series of (co)poly(ether sulfone)s possessing pendant norbornenyl groups was synthesized by nucleophilic aromatic substitution polycondensation of varying molar ratio of BPA-NB and bisphenol-A (BPA) with bis(4-fluorophenyl) sulfone. Inherent viscosity values and number average molecular weights of (co)poly (ether sulfone)s were in the range 0.67-1.01 dL/g and 75,400-1,16,300 g/mol, respectively indicating the formation of reasonably high molecular weight polymers. Tough, transparent, and flexible films could be cast from chloroform solutions of these (co)poly(ether sulfone)s. (Co)poly(ether sulfone)s were characterized using FT-IR, H-1 NMR and C-13 NMR spectroscopy, XRD, TGA and DSC analysis. The formation of random copoly(ether sulfone)s was demonstrated by( 13)C NMR analysis. The incorporation of BPA-NB into (co)poly(ether sulfone)s resulted into improvement in Tg values. BPA-NB-based (co)poly(ether sulfone)s offered possibilities for post -modifications involving either methoxyl or norbornenyl groups. A representative copoly(ether sulfone) (PSU-NB-2) possessing pendant norbornenyl groups was chemically modified via thiol-ene reaction with three representative thiol compounds, namely, 1-dodecanethiol, 2-furanmethanethiol and 2-mercaptoethanol to yield corresponding post-modified polymers in a quantitative manner. Additionally, it was demonstrated that copoly (ether sulfone) possessing pendant norbornenyl groups could be used to form insoluble cross-linked gel in the presence of a multifunctional thiol cross-linker.
Keywords: (Co)poly(ether sulfone)s; bisphenol; Cross -linking; Pendant norbornenyl groups; Thiol-ene reaction

Pseudo-boehmite AlOOH supported NGr composite-based air electrode for mechanically rechargeable Zn-air battery applications - Kharabe, Geeta Pandurang; Manna, Narugopal; Nadeema, Ayasha; Singh, Santosh K.; Mehta, Shweta; Nair, Aathira; Joshi, Kavita; Kurungot, Sreekumar (Journal of Materials Chemistry A, 2022)
Both mechanically and electrically rechargeable zinc-air batteries (ZABs) have received much interest due to their high energy density and suitability for mobile and stationary applications. However, their commercialization has been impeded by the lack of robust, low-cost and environmentally benign catalyst materials that can be easily scaled up. In this context, the present work introduces a new type of transition metal-free catalytic material (AlOOH/NGr) by anchoring the pseudo-boehmite phase of aluminium oxyhydroxide (AlOOH) nanosheets over nitrogen-doped graphene (NGr) via a single-step and straightforward hydrothermal process. Furthermore, density functional theory (DFT) based computation demonstrates that the nucleation of AlOOH starts from the N-sites and points towards the strong surface interaction between AlOOH and NGr via doped nitrogen. AlOOH/NGr consisting of thin layered pseudo-boehmite sheets uniformly distributed over NGr has displayed an oxygen reduction reaction onset potential of 0.83 V and a half-wave potential of 0.72 V, along with good catalytic durability in alkaline medium. With this, AlOOH/NGr, when used as an air electrode for fabricating a primary Zn-air battery, the system has exhibited an open circuit voltage of similar to 1.27 V with a flat discharge profile at a current rate of 10 mA cm(-2). The fabricated system delivered a specific capacity of similar to 720 mA h g(-1) and a high power density of 204 mW cm(-2) and is comparable to the counterpart system based on the state-of-the-art Pt/C (20 wt% Pt) cathode. Additionally, the homemade battery was able to maintain its performance after 4 times of mechanical recharging of the battery, which lasted for more than 35 h at a discharge current density of 10 mA cm(-2). Thus, we have uncovered the potential of an earth-abundant metal-based catalytic system for fabricating and demonstrating a robust mechanically rechargeable zinc-air battery.

Reactivity of four coordinate iridium complex towards hydrogen: an experimental and computational study - Agrawal, Nisha K.; Dash, Soumya R.; Vanka, Kumar; Nethaji, Munirathinam; Jagirdar, Balaji R. (Journal of Organometallic Chemistry, 2022)
Reaction of a four coordinate, 16-electron Ir complex, [Ir-(iPr)4(POCOP)(PPh3)] (4 ) (((iPr)4)(POCOP= 2,6-bis(di-isopropyl phosphinito)benzene, kappa(3)-C6H3-1,3-[OP((iPr))(2)](2)), with H-2 resulted in an oxidative addition product, cis-dihydride complex, cis-[Ir(H)(2) ((iPr)4)(POCOP)(PPh3)] ( cis-5 ) presumably via the intermediacy of a sigma complex, [Ir(eta(2)-H-2)((iPr)4)(POCOP)(PPh3)]. The cis-dihydride complex completely isomerizes to the trans-dihydride complex trans-[Ir(H)(2) ((iPr)4)(POCOP)(PPh3)] ( trans-5 ) under ambient conditions in about 3 h. It was found that the steric and electronic features on the iridium center have significant influence on the approach of H-2 onto the metal center followed by oxidative addition and isomerization. The isomerization process was studied in detail and all the mechanistic aspects have been elucidated using a combination of both experimental work and computation. The cis-dihydride complex isomerizes to the trans-dihydride by compensating the trans influence of the strongly trans-directing hydride ligand. A mechanism involving the exchange of the position of PPh3 with a hydride ligand cis to itself via PPh3 dissociation and re-coordination thereby resulting in the formation of the trans-dihydride complex, has been proposed for the isomerization. The cis-dihydride was found to be a highly active catalyst for hydrogenation of ethy-lene. A competing reactivity study of cis-dihydride between isomerization versus insertion of C2H4 into the Ir-H bond, was studied experimentally and computationally. (c) 2022 Elsevier B.V. All rights reserved.
Keywords: Hydrogenation; Insertion; iridium complex; isomerization; Oxidative addition; Reductive elimination

Reference quality genome sequence of Indian pomegranate cv. `Bhagawa' (Punica granatum L.) - Roopa Sowjanya, P.; Shilpa, Parashuram; Patil, Goudappa Prakash; Babu, Dhinesh Karuppannan; Sharma, Jyotsana; Sangnure, Vipul R.; Mundewadikar, Dhananjay M.; Natarajan, Purushothaman; Marathe, Arvind Rajiv; Reddy, Umesh K.; Singh, Vikram Nripendra (Frontiers in Plant Science, 2022)
Pomegranate is an important fruit crop for ensuring livelihood and nutrition security in fragile semi-arid regions of the globe having limited irrigation resources. This is a high-value, nutritionally rich, and export-oriented agri-commodity that ensures high returns on investment to growers across the world. Although it is a valuable fruit crop, it has received only a limited genomics research outcome. To fast-track the pomegranate improvement program, de novo whole-genome sequencing of the main Indian cultivar `Bhagawa' was initiated by the Indian Council of Agricultural Research-National Research Center on Pomegranate (ICAR-NRCP). We have demonstrated that a combination of commercially available technologies from Illumina, PacBio, 10X Genomics, and BioNano Genomics could be used efficiently for sequencing and reference-grade de novo assembly of the pomegranate genome. The research led to a final reference-quality genome assembly for `Bhagawa' of 346.08 Mb in 342 scaffolds and an average N50 of 16.12 Mb and N90 of 1088.62 Kb. This assembly covered more than 98% of the estimated pomegranate genome size, 352.54 Mb. The LTR assembly index (LAI) value of 10 and 93.68% Benchmarking Universal Single-Copy Orthologs (BUSCO) completeness score over the 1,440 ortholog genes of the completed pomegranate genome indicates the quality of the assembled pomegranate genome. Furthermore, 29,435 gene models were discovered with a mean transcript length of 2,954 bp and a mean coding sequence length 1,090 bp. Four transcript data samples of pomegranate tissues were mapped over the assembled `Bhagawa' genome up to 95% significant matches, indicating the high quality of the assembled genome. We have compared the `Bhagawa' genome with the genomes of the pomegranate cultivars `Dabenzi' and `Taishanhong.' We have also performed whole-genome phylogenetic analysis using Computational Analysis of Gene Family Evolution (CAFE) and found that Eucalyptus grandis and pomegranate diverged 64 (60-70) million years ago. About 1,573 protein-coding resistance genes identified in the `Bhagawa' genome were classified into 32 domains. In all, 314 copies of miRNA belonging to 26 different families were identified in the `Bhagawa' genome. The reference-quality genome assembly of `Bhagawa' is certainly a significant genomic resource for accelerated pomegranate improvement.
Keywords: genome sequencing; hybrid genome assembly; Long Terminal Repeats Assembly Index (LAI); PacBio; pomegranate

Reinforcement of electrospun polyurethane fibers with resorcinol-formaldehyde resin - Nair, Kiran Sukumaran; James, Nirmala Rachel (Journal of Applied Polymer Science, 2022)
This work reports a simple method to improve the properties of electrospun nanofibers. The procedure involves developing nanofibers using electrospinning followed by liquid infiltration to reinforce the fibers. Coating of polyurethane nanofibers (PUN) with resorcinol-formaldehyde (RF) significantly improves the properties of PUN. Furthermore, the morphology of fiber interface and the properties of RF coated fibers indicate that RF resin reinforces the interface between the fibers. The method leads to improvement in mechanical properties of PUN. An improvement of about 94% and 281% in mechanical properties like tensile strength and modulus, respectively, compared to neat PUN fibers is achieved by coating with 20% wt/vol of RF solution.
Keywords: Dynamic mechanical analysis; electrospinning; liquid infiltration; polyurethane; reinforced nanofibers; resorcinol-formaldehyde

Role of facet in the competitive pathway of ethylene epoxidation - Nair, Aathira; Kenge, Nivedita; Joshi, Kavita (Surface Science, 2022)
Ethylene epoxide (EtO) is used as raw material for a broad range of products from pharmaceuticals and plastics to paints and adhesives. Although the reaction of ethylene interacting with preadsorbed oxygen on Ag surface is known for decades, the underlying mechanism of EtO formation is not completely understood. Successful investigation of oxametallacycle (OMC) intermediate common to selective as well as non-selective pathways has ensured at least 50% selectivity. The current study brings out the electronic signatures of distinct conformers of OMC stabilised on two different facets of Ag viz. (100) and (111). There are subtle differences between OMC conformers observed on these two facets with near-eclipsed on Ag(100) and near-staggered on Ag(111). A detailed analysis of Ag-O, C-O, C-C, and Ag-C interactions along with projected Density of States (pDOS) and projected Crystal Orbital Hamilton Population (pCOHP) imply towards ring closure on Ag(100) and hydrogen transfer on Ag(111). Finally, our understanding based on electronic and structural signatures are backed up by activation barriers computed through NEB calculations. Activation barrier for EtO is lower on (100) as compared to (111) facet. Thus, our study sheds light on how these differences between OMC affect the selectivity towards EtO.
Keywords: Ag(100); Ag(111); DFT; epoxidation; Ethylene Oxide (EtO); OMC

Ru, Pd doped WO3 nanomaterials: a synergistic effect of noble metals to enhance the acetone response properties - Kodam, Pavan M.; Ghadage, Pandurang A.; Nadargi, Digambar Y.; Shinde, K. P.; Mulla, Imtiaz S.; Park, J. S.; Suryavanshi, Sharad S. (Ceramics International, 2022)
Noble metals (NMs) have an enormous impact on the intrinsic properties of the metal oxides. We report the synergistic effect of Ruthenium (Ru) and Palladium (Pd) noble metals on the enhancement of gas sensing properties of pure tungsten oxide (WO3). The gas sensing material is synthesized by simple and straight forward precipitation route, and its physico-chemical analyses are determined using XRD, FESEM, TEM/HRTEM, FFT, UV-Vis, XPS, EDAX, and BET measurements. Use of the developed material as a gas sensor is evaluated using several target gases (oxidizing as well as reducing), with acetone showing the best selectivity. The noble metal doping and hence catalytic action improved the gas response qualities. The synergistic effect of Ru and Pd on WO3 gas response properties are identified, where the effect is 99.80% sensitivity, and lower response/recovery time (10 s and 2 min) at 300 degrees C operating temperature. Nonetheless, the sensors displayed better gas sensing properties even at lower operating temperatures ranging from 200 to 275 degrees C. In addition, the synergistic effect has displayed the dramatic enhancement in the sensitivity to 76.44% at barely 10 ppm acetone concentration. This particular result will undoubtedly be helpful for diagnostic purpose of diabetic patients, and a strong candidate for prospective gas sensing applications, particularly acetone.
Keywords: Acetone vapours; Precipitation route; Ru -Pd doping; synergistic effect; WO3

Scalable mechanochemical synthesis of beta-ketoenamine-linked covalent organic frameworks for methane storage - Asokan, Kiran; Patil, Manoj Krishnat; Mukherjee, Shatabdi Porel; Sukumaran, Santhosh Babu; Nandakumar, T. (Chemistry-An Asian Journal, 2022)
In the current scenario of increased pollution and releasing toxic gases by burning petroleum products, switching to natural gas is more promising for reducing CO2 emissions and air pollutants. Hence, research on Liquefied Natural Gas and Compressed Natural Gas is gaining more value. However, natural gas primarily consists of CH4, which has less energy density than conventional fuels. Interestingly, since the C-H ratio of CH4 gas is 1 : 4, it is easily combustible, gives less carbon footprint, and reduces unburnt hydrocarbon pollution. Hence, research on storing and transporting CH4 has utmost importance, and porous materials are one of the suitable candidates for storing CH4. Herein we report the scalable synthesis of highly porous and crystalline covalent organic frameworks for storing CH4 at room temperature and pressure. Two COFs, namely, Tp-Azo and Tp-Azo-BD(Me)(2), synthesized in 1 kg at similar to 45 g batch scale using a Planetary mixer, displayed a maximum BET surface area of around 3345 m(2)/g, and 2342 m(2)/g and CH4 storage of 174.10 cc/cc and 151 cc/cc, respectively. A comparison of the CH4 sorption of Tp-Azo and Tp-Azo-BD(Me)(2) COFs synthesized in different batches has a variation of only +/- 5 cc/cc and shows the consistency in bulk scale synthesis of COFs. The cyclic equilibrium CH4 adsorption studies showed the COFs are stable with consistent CH4 adsorption and desorption cycles. The present study is a step towards the scalable mechanochemical synthesis of COFs for gas storage applications.
Keywords: CH4 storage; COF; porous material; scalable synthesis

Silk fibroin and recombinant elastin blend nano-coatings for implantable medical devices - Joseph, Emmanuel; Kane, Kartiki; Parekh, Nimisha; Nisal, Anuya; Janorkar, V. Amol (Materials Today Communications, 2022)
Silicone breast implants are conventionally used to reconstruct the shape and size of the breast in breast cancer patients. However, rate of failure of implants due to formation of capsular contracture is significantly high. Recent studies have shown that coating the surface of the implant with a biocompatible polymer can mitigate this risk. Here, we have modified the surface of implant using a biocompatible natural biopolymer silk fibroin (SF). Further, we have developed formulations of SF with a recombinantly produced elastin-like-peptide (ELP) and compared their performance with a known anti-fouling hydrophilic polymer - polyethylene oxide (PEO). Microscopic and spectroscopic characterization confirm the formation of uniform coatings. These coatings have been also characterized for their ability to resists crack formation. Further, the coatings have been evaluated for their biological performance. Our studies show that addition of 25 wt% of ELP to SF significantly enhances the crack resistance for the coatings. In addition, SF/ELP coatings reduce the adsorption of blood plasma proteins by more than 80 %. Preliminary analysis shows that the SF/ELP blend coatings are non-cytotoxic and support adhesion, growth and proliferation of fibroblast cells. The study therefore demonstrates that SF/ELP coatings have the potential to mitigate the risk of breast implant failure.
Keywords: Blood plasma; Crack resistance; Protein adsorption; Recombinant elastin; Silk fibroin

Silk fibroin microparticle scaffold for use in bone void filling: safety and efficacy studies - Deshpande, Rucha; Shukla, Swati; Kale, Amod; Deshmukh, Narendra; Nisal, Anuya; Venugopalan, Premnath (ACS Biomaterials Science & Engineering, 2022)
Silk fibroin (SF) is a natural biocompatible protein polymer extracted from cocoons of silkworm Bombyx mori. SF can be processed into a variety of different forms and shapes that can be used as scaffolds to support bone regeneration. Threedimensional (3D) SF scaffolds have shown promise in bone-void -filling applications. In in vitro studies, it has been demonstrated that a microparticle-based SF (M-RSF) scaffold promotes the differentiation of stem cells into an osteoblastic lineage. The expression of differentiation markers was also significantly higher for M-RSF scaffolds as compared to other SF scaffolds and commercial ceramic scaffolds. In this work, we have evaluated the in vitro and in vivo biocompatibility of M-RSF scaffolds as per the ISO 10993 guidelines in a Good Laboratory Practice (GLP)-certified facility. The cytotoxicity, immunogenicity, genotoxicity, systemic toxicity, and implantation studies confirmed that the M-RSF scaffold is biocompatible. Further, the performance of the MRSF scaffold to support bone formation was evaluated in in vivo bone implantation studies in a rabbit model. Calcium sulfate (CaSO4) scaffolds were chosen as reference material for this study as they are one of the preferred materials for bone-void -filling applications. M-RSF scaffold implantation sites showed a higher number of osteoblast and osteoclast cells as compared to CaSO4 implantation sites indicating active bone remodeling. The number density of osteocytes was double for M-RSF scaffold implantation sites, and these M-RSF scaffold implantation sites were characterized by enhanced collagen deposition, pointing toward a finer quality of the new bone formed. Moreover, the M-RSF scaffold implantation sites had a negligible incidence of secondary fractures as compared to the CaSO4 implantation sites (similar to 50% sites with secondary fracture), implying a reduction in postsurgical complications. Thus, the study demonstrates that the M-RSF scaffold is nontoxic for bone-void -filling applications and facilitates superior healing of fracture defects as compared to commercial calcium-based bone void fillers.
Keywords: Biocompatibility; biological safety; bone void filler; ISO 10993; M-RSF; Serioss; Silk fibroin

Silver-catalyzed [3 + 3]-annulation cascade of alkynyl alcohols and α,β-unsaturated ketones for the regioselective assembly of chromanes - Nakate, Ashwini K.; Thorat, Sagar S.; Jain, Shailja; Rama Krishna, Gamidi; Vanka, Kumar; Kontham, Ravindar (Organic Chemistry Frontiers, 2022)
An unprecedented Ag(i)-catalyzed [3 + 3]-annulation of alkynyl alcohols (5-hexyn-1-ols) and α,β-unsaturated ketones is reported to construct simple to complex chromanes. This transformation begins with hydroalkoxylation of alkynol through C–C triple bond activation to give cyclic-enol ether, followed by intermolecular 1,4-addition and intramolecular 1,2-addition of enol ethers onto the enone and oxidative aromatization or Grob-type elimination steps. Facile reaction conditions, broad substrate scope, good to excellent yields, and atom economy are the salient features of this protocol. Isolation of the active pyran-tethered cyclohexadiene reaction intermediate, additional supporting experiments, and DFT calculations strongly support the experimental findings and corroborate our proposed mechanism.

Spinel magnesium ferrite (MgFe2O4): a glycine-assisted colloidal combustion and its potentiality in gas-sensing application - Nadargi, Digambar; Umar, Ahmad; Nadargi, Jyoti; Patil, Jayvant; Mulla, Imtiaz; Akbar, Sheikh; Suryavanshi, Sharad (Chemosensors, 2022)
Herein, we describe the facile synthesis of spinel MgFe2O4 ferrite and its potential use as a gas sensor using a straightforward and reliable sol-gel approach, i.e., the glycine-assisted auto-combustion route. The novelty in obtaining the sensing material via the auto-combustion route is its inherent simplicity and capability to produce the material at an industry scale. The said cost-effective process makes use of simple metal salts (Mg and Fe-nitrates) and glycine in an aqueous solution, which leads to the formation of spinel MgFe2O4 ferrite. A single-phase crystallinity with crystallite sizes ranging between 36 and 41 nm was observed for the synthesized materials using the X-ray diffraction (XRD) technique. The porous morphologies of the synthesized materials caused by auto-ignition during the combustion process were validated by the microscopic investigations. The EDS analysis confirmed the constituted elements such as Mg, Fe, and O, without any impurity peaks. The gas-sensing ability of the synthesized ferrites was examined to detect various reducing gases such as LPG, ethanol, acetone, and ammonia. The ferrite showed the highest response (>80%) toward LPG with the response and recovery times of 15 s and 23 s, respectively. Though the sensor responded low toward ammonia (similar to 30%), its response and recovery times were very quick, i.e., 7 s and 9 s, respectively. The present investigation revealed that the synthesized ferrite materials are good candidates for fabricating high-performance sensors for reducing gases in real-world applications.
Keywords: Gas sensors; glycine combustion; MgFe2O4; reducing gases

Sponge microflowers of NiCo2O4: a versatile material for high performance supercapacitor - Ghadage, Ambar; Kodam, Pavan; Nadargi, Digambar; Shinde, K. P.; Mulla, Imtiaz; Park, J. S.; Suryavanshi, Sharad (Journal of Porous Materials, 2022)
We report the development of well optimised NiCo2O4 microflowers for high performance supercapacitor application. The efforts were made to optimise the electrode material by tuning the synthetic as well as electrolyte concentration parameters such as (i) hydrothermal reaction temperature, (ii) hydrothermal reaction time, (iii) sintering temperature, and (iv) electrolyte concentration. The physico-chemical and supercapacitive properties were analysed using TGA, XRD, SEM/TEM/HRTEM, XPS, BET, and electrochemical measurements. The well optimised electrode material was obtained at 150 degrees C hydrothermal reaction temperature, 12 h of hydrothermal reaction time, 300 degrees C sintering temperature, and 3 M KOH electrolyte concentration. The optimised sample displayed high specific -capacitance (1478 F/g), -energy density (16.5 Wh/kg), and -power density (248 W/kg). The specific capacitance can be retained to 97.61% after 1000 cycles. The developed NiCo2O4 microflower structures are well optimised and offer great promise for future industrial applications.
Keywords: hydrothermal; Microflowers; Nickel cobaltite; supercapacitor

Structure-property insights into chiral thiophene copolymers by direct heteroarylation polymerization - Nikam, Shrikant B.; Singh, Chandrodai Pratap; Krishnamurty, Sailaja; Asha, S. K. (European Polymer Journal, 2022)
Chiral thiophene copolymers with fluorene as co monomer are designed having N-Boc-L-glutamic acid-1-tert-butyl ester as a chiral substituent located either on the thiophene unit or the fluorene unit with varying spacer length. The atom-economic direct heteroarylation polymerization (DHAP) method is utilized for the polymerization. Gibb's free energy (delta G) for polymerization determined using DFT calculations indicate difficulty in achieving high molar mass when the bulky chiral substituents are attached through short spacer to the backbone. The experimental observations are in agreement with the theoretical calculations with no polymer-ization or very low molar mass sticky compounds obtained for reactions with predicted + & UDelta;G values. Structure -property relationship are compared for two chiral polymers -P4 and P5 having the chiral substitution on thiophene and fluorene units respectively. No CD signal is observed in THF-a good solvent where the polymers are molecularly dissolved. Intense bisignated CD signal is observed for both polymers upon addition of methanol - a poor solvent, to their THF solution. The bisignate CD signal with maxima at lower wavelength and inflection point associated with the pi-pi* absorption band is characteristic of exciton coupling between polymer chains in a left handed helical orientation. Small differences are observed in the intensity of the CD signal for the polymers P4 and P5 highlighting the impact of steric hindrance of bulky pendant groups on polymer conformation. DHAP is an atom economic polymerization procedure that can be gainfully utilized for developing chiral conjugated polymers.
Keywords: chiral; DFT; Direct heteroarylation polymerization; Gibb?s free energy; Steric Hindrance

Studies directed toward the synthesis of hedycoropyrans: total synthesis of des-hydroxy (-)-hedycoropyran B (ent-rhoiptelol B) - Kataria, Priyanka; Nomula, Rajesh; Kontham, Ravindar (Organic & Biomolecular Chemistry, 2022)
A full account of our efforts directed towards the synthesis of the diarylheptanoid-derived natural products hedycoropyrans that led to the total synthesis of ent-rhoiptelol B is described. In this endeavor, we have attempted two distinct synthetic strategies to access hedycoropyrans A and B, which led us to establish a facile synthetic route for des-hydroxy (-)-hedycoropyran B (ent-rhoiptelol B) from simple and readily accessible building blocks of 4-allylanisole and vanillin, employing Sharpless asymmetric epoxidation, CBS reduction, and an intramolecular AgOTf-catalyzed oxa-Michael reaction of suitably functionalized hydroxy-ynone as key transformations. The investigations disclosed herein will provide insights into designing novel synthetic routes for THP-DAH-derived natural products.

Studies directed toward the total synthesis of nannocystin A - Nomula, Rajesh; Pratapure, Madhukar S.; Kontham, Ravindar (ChemistrySelect, 2022)
A full account of our efforts directed toward the stereoselective total synthesis of nannocystin A, a macrocyclic myxobacterial metabolite, is presented. In this endeavor, we have attempted two distinct synthetic routes to access polyketide fragment (C1-C11) of macrocyclic depsipeptide (21-membered) natural product from readily accessible building blocks 1,3-propanediol and benzaldehyde employing Evans aldol, CBS reduction, Heck cross-coupling, and Sharpless asymmetric epoxidation as key transformations. Ultimately, accomplished the synthesis of the complete skeleton (21-membered precursor for macrocyclic depsipeptide) of the nannocystin A possessing desired stereochemistry and functional groups.
Keywords: amidation; Depsipeptide; Evans aldol reaction; Macrocycle; Nannocystins

Study on anisotropy in wire arc additively manufactured Inconel 625 multi-layered wall and its correlation with molten pool thermal history - Nagallapati, Vishwanath; Choudhary, Amit; Torris, Arun; Muvvala, Gopinath; Dadasaheb, Sagar Pawar; Gudur, Srinath Ellaswamy (Materials Science and Engineering A-Structural Materials Properties Microstructure and Processing, 2022)
In the present study, the variation in molten pool thermal history with layer number during wire arc additive manufacturing of Inconel 625 wall was investigated. Further, its effect on the evolution of microstructure and anisotropy in mechanical and corrosion properties was reported. During the deposition process, the molten pool thermal history was monitored using a non-contact type IR pyrometer operating at 1.6 mu m wavelength. A total number of 40 layers were deposited, building a wall of 60 mm height. With an increase in layer number, the molten pool lifetime and cooling rate were found to increase and decrease, respectively, resulting in coarse grains and increased elemental segregation or Laves phase formation. To investigate its effect on mechanical properties, the samples were collected in a skewed fashion along the height with orientation in the deposition direction. The tensile specimens collected close to the substrate exhibited better strength and ductility, while the samples from the top location of the wall exhibited a relatively brittle mode of fracture, which was investigated by carrying out the fracture surface analysis using SEM. Corrosion test was also conducted along the height of the wall, wherein the samples close to substrate exhibited better corrosion resistance due to refined microstructure and low elemental segregations. Further, EDS, XRD analysis and hardness test were carried out to investigate the elemental composition, variation in phases and hardness with layer number, respectively.
Keywords: anisotropy; Layer number; mechanical properties; Molten pool thermal history; Wire arc additive manufacturing

Superior processability of Antheraea mylitta silk with cryo-milling: performance in bone tissue regeneration - Parekh, Nimisha; Bijosh, C. K.; Kane, Kartiki; Panicker, Alaka; Nisal, Anuya; Wangikar, Pralhad; Agawane, Sachin (International Journal of Biological Macromolecules, 2022)
Non-mulberry silk polymers have a promising future in biomedical applications. However, the dissolution of nonmulberry silk fiber is a still challenge and this poor processability has limited the use of this material. Here, we report a unique protocol to process the Antheraea mylitta (AM) silk fiber. We have shown that the cryo-milling of silk fiber reduces the beta sheet content by more than 10% and results in an SF powder that completely dissolves in routine solvents like trifluoroacetic acid (TFA) within few hours to form highly concentrated solutions (\~20 wt %). Further, these solutions can be processed using conventional processing techniques such as electrospinning to form 3D scaffolds. Bombyx mori (BM) silk was used as a control sample in the study. In-vitro studies were also performed to monitor cell adhesion and proliferation and hMSCs differentiation into osteogenic lineage. Finally, the osteogenic potential of the scaffolds was also evaluated by a 4-week implantation study in rat calvarial model. The in-vitro and in-vivo results show that the processing techniques do not affect the biocompatibility of the material and the AM scaffolds support bone regeneration. Our results, thus, show that cryo-milling facilitates enhanced processability of non-mulberry silk and therefore expands its potential in biomedical applications.
Keywords: Bone tissue engineering; Calvarial defect; hMSCs; Non-mulberry silk fiber; Processing technique

Synthesis and antimycobacterial screening of a novel series of alpha-amino acids containing thiazole linker - Nalawade, Jitendra L.; Mhaske, Pravin C.; Shinde, Abhijit D.; Chavan, Abhijit P.; Abhale, Yogita K.; Sarkar, Dhiman; Bobade, Vivek D. (ARKIVOC, 2022)
A small focused library of uncommon (S)-2-amino-3-(4-(((4-methyl-2-arylthiazol-5-yl)methyl)amino)phenyl) propanoic acid (5a-e) and (S)-2-amino-3-(4-(((2-arylthiazol-4-yl)methyl)amino)phenyl)propanoic acid (9a-d) derivatives have been efficiently synthesized by employing molecular simplification. The title compounds were screened for inhibitory activity against Mycobacterium tuberculosis H37Ra (MTB) and Mycobacterium bovis (BCG) strains. The cytotoxicity study was conducted against primary Human Umbilical Vein Endothelial Cells (HUVECs), on two different human tumor cells HeLa, and HCT 116 and was observed non-toxic to host cells.
Keywords: Amino acid; antibacterial activity; Cytotoxicity; Mycobacterium tuberculosis; synthesis; Thiazole

Synthesis and characterization of partially biobased aromatic (Co)polycarbonates containing biphenylene units and pendant pentadecyl chains - Ichake, Amol B.; Nagane, Samadhan S.; Jadhav, Uday A.; Torris, Arun; Grau, Etienne; Cramail, Henri; Wadgaonkar, Prakash P. (Macromolecular Chemistry and Physics, 2022)
2-Pentadecyl-[1,1''-biphenyl]-4,4''-diol (PBD) is synthesized starting from cashew nut shell liquid-a by-product of cashew processing industry. A new series of partially biobased aromatic (co)polycarbonates possessing biphenylene units and pendant pentadecyl chains is synthesized by solution polycondensation of PBD or varying compositions of PBD and bisphenol-A with triphosgene in dry dichloromethane. Inherent viscosities and number average molecular weights of (co)polycarbonates are in the range 0.51-1.24 dL g(-1) and 18 x 10(3)- 43.4 x 10(3) g mol(-1), respectively indicating the formation of reasonably high molecular weight polymers. Flexible, transparent, and free-standing films of (co)polycarbonates can be cast from chloroform solution. (Co)polycarbonates are characterized using Fourier transform infrared spectroscopy (FTIR), H-1 NMR, C-13 NMR spectroscopy, X-ray diffraction (XRD), differential scanning calorimetry, and thermogravimetric analysis. T-10 and T-g values of (co)polycarbonates are in the range 417-433 and 8-147 degrees C, respectively. It is demonstrated that the T-g values can be tuned by incorporation of appropriate mol% of PBD as a comonomer in Bisphenol-A-based copolycarbonates. The lowering of the T-g values of (co)polycarbonates can be attributed primarily to the packing disruptive effect of flexible pentadecyl chains. Furthermore, the effect of incorporation of PBD as a comonomer on water contact angle values of (co)polycarbonates is evaluated.
Keywords: aromatic polycarbonates; biobased bisphenol; Cashew nut shell liquid; pentadecyl chain; Renewable resources

Synthesis and ionic conductivity of calcium-doped ceria relevant to solid oxide fuel cell applications - Momin, Naeemakhtar; Manjanna, J.; Kobayashi, Satoru; Aruna, S. T.; Kumar, S. Senthil; Nayaka, G. P. (Materials Advances, 2022)
Towards the development of green energy devices, it is necessary to focus on commercial electrolyte materials for intermediate temperature solid oxide fuel cells (IT-SOFCs). Ca-doped ceria (CDC) samples having a composition of Ce(1−x)CaxO2−δ (0.03 ≤ x ≤ 0.1) were synthesized by a facile solid-state route and sintered at a lower temperature (1473 K). X-ray diffraction, Raman, X-ray photoelectron, Fourier-transform infrared, UV–VIS diffuse reflectance, field emission scanning electron microscopy – energy dispersive X-ray with elemental mapping, and electrochemical impedance spectroscopy techniques were used for the characterization of these CDC samples. The 0.10 CDC showed high oxide ion conductivity of 8.01 × 10−3 S cm−1 at 973 K with a lower activation energy of 0.78 eV. The 0.03 CDC, 0.05 CDC, and 0.07 CDC samples exhibited ionic conductivities of 1.66 × 10−4, 4.42 × 10−3, and 5.76 × 10−3 S cm−1 at 973 K with activation energies of 1.65, 1.01, and 0.92 eV, respectively. The present work aims to develop Ca-doped ceria as economically viable electrolytes for IT-SOFCs.

Synthesis, characterization and UV-crosslinking of aromatic (Co)polycarbonates bearing pendant azido groups - Nagane, Samadhan S.; Kuhire, Sachin S.; Ichake, Amol B.; Talanikar, Aniket A.; Lochab, Bimlesh; Wadgaonkar, Prakash P. (ChemistrySelect, 2022)
A new series of (co)polycarbonates bearing pendent azido groups was synthesized by polycondensation of varying molar proportions of 4, 4'-(5-azidopentane-2, 2-diyl) diphenol and bisphenol-A with triphosgene. The chemical structures, compositions and random nature of (co)polycarbonates were confirmed by NMR spectroscopy. Inherent viscosities and number-average molecular weights of (co)polycarbonates were in the range 0.63-0.77 dL g(-1) and 35,400-43,400 g mol(-1), respectively indicating the formation of reasonably high molecular weight polymers. (Co)polycarbonates could be cast into tough, transparent and flexible films from chloroform solutions. (Co)polycarbonates were further characterized using IR spectroscopy, XRD, TGA and DSC. The thermal crosslinking of (co)polycarbonates bearing pendant azido groups was studied by DSC analysis. Independently, (co)polycarbonates bearing pendant azido groups were exposed to UV irradiation at wavelength of 254 nm and decomposition reaction of azido groups was monitored by FT-IR spectroscopy. The complete decomposition of azido groups was observed with exposure time of 30 min. The formed cross-linked (co)polycarbonates exhibited improved % char yield values compared to parent (co)polycarbonates. The measurement of mechanical properties of representative crosslinked (co)polycarbonates indicated increase in tensile strength and Young's modulus and decrease in % elongation compared to corresponding parent linear (co)polycarbonates.
Keywords: Aromatic polycarbonate; Pendant azido group; solution polycondensation; Triphosgene; UV-crosslinking

Synthesis of ternary cocrystals, salts, and hydrates of acefylline with enhanced dissolution and high permeability - Allu, Suryanarayana; Garai, Abhijit; Chernyshev, Vladimir V.; Nangia, Ashwini K. (Crystal Growth & Design, 2022)
Acefylline (ACF) is a stimulant xanthine derivative drug, which is formulated as a piperazine salt for the treatment of bronchial asthma. ACF falls under BCS class IV category of low solubility and poor permeability, which together limit the bioavailability and efficacy of the drug. In this work, ACF binary and ternary cocrystals, salts–cocrystals, and their polymorphs are synthesized by cocrystallization with several coformers. Two different methods were adopted for the supramolecular assembly of the ternary systems A.B.C: (1) first, binary adducts A.B or A.C were crystallized by grinding a slurry of the components in a suitable solvent and then C was added and grinding was continued; and (2) all three components were taken in a solvent slurry and ground together. The former method was found to be superior in affording the ternary salt/cocrystal. The role of laboratory seeding is implicated to explain the variation in crystallization results at different stages of the project. Crystal structures of the product’s binary and ternary systems were solved by single-crystal X-ray diffraction and powder X-ray diffraction data for structure solution. The crystal structures show the recurrence of carboxylate–pyridinium and imidazole–acid heterosynthons in the binary and ternary adducts. The intermolecular interactions between ACF and the coformer are analyzed by Hirshfeld surfaces, 2D fingerprint plots, and an energy framework. The permeability of ACF increases in binary and ternary systems with selected coformers. The fast dissolution and high permeability of ACF-PIP make this salt an improved crystalline formulation of acefylline.

Temporal analysis of melanogenesis identifies fatty acid metabolism as key skin pigment regulator - Sultan, Farina; Basu, Reelina; Murthy, Divya; Kochar, Manisha; Attri, Kuldeep S.; Aggarwal, Ayush; Kumari, Pooja; Dnyane, Pooja; Tanwar, Jyoti; Motiani, Rajender K.; Singh, Archana; Gadgil, Chetan; et al. (Plos Biology, 2022)
Therapeutic methods to modulate skin pigmentation has important implications for skin cancer prevention and for treating cutaneous hyperpigmentary conditions. Towards defining new potential targets, we followed temporal dynamics of melanogenesis using a cell-autonomous pigmentation model. Our study elucidates 3 dominant phases of synchronized metabolic and transcriptional reprogramming. The melanogenic trigger is associated with high MITF levels along with rapid uptake of glucose. The transition to pigmented state is accompanied by increased glucose channelisation to anabolic pathways that support melanosome biogenesis. SREBF1-mediated up-regulation of fatty acid synthesis results in a transient accumulation of lipid droplets and enhancement of fatty acids oxidation through mitochondrial respiration. While this heightened bioenergetic activity is important to sustain melanogenesis, it impairs mitochondria lately, shifting the metabolism towards glycolysis. This recovery phase is accompanied by activation of the NRF2 detoxication pathway. Finally, we show that inhibitors of lipid metabolism can resolve hyperpigmentary conditions in a guinea pig UV-tanning model. Our study reveals rewiring of the metabolic circuit during melanogenesis, and fatty acid metabolism as a potential therapeutic target in a variety of cutaneous diseases manifesting hyperpigmentary phenotype.

Tetrazoloquinoline-1,2,3-triazole derivatives as antimicrobial agents: synthesis, biological evaluation and molecular docking study - Shaikh, Mubarak H.; Subhedar, Dnyaneshwar D.; Akolkar, Satish V.; Nagargoje, Amol A.; Khedkar, Vijay M.; Sarkar, Dhiman; Shingate, Bapurao B. (Polycyclic Aromatic Compounds, 2022)
In search of new active molecules, a small focused library of tetrazoloquinoline-based 1,2,3-triazoles has been efficiently preparedviaclick chemistry approach. Several derivatives were found to be exhibiting promising antimicrobial and antioxidant activity characterized by their lower minimum inhibitory concentration values. All the synthesized compounds exhibited excellent antibacterial activity against Gram negative bacteriaE. coliandF. devoransand antifungal activity againstC. albicansandA. niger. Further, these compounds were tested for their antitubercular activity against dormantMTB H37Raand dormantM. bovis BCGusing XRMA assay protocol and showed no significant activity. Also, the synthesized compounds were found to have potential antioxidant activity with IC(50)range = 12.48-50.20 mu g/mL. Furthermore, to rationalize the observed biological activity data, the molecular docking study also been carried out against the active site of fungalC. albicansenzyme P450 cytochrome lanosterol 14 alpha-demethylase, which revealed a significant correlation between the binding score and biological activity for these compounds. The results of thein vitroandin silicostudy suggest that the triazole-incorporated tetrazoloquinolines may possess the ideal structural requirements for further development of novel therapeutic agents.
Keywords: 1; 2; 3-Triazole; ADME prediction; Antimicrobial; Antioxidant; Docking study

Thermal and crystallization behaviour of polyphenylene sulfide in engineering polymer blends with HDPE - Nadkarni, V. M.; Shingankuli, V. L.; Jog, J. P. (International Polymer Processing, 2022)
The thermal and crystallization behaviour of polyphenylene sulfide (PPS) in its blends with high density polyethylene (HDPE) is reported. Three grades of HDPE ranging in MFI from 0.4 to 52 were used in the investigation. The effect of composition and molecular weight of HDPE on the crystallization process and morphology of PPS in the blends has been investigated by the technique of Differential Scanning Calorimetry (DSC). In the blends, PPS crystallizes in presence of molten HDPE. It is observed that the morphology of PPS in terms of crystallite size and crystallite size distribution in the blends is significantly affected by blending with HDPE. The temperature onset of melting was found to increase with increasing HDPE content and the melting peak width was found to decrease with increasing HDPE content. This indicates a larger crystallite size and a narrower crystallite size distribution of PPS in blends. The effect is more pronounced in HDPE-rich compositions. The extent of the variation in the temperature onset of melting and peak width were comparable for all the grades of HDPE. The degree of crystallinity of PPS in the blends is reduced significantly (55-70%) in HDPE-rich blends. Therefore, it is concluded that the crystallization of PPS is affected by the presence of HDPE melt. The crystallization scans of PPS in the blends, obtained in the cooling mode, did not show any evidence of accelerated nucleation. On the other hand, a marginal reduction in the temperature onset of crystallization was observed. The temperature range of crystallization of PPS in the blends was found to be less for all compositions except for 90/10 (PPS/HDPE). In summary it is concluded that blending of HDPE with PPS influences the crystal growth of PPS significantly although the effect on its homogeneous nucleation is also considerable. As a result, the morphology of PPS crystallized in blends is different from that of the homopolymer. The changes in the morphology of PPS are not sensitive to the molecular weight of HDPE probably because of the high temperature of PPS crystallization relative to the melting point of HDPE.

Thermodynamics and its correlation with dynamics in a mean-field model and pinned systems: a comparative study using two different methods of entropy calculation - Nandi, Ujjwal Kumar; Patel, Palak; Moid, Mohd; Nandi, Manoj Kumar; Sengupta, Shiladitya; Karmakar, Smarajit; Maiti, Prabal K.; Dasgupta, Chandan; Bhattacharyya, Sarika Maitra (Journal of Chemical Physics, 2022)
A recent study introduced a novel mean-field model system where each particle over and above the interaction with its regular neighbors interacts with k extra pseudo-neighbors. Here, we present an extensive study of thermodynamics and its correlation with the dynamics of this system. We surprisingly find that the well-known thermodynamic integration (TI) method of calculating the entropy provides unphysical results. It predicts vanishing of the configurational entropy at temperatures close to the onset temperature of the system and negative values of the configurational entropy at lower temperatures. Interestingly, well below the temperature at which the configurational entropy vanishes, both the collective and the single-particle dynamics of the system show complete relaxation. Negative values of the configurational entropy are unphysical, and complete relaxation when the configurational entropy is zero violates the prediction of the random first-order transition theory (RFOT). However, the entropy calculated using the two-phase thermodynamics (2PT) method remains positive at all temperatures for which we can equilibrate the system, and its values are consistent with RFOT predictions. We find that with an increase in k, the difference in the entropy computed using the two methods increases. A similar effect is also observed for a system where a randomly selected fraction of the particles are pinned in their positions in the equilibrated liquid. We show that the difference in entropy calculated via the 2PT and TI methods increases with pinning density.

Toxicity and preventive approaches of Fusarium derived mycotoxins using lactic acid bacteria: state of the art - Navale, Vishwambar D.; Vamkudoth, Koteswara Rao (Biotechnology Letters, 2022)
Mycotoxin contamination of food and feed is a serious food safety issue and causes acute and chronic diseases in humans and livestock. Climatic and agronomic changes helps in the proliferation of fungal growth and mycotoxin production in food commodities. Mycotoxin contamination has attracted global attention due to its wide range of toxicity to humans and animals. However, physical and chemical management approaches in practice are unsafe for well-being due to their health-hazardous nature. Various antibiotics and preservatives are in use to reduce the microbial load and improve the shelf life of food products. In addition, the use of antibiotic growth promotors in livestock production may increase the risk of antimicrobial resistance, which is a global health concern. Due to their many uses, probiotics are helpful microbes that have a significant impact on food and nutrition. Furthermore, the probiotic potential of lactic acid bacteria (LAB) is employed in various food and feed preparations to neutralize mycotoxins, antimicrobial activities, balance the gut microbiome, and various immunomodulatory activities in both humans and livestock. In addition, LAB produces various antimicrobials, flavouring agents, peptides, and proteins linked to various food and health care applications. The LAB-based processes for mycotoxin management are more effective, eco-friendly, and low-cost than physical and chemical approaches. The toxicity, novel preventive measures, binding nature, and molecular mechanisms of mycotoxins' detoxification using LAB have been highlighted in this review.
Keywords: Food safety; Fusarium species; Lactic acid bacteria; management; Mycotoxin

Tuning the hybridization and charge polarization in metal nanoparticles dispersed over Schiff base functionalized SBA-15 enhances CO2 capture and conversion to formic acid - Cherevotan, Arjun; Ray, Bitan; Yadav, Anish; Bagchi, Debabrata; Singh, Ashutosh Kumar; Riyaz, Mohd; Churipard, Sathyapal R.; Naral, Vinay; Kaur, Komalpreet; Gautam, Ujjal K.; Vinod, Chathakudath P.; Peter, Sebastian C. (Journal of Materials Chemistry A, 2022)
Different Schiff base functionalized SBA-15 materials were synthesized through condensation reactions between 3-aminopropyltriethoxysilane (APTES) and different aldehydes (glutaraldehyde and butyraldehyde) over a mesoporous silica, SBA-15 (APTES-GLU/SBA-15 and APTES-BUT/SBA-15). Both static and dynamic experiments have been used for testing the CO2 capture efficiency of these materials. The hybridization of the N atom in APTES has been tuned from sp(3) to sp(2) upon condensation facilitating optimum CO2 capture in the direct synthesis of APTES-GLU/SBA-15. The undesirable oxides of nitrogen have been removed during the synthesis process to improve the CO2 capture efficiency. These materials were employed as supports for Pd-Ag and Pd-Ni bimetallic systems for the selective conversion of the captured CO2 to formic acid (FA) in 0.5 M KHCO3 solution. The Pd-Ni catalyst system exhibited enhanced CO2 to FA conversion activity compared to other heterogeneous systems, which is similar to 4 times better than that of the Pd-Ag system in this study. The X-ray absorption studies over the catalyst material confirmed that the relatively electron-deficient Ni in Pd-Ni compared to Ag in Pd-Ag favoured higher charge polarization between the metals in the Pd-Ni system enhancing the CO2 to FA conversion. The experimental observations are well supported by the DFT calculations.

Two antibacterial spiro compounds from the roots of Artemisia pallens wall: evidence from molecular docking - Honmore, Varsha S.; Natu, Arun D.; Khedkar, Vijay M.; Arkile, Manisha A.; Sarkar, Dhiman; Rojatkar, Supada R. (Natural Product Research, 2022)
Bioassay-guided isolation from acetone extract of the roots of Artemisia pallens Wall yielded two spiro compounds (1 and 2). The structures of these compounds were determined on the basis of spectroscopic techniques such as IR, MS, 1 D and 2 D- NMR. The acetone extract, fractions and the isolated two compounds were investigated for their antibacterial activity against two gram negative (E. coli, P. aeruginosa) and two gram positive (S. aureus, B. subtilis) bacterial strains. Compound (2) showed the best spectra of activity with IC50 and MIC values between 2.48-3.08 and 12.78 - 21.77 mu M and Compound (1) with 2.57-3.69 and 38.17 - 80.57 mu M, respectively, for the four bacterial strains, whereas inactive against Mycobacterium tuberculosis. Molecular docking study could further help in understanding the various interactions between these compounds and DNA gyrase active site in detail and thereby could provide valuable insight into the mechanism of action.
Keywords: antibacterial activity; antimycobacterial activity; Artemisia pallens; Asteraceae; Molecular docking; spiro compound

Ultrahigh capacitance of NiCo2O4/CeO2 mixed metal oxide material for supercapacitor applications - Santhosh, G.; Nayaka, G. P.; Bhatt, Aarti S. (Journal of Alloys and Compounds, 2022)
Pertaining to research on energy consumption and energy storage systems, new and efficient mixed metal oxides of NiCo2O4/CeO2 as pseudo-capacitor materials have been successfully prepared by sol-gel combustion method. The synthesized unique spinel nanomaterials have been analyzed for structural and morphological characterization by FT-IR, XRD, XPS and electron microscopy techniques. The mesoporous structure and large specific surface area of the synthesized nanomaterials provide an easy channel for ion mobility rendering an effortless redox process at the electrode electrolyte interface. As a consequence, it is observed that NiCo2O4 mixed with 10% of CeO2 exhibits an excellent specific capacitance of 1355 Fg(-1) at 5 Ag-1 along with a high cycling stability with only 4.7% capacity loss at the end of 6000 cycles at a charge-discharge current density of 10 Ag-1. The results obtained are in par with some of the recent electrode materials used for supercapacitors suggesting the possible employment of NiCo2O4/CeO2 mixed metal oxides in energy storage applications. (C) 2021 Elsevier B.V. All rights reserved.
Keywords: Charge-discharge; cyclic voltammetry; NiCo2O4/CeO2; specific capacitance; supercapacitor

Ultra-high performance liquid chromatography Q-Orbitrap MS/MS-based profiling and quantification of limonoids in Meliaceae plants - Mulani, Fayaj A.; Nandikol, Sharvani S.; Kajjihundi, Jagadeesh S.; Pathappa, Niranjana; Puttappa, Sharanappa; Thulasiram, V. Hirekodathakallu (Analytical and Bioanalytical Chemistry, 2022)
Meliaceae plants have been extensively used in agriculture, folklore, and traditional medicine. They are the major storehouses for structurally diverse limonoids (meliacins) possessing various bioactivities like antifeedant, insecticidal, antimicrobial, etc. However accurate detection of these tetranortriterpenes from the vast pool of metabolites in plant tissue extracts or biological sample is a crucial challenge. Though the mass spectrum (MS) provides the molecular mass and the corresponding elemental composition, it cannot be relied precisely. The exact identification of a specific metabolite demands the MS/MS spectrum containing the signature product ions. In the present study, we have developed the UHPLC Q-Orbitrap-based method for identification, quantification, and characterization of limonoids in different plant tissue extracts requiring minimum plant material. Using this method, we carried out the limonoid profiling in different tissue extracts of sixteen Meliaceae plants and the identification of limonoids was performed by comparing the retention time (RT), ESI-(+)-MS spectrum, and HCD-MS/MS of the purified fifteen limonoids used as reference standards. Our results revealed that early intermediates of the limonoid biosynthetic pathway such as azadiradione, epoxyazadiradione, and gedunin occurred more commonly in Meliaceae plants. The MS/MS spectrum library of the fifteen limonoids generated in this study can be utilized for identification of these limonoids in other plant tissue extracts, botanical fertilizers, agrochemical formulations, and bio pesticides.
Keywords: LC-HRMS; LC-MS/MS; Limonoids; Meliaceae; Natural product; Quantification

Understanding the effect of sodium polyphosphate on improving the chemical stability of Ti3C2Tz MXene in water - Huang, Shuohan; Natu, Varun; Tao, Jingyi; Xia, Yumin; Mochalin, Vadym N.; Barsoum, Michel W. (Journal of Materials Chemistry A, 2022)
Degradation of MXenes in aqueous environments severely limits the application and industrialization of this large family of two-dimensional (2D) materials. Hydrolysis and oxidation are now considered as two main degradation mechanisms and while significant efforts have been directed to prolonging the shelf-life of MXenes, separating and studying their degradation mechanisms have lagged behind. Herein, gas analysis via gas chromatography and Raman spectroscopy were used to investigate the effect of sodium polyphosphate, PP, on the degradation of Ti3C2Tz MXene. Transmission and scanning electron microscopies, as well as X-ray photoelectron spectroscopywere also used as complimentary techniques to support conclusions derived from gas analysis and to confirm the extent of degradation via characterization of solid reaction products. Based on these studies we have determined that the addition of PP to an equal mass of Ti3C2Tz solution can effectively suppress hydrolysis and protect Ti3C2Tz from degradation.

Understanding unfolding and refolding of the antibody fragments (Fab). II. Mapping intra and inter-chain disulfide bonds using mass spectrometry - Nainwal, Neeraj; Chirmade, Tejas; Gani, Kayanat; Rana, Sunil; Bhambure, Rahul (Biochemical Engineering Journal, 2022)
Disulfide bond formation in recombinant protein therapeutics has a significant impact on the integrity and biological activity of the drug product. Formation of the disulfide linkage is the key rate-limiting step in in vitro refolding and overall manufacturing of the antibody fragments (Fab). This investigation is focused on mapping the intra, and inter-chain disulfide bonds in the in vitro refolded antibody fragments by using mass spectrometry (MS). Biosimilar rHu Ranibizumab and rHu Certolizumab expressed using E. coli were selected for the study. Both Fabs contain ten cysteine residues leading to two intra-chain disulfide bonds on each subunit and a single interchain disulfide linkage. rHu Certolizumab has an additional cysteine which is unpaired and used for pegylation. The amino acid sequence in the disulfide-bonded peptides was confirmed by Collision-induced dissociation (CID), Electron transfer dissociation (ETD) and High-energy collision dissociation (HCD). The light chain (LC) intra-chain disulfide is formed between Cys23-Cys88 and Cys134-Cys194 in both the Fabs. The heavy chain (HC) intra-chain disulfides are formed between Cys22-Cys96 and Cys150-Cys206 in rHu Ranibizumab. LC and HC subunits of rHu Ranibizumab are covalently linked by disulfide linkage formed between Cys214 of LC and Cys226 of HC. This study suggests that information from multiple MS platforms and orthogonal methods for peptide fragmentation can be effectively used to map disulfide linkages in biosimilar therapeutic proteins.
Keywords: Antibody fragments (Fab); Collision-induced dissociation; Electron transfer dissociation; High-energy collision dissociation; in vitro refolding; Ranibizumab

Viscoelastic covalent organic nanotube fabric via macroscopic entanglement - Koner, Kalipada; Das, Susobhan; Mohata, Shibani; Duong, Nghia Tuan; Nishiyama, Yusuke; Kandambeth, Sharath; Karak, Suvendu; Reddy, C. Malla; Banerjee, Rahul (Journal of the American Chemical Society, 2022)
Covalent organic nanotubes (CONTs) are one-dimensional porous frameworks constructed from organic building blocks via dynamic covalent chemistry. CONTs are synthesized as insoluble powder that restricts their potential applications. The judicious selection of 2,2'-bipyridine-5,5'-dicarbaldehyde and tetraaminotriptycene as building blocks for TAT-BPy CONTs has led to constructing flexible yet robust and self-standing fabric up to 3 mu m thickness. The TAT-BPy CONTs and TAT-BPy CONT fabric have been characterized by solid-state one-dimensional (1D) C-13 CP-MAS, two-dimensional (2D) C-13-H-1 correlation NMR, 2D H-1-H-1 DQ-SQ NMR, and 2D N-14-H-1 correlation NMR spectroscopy. The mechanism of fabric formation has been established by using high-resolution transmission electron microscopy and scanning electron microscopy techniques. The as-synthesized viscoelastic TAT-BPy CONT fabric exhibits high mechanical strength with a reduced modulus (E-r) of 8 (+/- 3) GPa and hardness (H) of 0.6 (+/- 0.3) GPa. Interestingly, the viscoelastic fabric shows time-dependent elastic depth recovery up to 50-70%.

Viscoelastic liquid from regenerated silk fibroin in the silk i conformation: a writeable and shapeable material - Kumar, Raj; Joseph, Emmanuel; Chaudhari, Atul; Nisal, Anuya; Sharma, Kamendra P. (ACS Applied Polymer Materials, 2022)
Regenerated silk fibroin (RSF) has acquired enormous attention because of its exceptional toughness, strength, and biocompatible nature. These properties make RSF a potential candidate for the fabrication of different types of materials. However, processing even a dilute aqueous solution of RSF leads to a conformational transformation from a random coil/helix-rich (silk I) to a beta-sheetrich (silk II) state. As a consequence, RSF tends to form aggregates and loses its toughness. Working in a direction to address this problem, an aqueous solution of regenerated silk fibroin has been modified with a dual layer of polyethylenimine (PEI) and a PEG-based polymer surfactant (PS). Upon freeze-drying, the RSF-polymer complex forms a solvent-free RSF bioconjugate system and exhibits a soft solid to liquid melting transition at similar to 45 degrees C. The sequential modification with PEI and PS preserves the native-like random coil conformation of RSF up to at least 8 months of storage by not allowing interchain interactions that can lead to aggregation. Rheological and small-angle X-ray scattering measurements show that the solvent-free system is viscoelastic and exhibits a higher order microstructure mediated by the packing of the PS chains, respectively. Temperature-dependent soft solid-liquid-like dual behavior offers applications in injection-based writing, compression molding, and shaping RSF bioconjugates into various types of geometries. Furthermore, the mechanical properties of the RSF bioconjugate system can be modulated by crosslinking with glutaraldehyde vapor at 50 degrees C.
Keywords: RSF liquid; RSF soft solid; silk I conformation; silk liquid; viscoelastic

2D layered nanomaterials as fillers in polymer composite electrolytes for lithium batteries - Vijayakumar, Vidyanand; Ghosh, Meena; Asokan, Kiran; Sukumaran, Santhosh Babu; Kurungot, Sreekumar; Mindemark, Jonas; Brandell, Daniel; Winter, Martin; Nair, Jijeesh Ravi (Advanced Energy Materials, 2023)
Polymer composite electrolytes (PCEs), i.e., materials combining the disciplines of polymer chemistry, inorganic chemistry, and electrochemistry, have received tremendous attention within academia and industry for lithium-based battery applications. While PCEs often comprise 3D micro- or nanoparticles, this review thoroughly summarizes the prospects of 2D layered inorganic, organic, and hybrid nanomaterials as active (ion conductive) or passive (nonion conductive) fillers in PCEs. The synthetic inorganic nanofillers covered here include graphene oxide, boron nitride, transition metal chalcogenides, phosphorene, and MXenes. Furthermore, the use of naturally occurring 2D layered clay minerals, such as layered double hydroxides and silicates, in PCEs is also thoroughly detailed considering their impact on battery cell performance. Despite the dominance of 2D layered inorganic materials, their organic and hybrid counterparts, such as 2D covalent organic frameworks and 2D metal-organic frameworks are also identified as tuneable nanofillers for use in PCE. Hence, this review gives an overview of the plethora of options available for the selective development of both the 2D layered nanofillers and resulting PCEs, which can revolutionize the field of polymer-based solid-state electrolytes and their implementation in lithium and post-lithium batteries.
Keywords: 2D materials; clay minerals; covalent organic frameworks; metal-organic frameworks; MXene; polymer composite electrolyte; solid-state batteries

3D-printed polymer composite devices based on a ferroelectric chiral ammonium salt for high-performance piezoelectric energy harvesting - Sahoo, Supriya; Kothavade, Premkumar Anil; Naphade, Dipti R.; Torris, Arun; Praveenkumar, Balu; Zareba, Jan K.; Anthopoulos, Thomas D.; Shanmuganathan, Kadhiravan; Boomishankar, Ramamoorthy (Materials Horizons, 2023)
Three-dimensional printing (3DP) is an emerging technology to fabricate complex architectures, necessary to realize state-of-the-art flexible and wearable electronic devices. In this regard, top-performing devices containing organic ferro- and piezoelectric compounds are desired to circumvent significant shortcomings of conventional piezoceramics, e.g. toxicity and high-temperature device processibility. Herein, we report on a 3D-printed composite of a chiral ferroelectric organic salt {[Me3CCH(Me)NH3][BF4]} (1) with a biodegradable polycaprolactone (PCL) polymer that serves as a highly efficient piezoelectric nanogenerator (PENG). The ferroelectric property of 1 originates from its polar tetragonal space group P4(2), verified by P-E loop measurements. The ferroelectric domain characteristics of 1 were further probed by piezoresponse force microscopy (PFM), which gave characteristic `butterfly' and hysteresis loops. The PFM amplitude vs. drive voltage measurements gave a relatively high magnitude of the converse piezoelectric coefficient for 1. PCL polymer composites with various weight percentages (wt%) of 1 were prepared and subjected to piezoelectric energy harvesting tests, which gave a maximum open-circuit voltage of 36.2 V and a power density of 48.1 mu W cm(-2) for the 10 wt% 1-PCL champion device. Furthermore, a gyroid-shaped 3D-printed 10 wt% 1-PCL composite was fabricated to test its practical utility, which gave an excellent output voltage of 41 V and a power density of 56.8 mu W cm(-2). These studies promise the potential of simple organic compounds for building PENG devices using advanced manufacturing technologies.

Atomically dispersed manganese on graphene nanosheets as biocompatible nanozyme for glutathione detection in liver tissue lysate using microfluidic paper-based analytical devices - Baruah, Diksha J.; Thakur, Ashutosh; Roy, Esha; Roy, Kallol; Basak, Sumanjita; Neog, Dipankar; Bora, Himangsu K.; Konwar, Rituraj; Chaturvedi, Vikash; Shelke, Manjusha V.; Das, Manash R. (ACS Applied Materials & Interfaces, 2023)
Recently, single atom catalysts (SACs) featuring M-N-x (M = metal) active sites on carbon support have drawn considerable attention due to their promising enzyme-like catalytic properties. However, typical synthesis methods of SACs often involve energy-intensive carbonization processes. Herein, we report a facile one-pot, low-temperature, wet impregnation method to fully utilize M-N-4 sites of manganese phthalocyanine (MnPc) by decorating molecular MnPc over the sheets of graphene nanoplatelets (GNP). The synthesized MnPc@GNP exhibits remarkable peroxidase-mimic catalytic activity toward the oxidation of chromogenic 3,3 `,5,5(')-tetramethylbenzidine (TMB) substrate owing to the efficient utilization of atomically dispersed Mn and the high surface-to-volume ratio of the porous catalyst. A nanozyme-based colorimetric sensing probe is developed to detect important biomarker glutathione (GSH) within only 5 min in solution phase based on the ability of GSH to effectively inhibit the TMB oxidation. The high sensitivity and selectivity of the developed colorimetric assay enable us to quantitatively determine GSH concentration in different biological fluids. This work, for the first time, reports a rapid MnPc@GNP nanozyme-based colorimetric assay in the solid substrate by fabricating microfluidic paper-based analytical devices (mu PADs). GSH is successfully detected on the fabricated mu PADs coated with only 6.0 mu g of nanozyme containing 1.6 nmol of Mn in the linear range of 0.5-10 mu M with a limit of detection of 1.23 mu M. This work also demonstrates the quantitative detection of GSH in mice liver tissue lysate using mu PADs, which paves the way to develop mu PADs for point-of-care testing.
Keywords: colorimetricsensing; Glutathione; mu PADs; nanozyme; single atom catalyst; tissue lysate

Automated myocardial infarction and angina detection using second derivative of photoplethysmography - Neha, H. K.; Sardana, H. K.; Dahiya, N.; Dogra, N.; Kanawade, R.; Sharma, Y. P.; Kumar, S. (Physical and Engineering Sciences in Medicine, 2023)
Photoplethysmography (PPG) based healthcare devices have gained enormous interest in the detection of cardiac abnormalities. Limited research has been implemented for myocardial infarction (MI) detection. Moreover, PPG-based detection of angina is still a research gap. PPG signals are not always informative. Therefore, this research work presents the use of PPG signals and their second derivative to evaluate myocardial infarction and angina using a novel set of morphological features. The obtained morphological features are fed onto the feed-forward artificial neural network for the identification of the type of MI and unstable angina (UA). The initial experiments have been carried out on non-ambulatory (public) subjects for feature extraction and later evaluated on ambulatory (self-generated) databases. The intended method attains accuracy, sensitivity, and specificity of 98%, 97%, 98% on the public database and 94%, 94%, 94% on the self-generated database. The result shows that the proposed set of features can detect MI and UA with significant accuracy.
Keywords: Artificial neural network; Myocardial infarction detection; PPG; SDPPG; Unstable angina detection

Baby step in assembling and integrating the components of an artificial photosynthesis device with forced heterojunctions towards improved efficiency - Salgaonkar, Kranti N.; Bajpai, Himanshu; Mhamane, Nitin B.; Nalajala, Naresh; Chauhan, Inderjeet; Thakkar, Kavita; Joshi, Kavita; Gopinath, Chinnakonda S. (Journal of Materials Chemistry A, 2023)
How to achieve unassisted, economical, scalable, and sustainable artificial photosynthesis for liquid fuels/products with improved solar-to-fuel efficiency (STFE) to address a carbon-neutral economy remains a big question. To a large degree, the extent of charge separation at heterojunction interfaces and charge utilization determine the STFE. Towards this, BiVO3 is assembled from ionic-precursors into TiO2 pores, and integrated structurally and electronically with TiO2 on calcination as BiVO4 quantum dots (BVQDs). BVQDs in TiO2 (BVT) pores lead to an all-inorganic system with a sub-quadrillion number of heterojunctions in a 1 cm(2) device (contains similar to 25 mu g of BiVO4 (similar to 2.5 wt%) in the nanopores of similar to 975 mu g of TiO2 (similar to 97.5 wt%)) and facilitate artificial photosynthesis. We demonstrate 31-38% STFE with a photon to chemical conversion turn over frequency (ToF(P2C)) of 2.73 s(-1) with a 1 cm(2) wireless BiVO4-TiO2 artificial leaf (BVT-AL) device for HCHO and CH3OH. The sequential nature of CO2 reduction to HCHO and then to CH3OH is evident from the reaction results. (CO2)-C-13 isotopic labeling experiments confirm that the input CO2 is the source for product formation. A large increase in the photocurrent density and incident photon-to-current efficiency (IPCE) of BVT, over 100% for the BiVO4 photoanode in visible light, demonstrates and supports efficient visible light absorption, charge separation and migration to the redox sites. A device has been demonstrated to show sustainable activity in direct sunlight, and addresses scalability from 1 to 9 cm(2). Assuming no change (50% decrease) in the STFE, a 6.74 m(2) device is expected to convert 1 (0.5) kg h(-1) CO2 into C1-oxygenates in sunlight. DFT calculations carried out with anatase TiO2 (101) and BiVO4 (121) interfaces support many of the experimental findings, including electron flow from the latter to the former, and interaction of the oxygen of TiO2 with BiVO4 and vice versa at the interface towards forced heterojunctions.

Bacterial communities and diversity of western ghats soil: a study of a biodiversity hotspot - Ghare, Uma; Narvekar, Simran; Lodha, Tushar; Mallebhari, Rubiya; Dastager, Syed; Barvkar, Vitthal T.; Dhotre, Dhiraj; Karmalkar, Nitin R.; Pable, Anupama A. (Current Microbiology, 2023)
The Western Ghats is one of India's mega-diversity hotspots and an ecologically and geologically important area for the diversity of endemic plants and animals. The present study provides insights into the aerobic bacterial diversity and composition of the soils of North Western Ghats located in Maharashtra state (NWGM), India. The samples for the culture-dependent study were collected from 6 different locations namely Malshej Ghat, Bhimashankar, Lonavala, Mulshi, Tail-Baila, and Mahabaleshwar. A total of 173 isolates were obtained from the different samples, which belonged to Proteobacteria (43%), Firmicutes (36%), and Actinobacteria (19%). Sequences of 15 strains shared <= 98.7% similarity (a species cut-off) which represent potential novel species. Metagenomic analysis revealed the presence of Actinobacteria and Proteobacteria as the most dominant phyla at both MB and MG. However, both sites showed variation in the composition of rare phyla and other dominant phyla. This difference in bacterial community composition could be due to differences in altitude or other physicochemical properties. The functional prediction from the amplicon sequencing showed the abundance of carbohydrate, protein, and lipid metabolism which was corroborated by screening the isolated bacterial strains for the same. The present study has a unique take on microbial diversity and defines the importance of community assembly processes such as drift, dispersal, and selection. Such processes are relatively important in controlling community diversity, distribution, as well as succession. This study has shown that the microbial community of NWGM is a rich source of polysaccharide degrading bacteria having biotechnological potential.

Carbon black and chitin nanofibers for green tyres: preparation and property evaluation - Mathew, Mariya; Dominic, C. D. Midhun; Neenu, K. V.; Begum, P. M. Sabura; Dileep, P.; Kumar, T. G. Ajith; Sabu, Akshay Alax; Nagane, Dhiraj; Parameswaranpillai, Jyotishkumar; Badawi, Michael (Carbohydrate Polymers, 2023)
This research highlights the synergistic use of carbon black (CB) and chitin nanofibers (CHNFs) for developing green tyres for the first time. The CHNFs (12-30 nm) were prepared from chitin powder with the help of steam explosion and mild oxalic acid hydrolysis. The CHNFs were uniformly dispersed in natural rubber (NR) latex, dried, and mixed with CB in a two-roll mill to form NR/CB/CHNF composites. The NR/CB/CHNF composite at 1 phr CHNF loading exhibited tensile and tear strengths that were about 47 and 160 % greater than the NR-Neat, respectively. The dynamic mechanical analysis showed that the loss tangent (tan delta) at 60 degrees C was 50 % lower for the NR/CB/CHNF 1.0 composite than for the NR/CB50 composite. The study succeeded in developing a new green tyre tread formulation that would be helpful for attaining sustainability and a circular economy.
Keywords: carbon black; Chitin nanofibers; Green Tyre; natural rubber latex

Chemical bridge-mediated heterojunction electron transport layers enable efficient and stable perovskite solar cells - Patil, Pramila; Maibam, Ashakiran; Sangale, Sushil S.; Mann, Dilpreet Singh; Lee, Hyun-Jung; Krishnamurty, Sailaja; Kwon, Sung-Nam; Na, Seok-In (ACS Applied Materials and Interfaces, 2023)
Perovskite solar cells (PSCs) emerged as potential photovoltaicenergy-generating devices developing in recent years because of theirexcellent photovoltaic properties and ease of processing. However,PSCs are still reporting efficiencies much lower than their theoreticallimits owing to various losses caused by the charge transport layerand the perovskite. In this regard, herein, an interface engineeringstrategy using functional molecules and chemical bridges was appliedto reduce the loss of the heterojunction electron transport layer.As a functional interface layer, ethylenediaminetetraacetic acid (EDTA)was introduced between PCBM and the ZnO layer, and as a result, EDTAsimultaneously formed chemical bonds with PCBM and ZnO to serve asa chemical bridge connecting the two. DFT and chemical analyses revealedthat EDTA can act as a chemical bridge between PCBM and ZnO, passivatedefect sites, and improve charge transfer. Optoelectrical analysisproved that EDTA chemical bridge-mediated charge transfer (CBM-CT)provides more efficient interfacial charge transport by reducing trap-assistedrecombination losses at ETL interfaces, thereby improving device performance.The PSC with EDTA chemical bridge-mediated heterojunction ETL exhibiteda high PCE of 21.21%, almost no hysteresis, and excellent stabilityto both air and light.
Keywords: charge transfer; chemical bridge; electron transport layer; ethylenediaminetetraacetic acid; Perovskite solar cells; trap-assisted recombination

Cloning and expression of antibody fragment (Fab) II: Effect of expression hosts on light and heavy chain gene expression - Mehta, Deepa; Chirmade, Tejas; Nainwal, Neeraj; Bhambure, Rahul (Biochemical Engineering Journal, 2023)
Protein expression stoichiometry of individual subunits plays a critical role in the formation of multi-domain functional therapeutic proteins like antibody fragments. In this study, we have evaluated light to heavy chain ratio (LC: HC) of rHu Ranibizumab expressed using duet expression vector in six E. coli strains. The LC: HC ratio at the protein level was determined using RP-HPLC whereas transcript abundance of LC and HC at the mRNA level was determined using RTqPCR. Protein level study as well as the transcript abundance profiles of the LC and HC genes were observed to be differentially expressed across the E. coli strains. BL21 STAR (DE3) and Origami 2 strains resulted in a nearly equal expression ratio of LC and HC genes. Untargeted shotgun proteomics analysis was performed to identify the differentially expressed proteins. Total 1083 proteins were identified in the spectral IDA library, while 244 and 149 proteins were differentially expressed in Origami 2 and BL21 STAR (DE3) respectively. These proteins are associated with translation and nucleotide biosynthesis pathways. Ob-tained results provide insights into the impact of different E.coli host strains on LC: HC ratio, the probable reasons behind the unbalanced gene ratio, and provide useful transcriptomic and proteomics analysis protocols.
Keywords: E.coli host strains; Expression stoichiometry; Proteome analysis; rHu biosimilar Ranibizumab; Transcript abundance

Cocrystallization of multi-kinase inhibitor pazopanib with fenamic acids: improving dissolution and inhibiting cell migration - Rai, Sunil K.; Gunnam, Anilkumar; Roy, Debopriya; Rajput, Raveena; Kulkarni, Kiran; Nangia, Ashwini K. (CrystEngComm, 2023)
A multi-kinase inhibitor, pazopanib (PAZ) is cocrystallized with cyclooxygenase (COX) inhibitor fenamic acids to investigate the dissolution rate and inhibition of cell migration in VEGF-triggered HUVEC cells to test the efficacy of stoichiometric drug-drug combinations. Crystallization experiments at the sub-milligram level in an acetonitrile-methanol mixture yielded two drug-drug salt forms of PAZ with flufenamic acid (FFA) and niflumic acid (NFA) as PAZ+center dot FFA-center dot ACN (an acetonitrile solvate named as form I) and PAZ+center dot NFA-. Structures of the crystal forms were characterized by single crystal X-ray diffraction (SC-XRD) method. Crystal structures revealed that the presence of a 2-aminopyrimidine group in PAZ is a strong partner for the carboxyl group in all solid forms, forming an acidMIDLINE HORIZONTAL ELLIPSISpyrimidine heterosynthon with COX inhibitor fenamic acids. To perform dissolution experiments and cell line analysis, the scale-up of both salt forms were done in the acetonitrile-methanol mixture through crystallization, which showed a polymorphic transformation in the case of PAZ+center dot FFA-center dot ACN (an acetonitrile solvate named form II). The thermodynamic stability of PAZ+center dot FFA-center dot ACN (form II) and PAZ+center dot NFA- were analysed using slurry experiment under ambient conditions in pH 1.2 (0.1 N HCl) buffer medium and the residual solid phase was characterized by powder XRD, which showed that PAZ+center dot FFA-center dot ACN (form II) was a metastable solid form while PAZ+center dot NFA- was a stable solid form. The dissolution experiments at gastric pH 1.2 showed that the rate of dissolution of PAZ+center dot FFA-center dot ACN was 10 times higher than PAZ+center dot NFA-. The cell migration assay suggested that PAZ+center dot FFA-center dot ACN inhibited similar to 25% and PAZ+center dot NFA- inhibited similar to 20% migration of HUVEC cells compared to PAZ alone. These investigations suggested that the drug-drug salts PAZ+center dot FFA- and PAZ+center dot NFA- would be potential combo drug candidates for clinical trials. Multi-drug crystalline salts of pazopanib with fenamic acids exhibit enhanced dissolution and 20% higher inhibition in the migration of HUVEC cells compared to the reference drug.

Comparative study of the correlation between the structure and the dynamics for systems interacting via attractive and repulsive potentials - Sharma, Mohit; Nandi, Manoj Kumar; Bhattacharyya, Sarika Maitra (Journal of Chemical Physics, 2023)
We present the study of the structure-dynamics correlation for systems interacting via attractive Lennard-Jones (LJ) and its repulsive counterpart, the Weeks-Chandler-Andersen (WCA) potentials. The structural order parameter (SOP) is related to the microscopic mean-field caging potential. At a particle level, the SOP shows a distribution. Although the two systems have similar pair structures, their average SOP differs. However, this difference alone is insufficient to explain the well known slowing down of the dynamics in the LJ system at low temperatures. The slowing down can be explained in terms of a stronger coupling between the SOP and the dynamics. To understand the origin of this system specific coupling, we study the difference in the microscopic structure between the hard and soft particles. We find that for the LJ system, the structural differences of the hard and soft particles are more significant and have a much stronger temperature dependence compared to the WCA system. Thus, the study suggests that attractive interaction creates more structurally different communities. This broader difference in the structural communities is probably responsible for stronger coupling between the structure and dynamics. Thus, the system specific structure-dynamics correlation, which also leads to a faster slowing down in the dynamics, appears to have a structural origin. A comparison of the predictive power of our SOP with the local energy and two body excess entropy in determining the dynamics shows that in the LJ system, the enthalpy plays a dominant role and in the WCA system, the entropy plays a dominant role, and our SOP can capture both these contributions.

Concise approach for the synthesis of the tetracyclic framework of Lycibarbarines A and B - Shet, Manoj N.; Nechooli, Hemanth K.; Ramana, Chepuri V. (Tetrahedron Letters, 2023)
A simple approach for the construction of the tetracyclic spiroketal skeleton of Lycibarbarine A and B has been described. Employing a solvent free condition for epoxide opening with tetrahydroquinoline as a key reaction to couple both the fragments, an oxidation followed by TBAF-mediated silyl deprotection spiroketalization establishes the complete tetracyclic core present in these natural products. (c) 2023 Elsevier Ltd. All rights reserved.
Keywords: Chiral pool approach; D -Glyceraldehyde; Tetracyclic spiroketal; Total synthesis

Conversion of benzyl phenyl ether to monoaromatics in high-temperature aqueous ethanol solution under high-pressure carbon dioxide conditions - Taniguchi, Kenkichi; Kusumawati, Etty N.; Nanao, Hidetaka; Rode, Chandrashekhar V.; Sato, Osamu; Yamaguchi, Aritomo; Shirai, Masayuki (New Journal of Chemistry, 2023)
Solvolysis of benzyl phenyl ether (BPE), which is a model compound of lignin ether linkage, was studied in an aqueous ethanol solution, which can be obtained from bioethanol, under high-pressure carbon dioxide conditions. A batch study revealed that BPE solvolysis to monoaromatics (benzyl ethyl ether (BEE), benzyl alcohol (BA), and phenol (Ph)) proceeded in aqueous ethanol solution over 523 K and the addition of high-pressure carbon dioxide enhanced the initial solvolysis rate and suppressed the side reaction (hydrogenolysis to toluene (TL)). The ethanol molar fraction (ethanol-water volume ratio) is the key factor for the solvolysis reaction, and the highest monoaromatic yield of 72.9% (BEE 10.7%, BA 19.3%, Ph 37.9%, and TL 5.1%) was obtained in aqueous ethanol solution (2 cm(3) : 1 cm(3) = water:ethanol) at 598 K for 3 h under a pressure of 18 MPa of carbon dioxide. The solvolysis reaction proceeded continuously to produce monoaromatics with a flow system. A monoaromatic yield of 76.7% (BEE 8.6%, BA 19.7%, Ph 39.6%, and TL 8.9%) was obtained, and the formation rates were 2.7 x 10(-4) mmol min(-1) for BEE, 6.2 x 10(-4) mmol min(-1) for BA, and 12.4 x 10(-4) mmol min(-1) for Ph at 598 K under flowing water (26 mmol min(-1)), ethanol solution (4.1 mmol min(-1)), carbon dioxide (1.2 mmol min(-1)), and BPE (15.6 x 10(-4) mmol min(-1)) under a total pressure of 40 MPa.

Critical review on amorphous-crystalline heterostructured electrocatalysts for efficient water splitting - Singh, Manjinder; Cha, Dun Chan; Singh, Thangjam Ibomcha; Maibam, Ashakiran; Paudel, Dasu Ram; Nam, Dong Hwan; Kim, Tae Hyeong; Yoo, Sunghoon; Lee, Seunghyun (Materials Chemistry Frontiers, 2023)
Introducing complementary active materials in tandem as heterostructures of various shapes and sizes can significantly improve the physicochemical properties of the developed materials. Recently, the use of amorphous materials in conjunction with crystalline moieties as highly efficient electrocatalysts for water-splitting electrolyzers has surged rapidly. Excellent bifunctional activity for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) can be achieved from amorphous-crystalline-based materials owing to their remarkably conductive crystalline phase as well as their long-range disordered amorphous phase. In addition, the high specific surface area, disordered structure, and enhanced structural stability can accommodate various defects and strains that develop during in situ electrochemical reactions. Consequently, amorphous materials can be used as both surface-confined and volume-confined electrocatalysts. Although crystalline materials have better electronic properties as well as higher thermal and mechanical stability, they suffer from limited activity due to only surface-confined electrocatalysis. In this regard, the judicious integration of crystalline and amorphous active materials suitable for the OER and HER can tremendously enhance their bifunctional electrocatalytic activities owing to their synergistic effects. The variety in the choice of amorphous and crystalline counterparts presents ample opportunities for further exploration of the development of amorphous-crystalline heterostructured materials with unique properties. However, considering the recent massive developments in the understanding and protocols for fabricating such heterostructures, a critical review is vital for further advancement in this direction. Although some review papers have focused only on amorphous materials, including their synthesis methods, properties, and applications, no critical review that provides an overview emphasizing amorphous-crystalline heterostructures for electrocatalytic water-splitting applications has been published. In this regard, this review aims to present comprehensive details on the recent developments in the fabrication of different amorphous-crystalline heterostructures, the choice of the composition of each component, and the resulting physicochemical properties for the OER, HER, and overall water-splitting. It provides an in-depth understanding of amorphous-crystalline material synthesis protocols, their selection rationale, and their targeted physicochemical properties. This review also provides thought-provoking ideas and long-term perspectives for future research. This review presents comprehensive details on recent developments in the fabrication of different amorphous-crystalline heterostructures, their compositions, and the resulting physicochemical properties for OER, HER, and overall water splitting.

Dabrafenib-panobinostat salt: improving the dissolution rate and inhibition of BRAF melanoma cells - Rai, Sunil K.; Marverti, Gaetano; Gunnam, Anilkumar; Allu, Suryanarayana; Nangia, Ashwini K. (ACS Omega, 2023)
Cocrystallization of the drug-drug salt-cocrystal of the histone deacetylase inhibitor (HDACi) panobinostat (PAN) and b-rapidly accelerated fibrosarcoma (BRAF) inhibitor dabrafenib (DBF) afforded single crystals of a two-drug salt stabilized by N+-H center dot center dot center dot O and N+-H center dot center dot center dot N- hydrogen bonds between the ionized panobinostat ammonium donor and dabrafenib sulfonamide anion acceptor in a 12-member ring motif. A faster dissolution rate for both drugs was achieved through the salt combination compared to the individual drugs in an aqueous acidic medium. The dissolution rate exhibited a peak concentration (Cmax) of approximately 310 mg cm-2 min-1 for PAN and 240 mg cm-2 min-1 for DBF at a Tmax of less than 20 min under gastric pH 1.2 (0.1 N HCl) compared to the pure drug dissolution values of 10 and 80 mg cm-2 min-1, respectively. The novel and fast-dissolving salt DBF-center dot PAN+ was analyzed in BRAFV600E melanoma cells Sk-Mel28. DBF-center dot PAN+ reduced the dose-response from micromolar to nanomolar concentrations and lowered IC50 (21.9 +/- 7.2 nM) by half compared to PAN alone (45.3 +/- 12.0 nM). The enhanced dissolution and lower survival rate of melanoma cells show the potential of novel DBF-center dot PAN+ salt in clinical evaluation.

D-A-D-based unsymmetrical thiosquaraine dye for the dye-sensitized solar cells(dagger) - Jadhav, Avinash P.; Singh, Ambarish Kumar; Maibam, Ashakiran; Krishnamurty, Sailaja; Krishnamoorthy, Kothandam; Nithyanandhan, Jayaraj (Photochemistry and Photobiology, 2023)
In dye-sensitized solar cell, modulating the electronic properties of the sensitizer by varying the donor, pi-spacer, acceptor and anchoring groups help optimizing the structure of the dye for better device performance. Here, a donor-acceptor-donor-based unsymmetrical thiosquaraine sensitizer (SQ5S) has been designed and synthesized. Photophysical, electrochemical, theoretical and photovoltaic characterizations of SQ5S dye have been compared with its oxygen analog, SQ5. The incorporation of the sulfur atom in the acceptor unit of SQ5S dye showed an intense peak at 688 nm, which was 38 nm of red-shifted and showed the panchromatic light harvesting response with the onset of 850 nm compared with SQ5 dye. The LUMO and HOMO energy levels are well aligned with the conduction band of TiO2 and the redox potential of electrolyte for the charge injection and the dye-regeneration processes, respectively. Photovoltaic efficiency of 1.51% (V-OC 610 mV, J(SC) 3.07 mA cm(-2), ff 81%) has been achieved for SQ5S dye, whereas SQ5 showed the device performance of 5.43% (V-OC 723 mV, J(SC) 9.3 mA cm(-2), ff 80%). The decreased device performance for the dye SQ5S has been attributed to the favorable intersystem crossing process associated with the photoexcited SQ5S that reduces the driving force for the charge injection process.

Design and synthesis of piano-stool ruthenium(II) complexes and their studies on the inhibition of amyloid ? (1-42) peptide aggregation - Singh, Sain; Navale, Govinda R.; Agrawal, Sonia; Singh, Haobam Kisan; Singla, Labhini; Sarkar, Dhiman; Sarma, Manabendra; Choudhury, Anghuman Roy; Ghosh, Kaushik (International Journal of Biological Macromolecules, 2023)
Misfolding , protein aggregation have been linked to numerous human neurodegenerative disorders such as Alzheimer's, prion , Parkinson's diseases. Ruthenium (Ru) complexes have received considerable attention in studying protein aggregation due to their interesting photophysical and photo properties. In this study, we have synthesized the novel Ru complexes ([Ru(p-cymene)Cl(L-1)][PF6](Ru-1), and [Ru(p-cymene)Cl(L-2)][PF6](Ru-2)) and investigated their inhibitory activity against the bovine serum albumin (BSA) aggregation and the A beta 1-42 peptides amyloid formation. Several spectroscopic methods were used to characterize these complexes, and the molecular structure of the complex was determined by X-ray crystallography. Amyloid aggregation and inhi-bition activities were examined using the Thioflavin-T (ThT) assay, and the secondary structures of the protein were analyzed by circular dichroism (CD) spectroscopy and transmission electron microscopy (TEM). The cell viability assay was carried out on the neuroblastoma cell line, revealing that the complex Ru-2 showed better protective effects against A beta 1-42 peptide toxicity on neuro-2a cells than the complex Ru-1. Molecular docking studies elucidate the binding sites and interactions between the Ru-complexes and A beta 1-42 peptides. The exper-imental studies revealed that these complexes significantly inhibited the BSA aggregation and A beta 1-42 amyloid fibril formation at 1:3 and 1:1 molar concentrations, respectively. Antioxidant assays demonstrated that these complexes act as antioxidants, protecting from amyloid-induced oxidative stress. Molecular docking studies with the monomeric A beta 1-42 (PDB: 1IYT) show hydrophobic interaction, and both complexes bind preferably in the central region of the peptide and coordinate with two binding sites of the peptide. Hence, we suggest that the Ru-based complexes could be applied as a potential agent in metallopharmaceutical research against Alzheimer's disease.
Keywords: Aggregation; Amyloid ?(1-42) peptide; DFT computation; Fibrillization; Molecular docking; Ruthenium complexes

Developing a feeding assay system for evaluating the insecticidal effect of phytochemicals on Helicoverpa armigera - Mohite, Sharada D.; Patil, Yogita P.; Nichit, Vikram J.; Joshi, Rakesh S. (Jove-Journal of Visualized Experiments, 2023)
Helicoverpa armigera, a lepidopteran insect, is a polyphagous pest with a worldwide distribution. This herbivorous insect is a threat to plants and agricultural productivity. In response, plants produce several phytochemicals that negatively impact the insect's growth and survival. This protocol demonstrates an obligate feeding assay method to evaluate the effect of a phytochemical (quercetin) on insect growth, development, and survival. Under controlled conditions, the neonates were maintained until the second instar on a pre-defined artificial diet. These second-instar larvae were allowed to feed on a control and quercetin-containing artificial diet for 10 days. The insects' body weight, developmental stage, frass weight, and mortality were recorded on alternate days. The change in body weight, the difference in feeding pattern, and developmental phenotypes were evaluated throughout the assay time. The described obligatory feeding assay simulates a natural mode of ingestion and can be scaled up to a large number of insects. It permits one to analyze phytochemicals' effect on the growth dynamics, developmental transition, and overall fitness of H. armigera. Furthermore, this setup can also be utilized to evaluate alterations in nutritional parameters and digestive physiology processes. This article provides a detailed methodology for feeding assay systems, which may have applications in toxicological studies, insecticidal molecule screening, and understanding chemical effects in plant-insect interactions.

Domain shuffling and site-saturation mutagenesis for the enhanced inhibitory potential of amaranthaceae α-amylase inhibitors - Rane, Ashwini S.; Nair, Vineetkumar S.; Joshi, Rakesh S.; Giri, Ashok P. (Protein Journal, 2023)
Amaranthaceae a-amylase inhibitors (AAIs) are knottin-type proteins with selective inhibitory potential against coleopteran a-amylases. Their small size and remarkable stability make them exciting molecules for protein engineering to achieve superior selectivity and efficacy. In this report, we have designed a set of AAI pro- and mature peptides chimeras. Based on in silico analysis, stable AAI chimeras having a stronger affinity with target amylases were selected for characterization. In vitro studies validated that chimera of the propeptide from Chenopodium quinoa a-AI and mature peptide from Beta vulgaris a-AI possess 3, 7.6, and 4.26 fold higher inhibition potential than parental counterparts. Importantly, recombinant AAI chimera retained specificity towards target coleopteran a-amylases. In addition, to improve the inhibitory potential of AAI, we performed in silico site-saturation mutagenesis. Computational analysis followed by experimental data showed that substituting Asparagine at the 6th position with Methionine had a remarkable increase in the specific inhibition potential of Amaranthus hypochondriacus a-AI. These results provide structural-functional insights into the vitality of AAI propeptide and a potential hotspot for mutagenesis to enhance the AAI activity. Our investigation will be a toolkit for AAI's optimization and functional differentiation for future biotechnological applications.
Keywords: & alpha; -Amylase; -Amylase inhibitors; Amaranthaceae; Coleoptera; Peptide; Pest control

Effect of acidity and mesoporosity in H-USY on conversion of wheat straw to ethyl levulinate (Biofuel additive) - Heda, Jidnyasa; Niphadkar, Prashant; Nandanwar, Sachin; Bokade, Vijay (Journal of the Indian Chemical Society, 2023)
Cold flow properties of biodiesel can be improved by addition of additives especially ethyl levulinate (EL up to 20%). There are very limited information on synthesis of EL from actual raw biomass like wheat straw over heterogeneous catalyst. The present article elaborated on optimization of Acidity to Mesoporosity ratio in H-USY, which is crucial for its application in conversion of raw wheat straw to selective formation of EL in one-step. The acidity and mesoporosity is monitor by systematic post treatment of desilication and dealumination. Optimum acidity/mesoporosity ratio of 3.6 in HUSY resulted in to maximum EL yield of 24.5%, which is probably the highest so far.
Keywords: Acidity; Biofuel additive; Dealumination; Desilication; ethyl levulinate; H-USY; Mesoporosity; Wheat straw

Effective valorization of blackstrap molasses to poly gamma glutamic acid (γ-PGA) using L-glutamic acid independent feeding approach and its significance as drought mitigator in wheat plant - Nair, Pranav G.; Dharne, Mahesh S. (Industrial Crops and Products, 2023)
One of the finest approaches towards sustainable waste management is its effective valorization to value-added products (VAPs). Waste valorization is garnering considerable attention since it delivers substantial advantages, including environmental stability and a sustainable and viable platform for producing different VAPs. One such VAP is the poly gamma glutamic acid (& gamma;- PGA), an extortionate biopolymer known to date. Its exorbitant cost is the main barrier preventing & gamma;- PGA from becoming commercially viable. Hence, the key to the successful commercialization of & gamma;- PGA is its sustainable and cost-effective production. In the present study, the ability of Bacillus paralicheniformis NCIM 5769 to utilize molasses for & gamma;-PGA production with minimal nutrients was investigated. Results showed that 30% molasses combined with 2% ammonium nitrate was the optimal medium for & gamma;-PGA production. Additionally, the anti-drought activity of the synthesized & gamma;-PGA was evaluated on wheat plants showing significantly higher shoot length, biomass content, and germination rate compared to the control group. These findings suggest that & gamma;-PGA produced from molasses has the potential to be used as a drought mitigator in wheat plant, thereby achieving the mission of circular economy and sustainable development goal (SGD) 12, i.e. pursuing sustainability patterns for consumption & production.
Keywords: Anti-drought; circular economy; Poly gamma glutamic acid; Sustainable; Waste valorization

Efficient olefin epoxidation with high turnover rates over ordered mesoporous silica nanoparticles with uniform manganese sites - Negi, Sanjay Singh; Khatri, Prateek; Singh, Anand Pal (Microporous and Mesoporous Materials, 2023)
Olefin epoxidation has been studied over a series of mesoporous manganese silicate nanoparticles and tBuOOH. Partial substitution of Si by Mn in silica framework leads to highly dispersed, distorted Mn(III) sites, confirmed by various physicochemical analyses. High conversion and stable styrene oxide, stilbene oxide and epoxy cyclohexane yield have been achieved with MS75 with 1:1.5 ratio of olefin: oxidant. However, at faster reaction rates lower styrene oxide yield is observed at lower Mn-containing catalyst (MS100). High TON, TOF over manganese sites shows accessible monomeric Mn sites. Attributed to high reactant density at redox-active Mn silicate sites due to facile diffusion across shallow pore depth channels of nanoparticulate om-MSx and surface hydrophobic characteristics. The catalysts were found to be stable under recycling and filtration experiments. The excellent stability against leaching of active manganese species indicates stable sites and good textural properties in om-MSx, essential for extended activity.
Keywords: epoxidation; Manganese silicates; Mesoporous silica nanoparticles; Ordered mesoporous silica; pH adjustment

Efficient synthesis of optically active herbicide (S)-metolachlor via reductive ring opening of 2-methoxymethylaziridine - Nalla, Viswanadh; Mujahid, Mohammad; Sasikumar, Murugesan; Mujumdar, Prashant; Muthukrishnan, Murugan (Arkivoc, 2023)
An efficient synthesis of a well known chiral herbicide, (S)-metolachlor has been described using 2methoxymethylaziridine ring formation and reductive ring opening as key steps using commercially available (R)-epichlorohydrin. The present protocol delivers the required enantiomer of metolachlor in overall yield of 50.8% and high enantiopurity (>99%).
Keywords: Aziridine; Epoxide; Epoxide ring opening; herbicide synthesis; Metolachlor

Electrocatalytic hydrogen evolution mediated by an organotelluroxane macrocycle stabilized through secondary interactions - Narsimhulu, Gujju; Samuel, Calvin; Palani, Sathishkumar; Dasari, Sai Hemant Kumar; Krishnamoorthy, Kothandam; Baskar, Viswanathan (Dalton Transaction, 2023)
A discrete liphophilic organotelluroxane macrocycle has been found to catalyse the hydrogen evolution reaction (HER) by proton reduction efficiently. The macrocycle is synthesized via chloride abstraction from bis(p-methoxyphenyl) tellurium dichloride (p-MeOC6H5)2TeCl2 (1) by silver salts AgMX4 (MX4 = BF4-, and ClO4-) resulting in in situ generated di-cationic tetraorganoditelluroxane units; two such units are held together by two weak anions mu 2-MX4, bridging to form 12-membered di-cationic macrocycles [((p-MeO-C6H4)2Te)2(mu-O)(mu 2-F2BF2)2]2+ (2) and [((p-MeO-C6H4)2Te)2(mu-O)(mu 2-O2ClO2)2]2+ (3) stabilized via Te-(mu 2-BF4/ClO4), with secondary interactions. The charge is balanced by the presence of two more anions, one above and another below the plane of the macrocycle. Similar reaction at higher temperatures leads to the formation of telluronium salts R3TeX [X = BF4- (4), ClO4- (5)] as a major product. The BF4- anion containing macrocycle and telluronium salt were monitored using 19F NMR. HRMS confirmed the structural stability of all the compounds in the solution state. The organotelluroxane macrocycle 2 has been found to act as an efficient electrocatalyst for proton reduction in an organic medium in the presence of p-toluene sulfonic acid as a protic source. A discrete liphophilic organotelluroxane macrocycle has been found to catalyse hydrogen evolution reaction (HER) by proton reduction efficiently.
Keywords: Anion Transport; Proton-Reduction

Equilibrium adsorption of nitrogen, oxygen, and argon on silver-exchanged hierarchical ETS-10 - Shrotri, Aadesh R.; Niphadkar, Prashant S.; Bokade, Vijay V.; Nandanwar, Sachin U. (Journal of Chemical and Engineering Data, 2023)
Silver-exchanged hierarchical ETS-10(Ag-H-ETS-10) was synthesizedusing Ag+ exchange with hierarchical Engelhard titanosilicate(H-ETS-10) using silver nitrate solution. The physical propertiesof the adsorbent were analyzed using X-ray diffraction (XRD), BETsurface area, nitrogen adsorption-desorption, pore volume,energy dispersive spectroscopy (EDS), and high resolution-transmissionelectron microscopy (HR-TEM). N-2 physisorption data confirmedthat a micro-mesoporous (bimodal) structure was created in the Ag-H-ETS-10.The equilibrium adsorbent data of pure gases N-2, O-2, and Ar were investigated in the temperature range from 288to 318 K up to 10 bar. The equilibrium adsorption capacity of Ag-H-ETS-10was found to be 1.12 mmol g(-1) for N-2,0.87 mmol g(-1) for O-2, and 1.09 mmol g(-1) for Ar at 298 K and & SIM;10 bar. & SIM;20% higheradsorption capacity was found for N-2 and Ar in Ag-H-ETS-10compared to Ag-ETS-10. The higher sorption capacity was attributedto the formation of a bimodal structure and & pi;-complexation interactionby the Ag cation, which allows a multilayer of N-2 and Armolecules. The Sips isotherm model was well fitted for the Ag-H-ETS-10experimental data among Langmuir, Freundlich, Toth, and Temkin models.The measured equilibrium adsorption data for Ag-H-ETS-10 can be usefulfor the O-2 purification process.

Evaluation of Fe3O4 incorporated functionalized carbon nanotube self-standing buckypaper as electrodes for solid-state symmetric supercapacitor - Bhaviripudi, Vijayabhaskara Rao; Dwivedi, Pravin K.; Pabba, Durga Prasad; Aepuru, Radhamanohar; Nakate, Umesh T.; Espinoza-Gonzalez, Rodrigo; Shelke, V, Manjusha (Journal of Energy Storage, 2023)
Iron (II, III) oxide and carbonaceous materials drawn considerable attention in energy storage owing to their special features. In this study, simple reverse co-precipitation, acid functionalization and vacuum filtration methods adopted to synthesis Fe3O4 nanoparticles of size 11 nm and -COOH acid functionalized multi-wall carbon nanotubes (FMWCNT). And further used them to prepare and optimize Fe3O4 in FMWCNT as 15 wt% and 25 wt% self-standing buckypapers of around 30-mu m thickness as electrodes for solid-state symmetric capacitor in the form of coin cell. The results show that 15 wt% and 25 wt% of Fe3O4-FMWCNT buckypapers hybrid nanostructures have Fe3O4 nanoparticles successfully incorporated in FMWCNT. The 25 wt% Fe3O4-FMWCNT electrodes with charge transfer resistance of 140 Ohm showed high areal specific capacitance (Cs) 78.5 mF/cm2 and retained 80 % of its Cs until 800 cycles even at high current density of 1 mA/cm2, scan rate of 100 mV/s whereas 15 wt% Fe3O4-FMWCNT showed low Cs of 47 mF/cm2 and retained 80 % of its Cs over 5000 cycles whereas only FMWCNT show Cs is 36 mF/cm2 with 54 Ohm. Finally, a solid-state symmetric supercapacitor coin cell with self-standing 25 wt% Fe3O4-FMWCNT buckypaper showed an excellent power density of 129.5 mW cm-3 and energy density of 3.6 mWh cm-3 is the innovation of the current work. This is mainly attributed to the combined effect of pseudocapacitive behavior from Fe3O4 by faradaic reaction with additional charge transfer resistance and electric double layer (EDLC) behavior from FMWCNTs by non-faradaic of electronic, ionic transport during charging-discharging. As-made solid-state symmetric supercapacitor appears as a high-performance storage device without extra support of current collectors for practical applications and for fabri-cation of planar capacitors.
Keywords: Buckypaper; Power density; specific capacitance; Symmetric supercapacitor

Evaluation of the adhesive properties of vanillin-derived polyhydroxy urethanes - Ghuge, Gorakh Hiraman; Kambikanam, Karthika Vayalachery; Nair, Kiran Sukumaran (Journal of Applied Polymer Science, 2023)
Poly(hydroxy urethanes) (PHUs) have been considered attractive and safer variants of conventional polyurethanes (PUs). To improve the prerequisites of green and sustainable chemistry herein, we propose the synthesis and utilization of cyclic carbonate monomers majorly derived from vanillin, a lignin derivative, and CO2 for the development of PHUs. Kinetic evaluation on the polymerization temperature ascertained 80 degrees C as the optimum condition for PHU synthesis. The structural evaluation of PHUs was carried out by various spectroscopic techniques, such as FTIR, (HNMR)-H-1, and C-13-NMR, molar masses were determined by gel permeation chromatography (Mn varied between 2500 and 11,100 g/mol), and thermal properties evaluated by differential scanning calorimeter (Tg in the ranges of 28-42 degrees C), and thermogravimetric analysis (stable above 180 degrees C). Since the PHUs are enriched with pendant hydroxyl groups on their backbone which can promote adhesion, lap shear studies on the aluminum substrate exhibited a maximum shear strength of 1.65 +/- 0.37 MPa. This study demonstrates an attractive and environment-friendly pathway for developing novel PHUs network using renewable biobased resources and further explores its applicability as adhesives.
Keywords: adhesive; biobased cyclic dicarbonate; diamines; poly(hydroxyurethane)s; Vanillin

Facile one-pot synthesis of Cu x O/TiO2 photocatalysts by regulating Cu oxidation state for efficient solar H2 production - Rajendran, Sivaraj; Mani, Sunesh S.; Nivedhitha, Thazhath R.; Asoka, Anantha Krishnan; Arun, Pushkaran S.; Mathew, Thomas; Gopinath, Chinnakonda S. (ACS Applied Energy Materials, 2023)
Development of highly efficient CuxO/TiO2 photocatalysts by regulating the oxidation state of Cu exclusively in either single or mixed oxidation state(s) is desirable but difficult to achieve without employing any external reagents. The present work describes a one-pot synthesis strategy to obtain CuxO/TiO2 photocatalysts with Cu in +1 and/or +2 by using a suitable combination of ethylene diamine tetra acetic acid (EDTA) and ethylene diamine, carefully varying the Cu content, and heat treatment process. CuxO/TiO2 nanocomposite catalysts were characterized thoroughly by physicochemical methods. Textural analysis indicates a high dispersion of CuxO on porous TiO2 with p-n heterojunctions between them in CuxO/TiO2 catalysts. UV-visible spectral analysis suggests the presence of CuxO on TiO2 with significantly extended absorption from the UV to the visible region. X-ray photoelectron spectroscopy (XPS) analysis indicates a strong synergetic interaction between TiO2 and CuxO due to the comparable CB potential and p-n heterojunction at the interface among them. Photoelectrochemical studies demonstrate excellent charge-carrier separation efficiency, low charge-transfer resistance, and high double-layer capacitance with Cu2O/TiO2 photocatalysts. Photocatalytic efficacy of a CuxO/TiO2 nanocomposite in thin-film form has been demonstrated for solar hydrogen generation in sunlight. The incorporation of Cu+ in TiO2 largely improves the H-2 production, and all of the CuxO/TiO2 nanocomposites in thin-film form exhibited higher efficiency compared to their particulate/suspension counterpart. Among the composite catalysts, TiCu-1 in thin-film form, with Cu exclusively in +1 oxidation state, exhibited a high hydrogen production rate of 7.06 mmol/hg, which is 6 times higher than its suspension counterpart; also catalysts containing mixed Cu-oxidation states exhibited about 60-70% activity as that of TiCu-1. The superior performance of Cu2O/TiO2 nanocomposites in thin-film form was due to their enhanced light harvesting ability, high mass transfer rate, and easy accessibility of the reactant species to the active sites.
Keywords: heterojunction; Photocatalysis; Solar hydrogen; thin film; titania

Functionalized CNT-azobenzene-PVA-based self-healing aqueous gel as a conductive photo-responsive actuator - Narayanan, Aswini; Bhagyasree, T. M.; Torris, Arun; Babu, Sukumaran Santhosh (Journal of materials chemistry C, 2023)
Conductive gels have gained attention from researchers owing to potential applications in flexible displays, implantable medical devices, touch panels, wearable electronic skin, sensors, soft robotics, etc. Photo-responsive conductance switching gels can make their way into various applications, including contact-free remote-controlled manipulation of the materials, implantable synthetic organs, and optical switches. Herein, we report an aqueous gel with boronic acid containing azobenzene crosslinker as the light-responsive part that can undergo reversible cis-trans isomerization on irradiation with UV-vis light and catechol functionalized single-walled carbon nanotube as a conductive part producing a self-healing aqueous gel with PVA. The 3D crosslinked gel network formed through the formation of boronic ester and hydrogen bonding between hydroxyl and boronic acid groups was confirmed using scanning electron microscopy, X-ray microtomography, and rheological experiments. Rheology results show that gel is a viscoelastic material with immediate self-healing properties. The presence of functionalized SWCNT in the gel matrix enhances the stability and results in a conductivity of up to 3.5 S cm-1 with a loading of 5 wt%. The gel network exhibits a photoresponsive conductance switching from 10 to 60 mu A with UV and visible light irradiation, respectively. The molecular level motions during the isomerization of azobenzene lead to macroscopic dynamic changes that can find applications in soft actuators. The photoresponsive conductivity switching and dynamic movements of the films make the present material suitable for contact-free switching applications. Responsive conductive gels have gained attention owing to potential applications in flexible displays, implantable medical devices, touch panels, wearable electronic skin, sensors, soft robotics, and related areas.
Keywords: Cyclodextrins; Supramolecular Hydrogels,

Gas sensors and factors influencing sensing mechanism with a special focus on MOS sensors - Nadargi, Digambar Y. Y.; Umar, Ahmad; Nadargi, Jyoti D. D.; Lokare, Smita A. A.; Akbar, Sheikh; Mulla, Imtiaz S. S.; Suryavanshi, Sharad S. S.; Bhandari, Nagesh L. L.; Chaskar, Manohar G. G. (Journal of Materials Science, 2023)
Industrialization and its progress are very important for the economy and to move towards prosperity, stimulating innovation and creating jobs. Nonetheless, industrialization has negative impacts, if not done judiciously, such as pollution, increased greenhouse gas emissions, and global warming. Therefore, amenity-with-security is of fundamental significance in a new and dynamic lifestyle. A gas sensor is one of the crucial devices for monitoring and subsequently preserving the clean atmosphere among a number of other safety technologies. In-depth assessments of gas sensors and their necessity in the environment (air) pollution are provided in the current review. With a special emphasis on metal oxide semiconductor (MOS)-based gas sensors, the review includes a thorough study of gas sensors and the factors relating to sensing mechanisms. It not only describes the basic concepts and brief history of gas sensors, but also highlights the schemes responsible for improving the gas sensing properties and state-of-art literature review. These schemes include (1) surface engineering/morphological tuning and (2) bulk and surface doping. To keep scientific rigour and in-depth analyses, this review focuses on these two schemes only. In the doping area, the emphasis is given on graphene loading, decorated with nanoparticles of noble metals, spillover mechanism, and heterojunction (p-n, n-n, and p-p) formation. The conclusion summarizes the most optimized MOS gas sensors with enhanced gas sensing capabilities. The emphasis is given to formulate the article in such a way that it will be useful for the beginners who wish to explore the gas sensor research field, as well as to the established researchers to further improve the sensing capabilities of MOS gas sensors.

Genetic diversity of toxigenic Fusarium verticillioides associated with maize grains, India - Navale, Vishwambar D.; Sawant, Amol M.; Vamkudoth, Koteswara Rao (Genetics and Molecular Biology, 2023)
In the present investigation, prevalence, genetic diversity, and mycotoxin producing potential of Fusarium species associated with maize grain samples were studied from different geographical regions of India. The highest prevalence of Fusarium verticillioides was recorded as 88.52%, followed by F. coffeatum, F. foetens, and F. euwallaceae, 6.55%, 3.27%, and 1.63%, respectively. We isolated 54 strains of F. verticillioides, and their genetic diversity was studied by inter simple sequence repeats (ISSR). The ISSR fingerprints (AG) 8C and (AG) 8G showed 252 and 368 microsatellite sites in the genome of F. verticillioides and resulted in 99-100% repeatability and reproducibility. The Simpson (SID) and Shannon (H) indices (0.78 and 2.36) suggest that F. verticillioides strains exhibit moderate to high diversity. Molecular detection of fumonisin B1 (FB1) biosynthetic genes (FUM1 and FUM13) involved in FB1 production in F. verticillioides was confirmed by polymerase chain reaction (PCR). Furthermore, 91% of the strains were positive for FB1 production, which was affirmed by liquid chromatography with tandem mass spectrometry (LC-MS-MS). In-vitro appurtenance of F. verticillioides spores exhibited a high to moderate effect on the growth and development of the maize. The current finding demonstrated that most F. verticillioides strains showed a wide range of genetic diversity with varied toxigenic and pathogenic potentials. In conclusion, for the first time, F. coffeatum, F. foetens, and F. euwallaceae species were reported from maize grain samples in India. They were positive for FB1 and negatively affecting grain quality, which is a major concern in food safety.
Keywords: diversity; Food safety; Fusarium verticillioides; Mycotoxin; pathogenicity

Green synthesis of GO-loaded Ag/ZnO nanocomposites for methyl orange degradation - Nadargi, Digambar Y.; Nadargi, Jyoti D.; Tamboli, Mohaseen S.; Tamboli, Asiya M.; Mulla, Imitaz S.; Umar, Ahmad; Truong, Nguyen Tam Nguyen; Suryavanshi, Sharad S. (Journal of Materials Science-Materials in Electronics, 2023)
Nature is a perfect laboratory for creating novel nanomaterials for a variety of applications. A robust green synthesis approach to GO-loaded Ag/ZnO nanocomposite materials using medicinal plant extraction and their potential application in methyl orange dye degradation are reported. The straightforward technique employs zinc and silver nitrate precursors in an aqueous solution of medicinal plant extract, causing the precipitation process. Prior to photocatalytic investigations, the physico-chemical properties of the material are analysed using TG-DTA, XRD, FE-SEM, TEM, EDAX and BET. The developed material showcase hexagonal wurtzite structure of ZnO, with face-centered-cubic phase of Ag and AgCl. All the samples exhibit aggregated, irregular rounded grains, as expected in the precipitation synthesis process. Pristine ZnO showed 15.5% degradation efficiency towards methyl orange, which was further improved by doping Ag from 0.5 to 2 mol%. The catalyst with 1 mol% Ag doping resulted in the better photocatalytic activity (26.30%), which has again improved by loading the GO (27.46%). The outcome of this study provides the new insights to GO-loaded Ag/ZnO nanocomposites by green synthesis route, in view of photocatalytic applications.

Identification of new modulator of DNA repairing pathways based on natural product (±)-peharmaline A - Kulkarni, Akshay S.; Dash, Anshurekha; Shingare, Rahul D.; Chand, Jagdish; Manhas, Diksha; Singh, Aman; Nandi, Utpal; Goswami, Anindya; Reddy, D. Srinivasa (Bioorganic & Medicinal Chemistry, 2023)
The complex heterogenic environment of tumour mass often leads to drug resistance and facilitate chemo insensitivity triggering more malignant phenotypes among cancer patients. Major DNA-damaging cancer drugs have been consistently proven unsuccessful in terms of elevating chemo-resistance. (& PLUSMN;)-peharmaline A, a hybrid natural product isolated from seeds of Peganum harmala L. possesses significant cytotoxic activities. Herein, we have described the design, and synthesis of a novel library of close and simplified analogues around the anticancer natural product (& PLUSMN;)-peharmaline A and investigated their cytotoxic activities, which led to the identification of three structurally simplified lead compounds exhibiting better potency than parent natural product. Among them, demethoxy analogue of peharmaline A was further investigated for its anticancer potential eliciting demethoxy analogue as potent DNA-damage inducing agent attenuating the expression of the proteins responsible for the DNA damage repair. Therefore, this demethoxy analogue warrants detailed investigations for the confirmations of the molecular mechanism-based studies responsible for its anticancer activity.
Keywords: DNA damage; EMT; Pictet; Spengler reaction; Structure-activity relationship; Total synthesis

Inhibition of amyloid β1-42 peptide aggregation by newly designed cyclometallated palladium complexes - Saini, Rahul; Navale, Govinda R.; Singh, Sain; Singh, Haobam Kisan; Chauhan, Rahul; Agrawal, Sonia; Sarkar, Dhiman; Sarma, Manabendra; Ghosh, Kaushik (International Journal of Biological Macromolecules, 2023)
Uncontrolled amyloid aggregation is a frequent cause of neurodegenerative disorders such as prions and Alzheimer's disease (AD). As a result, many drug development approaches focus on evaluating novel molecules that can alter self-recognition pathways. Herein, we designed and synthesized the cyclometallated pyrene (Pd-1 and Pd-3) and anthracene (Pd-2) based palladium complexes ([Pd((L-1)Cl] Pd-1, [Pd(L-2)Cl](Pd-2), and [Pd(L-3)Cl] (Pd-3)). This study explores the effect of these complexes on the aggregation, fibrillation, and amyloid formation of bovine serum albumin (BSA) and A beta(1-42) peptide. Several spectroscopic methods were used to characterize all the Pd-complexes, and the molecular structure of Pd -3 was determined by X-ray crystallography. The secondary structures were studied using circular dichroism (CD) and transmission electron microscopy (TEM), while am-yloid aggregation and inhibitory activities were investigated using the Thioflavin-T (ThT) fluorescence assay. Molecular docking of the Pd-complex (Pd-3) was done using fibril (PDB: 2BEG) and monomeric (PDB: 1IYT) peptides using Auto-dock Vina. As a result, the hydrogen bonding and hydrophobic interaction between the aromatic rings of the Pd-complexes and the amino acids of amyloid-beta peptides significantly reduced the pro-duction of ordered beta-sheets of amyloid fibrils and protein aggregation in the presence of Pd-2 and Pd-3 complexes.
Keywords: A beta(1-42) peptide; Aggregation and molecular docking; Palladium complex

Inhibitory effect of curcumin-artemisinin co-amorphous on Tau aggregation and Tau phosphorylation - Dubey, Tushar; Sonawane, Shweta Kishor; Mannava, M. K. Chaitanya; Nangia, Ashwini K.; Chandrashekar, Madhura; Chinnathambi, Subashchandrabose (Colloid and Surfaces B-Biointerfaces, 2023)
Tau is a natively unfolded microtubule-associated protein. Tau neurofibrillary tangles are one of the hallmarks of Alzheimer's disease. The post-translational modifications of Tau lead to its pathological state. Phosphorylation is the key post-translational modification associated with Tauopathy. Curcumin is a polyphenolic compound pre-sent in the rhizomes of Curcuma longa. Curcumin has been reported to have remarkable medicinal properties in several diseases, but its poor solubility limits its therapeutic potency. Artemisinin is a sesquiterpene lactone, which has been known sience ancient times for its applications as a treatment for various diseases such as malaria, cancer, autoimmune disease, etc. In the present study, the potency of crystalline curcumin, crystalline artemisinin, and Cur-Art co-amorphous dispersion were evaluated against Tau pathology. The in-vitro ThS/ANS fluorescence and electron microscopy results suggested that curcumin and Cur-Art efficiently inhibited Tau aggregation. Furthermore, exposure to curcumin and Cur-Art co-amorphous restored the impaired nuclear transport in formaldehyde-stressed cells. Curcumin was also found to modulate the phosphorylation of Tau, which indicated the neuroprotective potency. Thus, curcumin and Cur-Art co-amorphous exhibit therapeutic potential against Tau protein in Alzheimer's disease.
Keywords: artemisinin; curcumin; Phosphorylation; Tau Aggregation

Isolation and molecular characterization of indigenous penicillium chrysogenum/rubens strain portfolio for penicillin V production - Sawant, Amol M.; Navale, Vishwambar D.; Vamkudoth, Koteswara Rao (Microorganisms, 2023)
Beta (beta)-lactam antibiotic is an industrially important molecule produced by Penicillium chrysogenum/rubens. Penicillin is a building block for 6-aminopenicillanic acid (6-APA), an important active pharmaceutical intermediate (API) used for semi-synthetic antibiotics biosynthesis. In this investigation, we isolated and identified Penicillium chrysogenum, P. rubens, P. brocae, P. citrinum, Aspergillus fumigatus, A. sydowii, Talaromyces tratensis, Scopulariopsis brevicaulis, P. oxalicum, and P. dipodomyicola using the internal transcribed spacer (ITS) region and the beta-tubulin (BenA) gene for precise species identification from Indian origin. Furthermore, the BenA gene distinguished between complex species of P. chrysogenum and P. rubens to a certain extent which partially failed by the ITS region. In addition, these species were distinguished by metabolic markers profiled by liquid chromatography-high resolution mass spectrometry (LC-HRMS). Secalonic acid, Meleagrin, and Roquefortine C were absent in P. rubens. The crude extract evaluated for PenV production by antibacterial activities by well diffusion method against Staphylococcus aureus NCIM-2079. A high-performance liquid chromatography (HPLC) method was developed for simultaneous detection of 6-APA, phenoxymethyl penicillin (PenV), and phenoxyacetic acid (POA). The pivotal objective was the development of an indigenous strain portfolio for PenV production. Here, a library of 80 strains of P. chrysogenum/rubens was screened for PenV production. Results showed 28 strains capable of producing PenV in a range from 10 to 120 mg/L when 80 strains were screened for its production. In addition, fermentation parameters, precursor concentration, incubation period, inoculum size, pH, and temperature were monitored for the improved PenV production using promising P. rubens strain BIONCL P45. In conclusion, P. chrysogenum/rubens strains can be explored for the industrial-scale PenV production.
Keywords: beta-tubulin gene; high-performance liquid chromatography; internal transcribed spacer region; Penicillium chrysogenum/rubens; phenoxymethyl penicillin

Luminescent 3D printed poly(lactic acid) nanocomposites with enhanced mechanical properties - Kothavade, Premkumar Anil; Yadav, Prashant; Nidhankar, Aakash D.; Torris, Arun; Pol, Harshawardhan; Kafi, Abdullah; Bateman, Stuart; Sukumaran, Santosh Babu; Shanmuganathan, Kadhiravan (Polymer Engineering and Science, 2023)
The three-dimensional (3D) printing of functional composite materials has gained tremendous interest in recent years. Nevertheless, research on 3D printing of luminescent composite materials is very limited, and the mechanical properties of such 3D-printed composites are poor. Herein, we report the preparation and characterization of a poly(lactic acid) (PLA) composite that, when 3D printed, exhibits enhanced toughness and high solid-state fluorescence quantum yield. Incorporation of only 1 wt% pyrene butyric acid modified cellulose nanofibers (PBA-m-CNF) and l0 wt% thermoplastic polyurethane (TPU) into PLA led to 223% increase in toughness and 21% increase in tensile modulus of PLA. Scanning electron microscopy (SEM) and X-ray microcomputed tomography (mu-CT) analysis of the fractured cross-sections of 3D printed composites revealed a ductile failure mode. The PLA/PBA-m-CNF1/TPU10 3D printed composite also exhibited a high solid-state fluorescence quantum yield of 38.35%. To the best of our knowledge, this is the first report to show both enhanced mechanical properties and high solid-state fluorescence emission for 3D printable PLA. Such functional PLA composites could have potential applications in the fabrication of complex-shaped sensors, optical light pipes, etc.
Keywords: 3D printing; Composite; fluorescence; Nanocellulose; poly(lactic acid); toughness

Metabolites from lactococcus lactis subsp. lactis: isolation, structure elucidation, and antimicrobial activity - Navale, Vishwambar D.; Borade, Balasaheb R.; Rama Krishna, Gamidi; Vamkudoth, Koteswara Rao; Kontham, Ravindar (ACS Omega, 2023)
Herein, we disclose the identification of novel metabolites from a potential probiotic strain, Lactococcus lactis subsp. lactis, obtained from traditional dairy milk samples collected in Maharashtra, India (in January 2021). Isolated metabolites include pyrazin-2-carboxamide [1, pyrazinamide, a potential antitubercular drug], 3,5-dihydroxy-6-methyl-2,3-dihydro-4H-pyran-4-one (2, DDMP), 2,4-di-tert-butylphenol (3), and hexadecanoic acid (4, palmitic acid). The chemical structures of these metabolites were elucidated through extensive 1D NMR (H-1 and C-13) and 2D NMR (HSQC, HMBC, and NOESY) analyses, high-resolution mass spectrometry, high-performance liquid chromatography, and single-crystal X-ray crystallography. Furthermore, these novel metabolites exhibited potent inhibitory activities against various bacteria, fungi, and yeast strains with minimum inhibitory concentrations ranging between 1.56 and 25 mu g/mL, and compounds 1 and 3 were found to be most active against a wide range of microbial strains tested.

Metal-organic framework-derived mesoporous B-doped CoO/Co@N-doped carbon hybrid 3D heterostructured interfaces with modulated cobalt oxidation states for alkaline water splitting - Cha, Dun Chan; Singh, Thangjam Ibomcha; Maibam, Ashakiran; Kim, Tae Hyeong; Nam, Dong Hwan; BabaRao, Ravichandar; Lee, Seunghyun (Small, 2023)
Heteroatom-doped transition metal-oxides of high oxygen evolution reaction (OER) activities interfaced with metals of low hydrogen adsorption energy barrier for efficient hydrogen evolution reaction (HER) when uniformly embedded in a conductive nitrogen-doped carbon (NC) matrix, can mitigate the low-conductivity and high-agglomeration of metal-nanoparticles in carbon matrix and enhances their bifunctional activities. Thus, a 3D mesoporous heterostructure of boron (B)-doped cobalt-oxide/cobalt-metal nanohybrids embedded in NC and grown on a Ni foam substrate (B-CoO/Co@NC/NF) is developed as a binder-free bifunctional electrocatalyst for alkaline water-splitting via a post-synthetic modification of the metal-organic framework and subsequent annealing in different Ar/H-2 gas ratios. B-CoO/Co@NC/NF prepared using 10% H-2 gas (B-CoO/Co@NC/NF [10% H-2]) shows the lowest HER overpotential (196 mV) and B-CoO/Co@NC/NF (Ar), developed in Ar, shows an OER overpotential of 307 mV at 10 mA cm(-2) with excellent long-term durability for 100 h. The best anode and cathode electrocatalyst-based electrolyzer (B-CoO/Co@NC/NF (Ar)(+)//B-CoO/Co@NC/NF (10% H-2)(-)) generates a current density of 10 mA cm(-2) with only 1.62 V with long-term stability. Further, density functional theory investigations demonstrate the effect of B-doping on electronic structure and reaction mechanism of the electrocatalysts for optimal interaction with reaction intermediates for efficient alkaline water-splitting which corroborates the experimental results.
Keywords: 3D heterostructures; B-doped metal-oxides; electrocatalysts; hydrogen evolution reactions; metal-organic frameworks; oxygen evolution reactions

MnXWO4 nanostructure-based catalysts for single-step oxidation of cyclohexane and methane to oxygenates - Prabu, Marimuthu; Manikandan, Marimuthu; Samal, Pragnya Paramita; Gurrala, Lakshmi Prasad; Mekala, Siva Prasad; Archana, Ramakrishnan; Nayak, Chandrani; Bhattacharyya, D.; Jha, S. N.; Krishnamurty, Sailaja; Raja, Thirumalaiswamy (ACS Applied Nano Materials, 2023)
Activation of the C-H bond in cyclohexane (CYH) and methane is a crucial step to obtain desirable oxygenated products using nanostructured catalyst and is a great challenge and an efficient route to mitigate the inauspicious effects of climate change. The active sites were identified using XRD, HR-TEM, SEM, N2 sorption analysis, TPR, Raman, XPS, TGA, in situ DRIFT, XAS, etc. In optimal reaction conditions, 46% of CYH was converted into adipic acid (AA) on MnxWO4 nanostructures within 6 h. The recyclability test confirmed the catalyst heterogeneity, which revealed no appreciable loss of catalytic activity even after three consecutive reactions. In situ DRIFT study reveals that CYH is oxidized to cyclohexanone and cyclohexanol (KA oil) and is further oxidized to AA via carboxylate intermediates. DFT studies disclosed that MnOx species are responsible for the C-H activation of CYH, and the Mn2+/Mn3+ redox centers play a vital role in the absorption of KA oil to form AA. Herein, we demonstrated the significant role of the ``MnOx'' species and that adequate Lewis and Bronsted acidic sites, redox centers of (Mn2+/Mn3+), and lattice oxygen are accountable for the CYH conversion toward the AA. Additionally, we have reported the oxidation of methane to methanol (146 mu mole per gram of catalyst) in the presence of water at 75 degrees C without over-oxidation products.
Keywords: Adipic Acid; C-H bond activation; Cyclohexane oxidation; methane activation; MnOx chain; Redox center

Modular TiO2-squaraine dyes/electrolyte interface for dye-sensitized solar cells with cobalt electrolyte - Singh, Ambarish Kumar; Sudhakar, Vediappan; Javaregowda, Bharathkumar H.; Bisht, Rajesh; Krishnamoorthy, Kothandam; Nithyanandhan, Jayaraj (Chemphotochem, 2023)
Strategies to diminish both charge recombination and aggregation of dyes on the photoanode by functionalizing the sensitizer with alkyl groups is the best approach to achieve high dyesensitized solar cell (DSSC) efficiency. Development of such a photoanode with NIR-active dyes which is compatible with a cobalt electrolyte is important to enhance the photovoltaic performance. In this report, alkyl-group-wrapped donor-acceptor-donor (D-A-D) based unsymmetrical squaraine dyes have been used for DSSC device characterization with a cobalt electrolyte. Surface passivation of photoanode was varied systematically by the extent of functionalization with alkyl groups to avoid charge recombination. DSSC device performance of 5.92% was achieved for an alkyl-group-wrapped squaraine dye with a cobalt electrolyte. Hence, appending the alkyl groups on the donor unit of squaraine dyes helps passivating the photoanode, whereas introducing hydrophilic groups provides a leaky surface where oxidized electrolyte species reach the titanium-metal-oxide surface which promotes the charge recombination process.
Keywords: counter-electrode; DSSC device efficiency; Dye-sensitized solar cells; Electrolytes; unsymmetrical squaraine dye

MXene surface terminations: a perspective - Natu, Varun; Barsoum, Michel W. (Journal of Physical Chemistry C, 2023)
Two-dimensional (2D) transition metal carbides and nitrides are among the newest, and probably largest, families of 2D materials that have been discovered. They have shown promise in many applications, such as electromagnetic shielding, energy storage devices like batteries and supercapacitors, transparent conductive electrodes, as catalysts for hydrogen production, and several others. Their general formula is Mn+1XnTz (n = 1-4) or M1.33XTz, where M is an early transition metal, X is carbon and/or nitrogen, and T-z represents various terminations present upon etching the Al layer. The first MXene discovered, Ti3C2Tz, was synthesized by etching aluminum (Al) from the nanolaminated MAX phase Ti3AlC2 using hydrofluoric acid (HF). Since the discovery of Ti3C2Tz in 2011, more than 30 other MXene chemistries have been reported with different M and X elements. It has been observed that, as expected, changing the MXene chemistry also influences the properties in the range of applications listed above, allowing us to tailor them according to what suits the application of interest the best. Unlike the success in tailoring the M and X elements over the years, attempts to engineer T-z was, until recently, a challenge. A series of recent discoveries and an improved understanding of MXene surface properties has now rendered the customization of T-z possible. This progress added a new ``knob'' that can be turned to further tune MXene properties. The majority of this Perspective is focused on surface terminations: their engineering, characterization, and effect on MXene properties.

Nanosilica from Averrhoa bilimbi juice pre-treated rice husk: preparation and characterization - Dominic, C. D. Midhun; Neenu, K. V.; Begum, P. M. Sabura; Joseph, Rani; Rosa, Derval dos Santos; Duan, Yongxin; Balan, Aiswarya; Ajithkumar, T. G.; Soumya, Mary; Shelke, Ankita; Parameswaranpillai, Jyotishkumar; Badawi, Michael (Journal of Cleaner Production, 2023)
The preparation of nanosilica from rice husk without using any concentrated mineral acids is a novel concept. This work proposes a bioleaching strategy to remove metallic impurities from rice husk for the preparation of nanosilica. Herein, nanosilica (BJRHS) was prepared by calcinating Averrhoa bilimbi juice pre-treated rice husks in a muffle furnace. The chemical and atomic structures of commercial precipitated silica (CS), rice husk ash (RHA), and BJRHS were analyzed using different analytical techniques. The optimal leaching time, calcination temperature, and calcination time were 1 h, 500 degrees C, and 6 h respectively. The particle size of BJRHS was found to be 6-12 nm, which is less than that of RHA and CS. The BET surface area of BJRHS (204 m2/g) was found to be greater than RHA (110.5 m2/g) and CS (172.1 m2/g). Mesoporous nanosilica with excellent surface area and purity was produced sustainably from rice husk which could be recommended to use in the field of catalysis, polymer technology, etc.
Keywords: Averrhoa bilimbi juice; Bioleaching; Nanosilica; rice husk

Non-confined gamma monoclinic sulfur cathode in carbonate electrolyte based room temperature K-S batteries - Pai, Rahul; Cardoza, Neal Amadeus; Natu, Varun; Barsoum, Michel W.; Kalra, Vibha (JOURNAL OF MATERIALS CHEMISTRY A, 2023)
Potassium-sulfur cells have garnered a lot of interest in grid storage chemistry due to the high abundance of both elements and hence their low cost. However, their development is hindered by the polysulfide shuttle effect and their dependency on electrolytes with limited commercial viability. The inability to use carbonate electrolytes is due to the irreversible reaction between it and PS, rendering the cell useless in the first few cycles. Here we expand our use of monoclinic & gamma;-sulfur in carbon nanofibers (& gamma;S-CNFs) to the potassium-sulfur, K-S, chemistry. Herein we show that using & gamma;-S enables the cells to run for 500 cycles at & SIM;900 mA h g(-1) in commercial carbonate electrolytes. We further attempt to understand the role of & gamma;S-CNFs in K-S cells with electrochemical characterization and postmortem spectroscopy. As far as we are aware this is the first application of & gamma;-S in K-S cells. Its outstanding performance should lead to new avenues for the development of this promising chemistry.

Norbornenyl-pendant aromatic (co)poly(ether ether ketone)s - Talanikar, Aniket A.; Nagane, Samadhan S.; Wadgaonkar, Prakash P.; Rashinkar, Gajanan S. (Journal of macromolecular science part A- pure and applied chemistry, 2023)
4, 4'-(Bicyclo (2.2.1) hept-5-en-2 yl methylene) bis (2-methoxyphenol) (BPA-NB) was utilized as a step-growth monomer for the synthesis of (co)poly(ether ether ketone)s (PEEK-NBs) via nucleophilic aromatic substitution polycondensation. A homo and five PEEK-NBs were synthesized by polycondensation of 4, 4'-difluorobenzophenone with BPA-NB and various compositions of BPA-NB and bisphenol-A, respectively. H-1 NMR spectroscopy confirmed the chemical structure and composition of PEEK-NBs. Inherent viscosity and number-average molecular weight values of PEEK-NBs were in the range 0.64 to 0.78 dL g(-1) and 62,670 to 84,470 g mol(-1), respectively, indicating the formation of polymers of reasonably high molecular weight. It was easy to dissolve PEEK-NBs in common organic solvents such as chloroform, dichloromethane, and tetrahydrofuran. Tough, transparent, and flexible films of PEEK-NBs could be cast from chloroform solution. X-Ray diffraction studies indicated amorphous nature of PEEK-NBs. Glass transition temperature (T-g) values, determined by DSC analysis, of PEEK-NBs were in the range 163 to190 degrees C and T-g values increased with the increase in mol % of BPA-NB. The post-polymerization modification of a representative PEEK-NB was demonstrated using two azido compounds, namely, 4-(azidomethyl)-7-methoxy-2H-chromen-2-one and 9-(azidomethyl)anthracene, via metal-free azide-alkene 1,3-dipolar cycloaddition reaction to obtain copoly(ether ether ketone)s appended with coumarinyl and anthracenyl moieties, respectively.
Keywords: (Co)poly(ether ether ketone)s; azide-alkene click reaction; norbornenyl groups; post-polymerization modification

Organocatalysed one-pot three component synthesis of 3,3′-disubstituted oxindoles featuring an all-carbon quaternary center and [spiro 2H-pyran-3,4′-indoline] - Nichinde, Chandrakant B.; Patil, Baliram R.; Chaudhari, Suryakant S.; Mali, Bhupendra P.; Gonnade, Rajesh G.; Kinage, Anil K. (RSC Advances, 2023)
A simple and efficient methodology for the one-pot synthesis of 3,3 `-disubstituted oxindoles featuring an all-carbon quaternary center has been demonstrated through l-proline catalysed three-component reaction based on sequential Knoevenagel condensation/Michael addition and also one-pot synthesis of spiro[2H-pyran-3,4 `-indoline] through consecutive Knoevenagel condensation/Michael addition/reduction/cyclization reactions from readily available isatin derivatives, malononitrile, and ketones. The present methodology presents several advantages, including simple reaction set-up, short reaction times, and easy to work-up. Also, this strategy offers broad substrate scope with excellent yields and high atom economy, under mild reaction conditions.

Palladium-catalyzed polar solvent empowered synthesis of hyper-branched ethylene oligomers and their applications - Birajdar, Rajkumar S.; Gonnade, Rajesh G.; Pol, Harshawardhan V.; Prabhu, M. Basava; Rokade, Dhammaraj; Nandimath, Sheetal; Chikkali, Samir H. (Polymer Chemistry, 2023)
In this contribution, we report the synthesis of two naphthoxy imine ligands, 2-(((2,6-dibenzhydryl-4-methoxyphenyl)imino)methyl)naphthalen-1-ol (L1) and 2-(((2,6-diisopropylphenyl)imino)methyl)naphthalen-1-ol (L2), with different steric and electronic features. L1 and L2 were treated with [(TMEDA)PdMe2] to obtain the corresponding neutral palladium(ii) complexes Cat.1 and Cat.2 in excellent yields. The identity of Cat.1 and Cat.2 was unambiguously ascertained using a combination of spectroscopic and analytical methods, including single-crystal X-ray diffraction. When exposed to 5 bar ethylene pressure, Cat.1 produced hyperbranched ethylene oligomers. The microstructure analysis of ethylene oligomers confirmed the existence of methyl, ethyl, propyl, and sec-butyl branches, with a molecular weight (M-n) of 500-1400 g mol(-1), a PDI of 1.46-2.10, and 67-106 branches per 1000 carbon atoms. The use of a polar solvent, tetrahydrofuran, led to a remarkable 3-fold increase in oligomerization activity without compromising the branching and molecular weight. The resultant hyperbranched ethylene oligomers were selectively monofunctionalized using industrially practiced hydroformylation, ozonolysis, and epoxidation, almost quantitatively. The hydroxy functionalized ethylene oligomer (F4) (5 wt%) was melt-compounded with LLDPE and Nylon-6 to produce a tough yet flexible blend with a higher strain-to-failure as compared to an uncompatibilized blend.

Palmitoylation of the glucagon-like peptide-1 receptor modulates cholesterol interactions at the receptor-lipid microenvironment - Naglekar, Amit; Chattopadhyay, Amitabha; Sengupta, Durba (Journal of Physical Chemistry B, 2023)
The G protein-coupled receptor (GPCR) superfamily of cell surface receptors has been shown to be functionally modulated by post-translational modifications. The glucagon-like peptide receptor-1 (GLP-1R), which is a drug target in diabetes and obesity, undergoes agonist-dependent palmitoyl tail conjugation. The palmitoylation in the C-terminal domain of GLP-1R has been suggested to modulate the receptor-lipid microenvironment. In this work, we have performed coarse-grain molecular dynamics simulations of palmitoylated and nonpalmitoylated GLP-1R to analyze the differential receptor-lipid interactions. Interestingly, the placement and dynamics of the C-terminal domain of GLP-1R are found to be directly dependent on the palmitoyl tail. We observe that both cholesterol and phospholipids interact with the receptor but display differential interactions in the presence and absence of the palmitoyl tail. We characterize important cholesterol-binding sites and validate sites that have been previously reported in experimentally resolved structures of the receptor. We show that the receptor acts like a conduit for cholesterol flip-flop by stabilizing cholesterol in the membrane core. Taken together, our work represents an important step in understanding the molecular effects of lipid modifications in GPCRs.

Pd loaded bismuth ferrite: a versatile perovskite for dual applications as acetone gas sensor and photocatalytic dye degradation of malachite green - Ghadage, Pandurang; Kodam, Pavan; Nadargi, Digambar; Patil, Suraj; Tamboli, Mohaseen; Bhandari, Nagesh; Mulla, Imtiaz; Park, Chinho; Suryavanshi, Sharad (Ceramics International, 2023)
Herein we report the palladium loaded bismuth ferrite for its bidirectional application as acetone gas sensor and photocatalytic dye degradation of malachite green. The motivation for loading Pd on bismuth ferrite (BFO) is due to its fascinating catalytic redox reactions causing faster adsorption and desorption of the oxygen molecules over the metal oxide. The planned perovskites were developed via surfactant assisted sol-gel auto-combustion route, and characterized their physico-chemical properties using XRD, SEM, TEM, HRTEM, EDAX, XPS and BET. The developed BFO showed the best selectivity towards acetone, whose response was 69% at 300 degrees C operating temperature for 500 ppm gas concentration. By tuning the surface area and catalytic behavior using CTAB and Pd loading, respectively, the enhancement in the gas response properties of BFO was achieved to 95% with the response and recovery time of 75 s and 104 s. The 1 wt% Pd loaded BFO showed the highest response (95%) in comparison to rest of the Pd loadings (0.5, 1.5 and 2.0 wt%). Moreover, the sunlight driven photocatalytic dye degradation of malachite green is carried out at 1 h exposure time. Here as well, 1 wt% Pd loaded BFO exhibited the maximum dye degradation efficiency of 51%. The results of this study demonstrate the developed perovskites have a significant potential for the use in dual applications such as acetone gas sensor and MG photocatalysis.
Keywords: Acetone sensor; Bismuth ferrite; Palladium loading; Photo dye -degradation

Photocatalytic setup for in situ and operando ambient-pressure X-ray photoelectron spectroscopy at MAX IV Laboratory - Klyushin, Alexander; Ghosalya, Manoj; Kokkonen, Esko; Eads, Calley; Jones, Rosemary; Nalajala, Naresh; Gopinath, Chinnakonda S.; Urpelainen, Samuli (Journal of Synchrotron Radiation, 2023)
The Ambient-Pressure X-ray Photoelectron Spectroscopy (APXPS) endstation at the SPECIES beamline at MAX IV Laboratory has been improved. The latest upgrades help in performing photo-assisted experiments under operando conditions in the mbar pressure range using gas and vapour mixtures whilst also reducing beam damage to the sample caused by X-ray irradiation. This article reports on endstation upgrades for APXPS and examples of scientific cases of in situ photocatalysis, photoreduction and photo-assisted atomic layer deposition (photo-ALD).
Keywords: APXPS; photo-ALD; Photocatalysis; solar simulator

Photoplethysmograph based arrhythmia detection using morphological features - Neha; Sardana, H. K.; Kanawade, R.; Dogra, N. (Biomedical Signal Processing and Control, 2023)
Photoplethysmography (PPG) is a non-invasive optical technique that is used for the detection of cardiovascular diseases. The paroxysmal nature of arrhythmic events and the lack of timely recorded data emphasize the need to develop an automated method for the identification of arrhythmias. The literature shows the detection of a single type of arrhythmia using PPG. However, limited research has been carried out for the detection of multiple types of arrhythmia. In this research work, a new set of morphological features have been proposed for the automated detection of multiple arrhythmias using rule-based and statistical learning-based approaches. The proposed work has been implemented on the retrospective dataset and validated on the prospective dataset. The results show that the rule-based arrhythmia detection method is equipollent to the statistical learning approach with an accuracy of 98.43%/94.16% on the retrospective dataset and 94.16%/93% on the prospective dataset.
Keywords: Arrhythmia; Machine learning algorithms; Photoplethysmography; Signal processing

Photo-stable, 1D-nanofilaments TiO2-based lepidocrocite for photocatalytic hydrogen production in water-methanol mixtures - Badr, Hussein O.; Natu, Varun; Neatu, Stefan; Neatu, Florentina; Kuncser, Andrei; Rostas, Arpad M.; Racey, Matthew; Barsoum, Michel W.; Florea, Mihaela (Matter, 2023)
Water and sunlight are the cleanest, most renewable, and abundant resources on Earth. Developing inexpensive, scalable photocatalysts that are highly stable for hydrogen (H-2) production has long been a cherished dream of humanity. Herein, we report on one-dimensional lepidocrocite-based sub-nanofilaments (NFs), approximate to 5 x 7 & Aring;(2) in cross-section, that generate H-2 from 80:20 v/v water/methanol mixtures when illuminated by simulated sunlight. The NFs were stable in the mixtures for times >4,300 h, 300 h of which were under irradiation. Apparent quantum yields as high as 11.7% were obtained. Based on deuterated water results, we conclude that water is the H-2 source. Further, no carbon dioxide (CO2) due to photocatalytic degradation of methanol was detected. Therefore, the NFs have strong green credentials and lucrative economic prospects for large scale up. We expect these NFs will lead to new lines for developing cheap and ultra-stable materials to produce H-2 photochemically for a long time.

Poly-gamma-glutamic acid biopolymer: a sleeping giant with diverse applications and unique opportunities for commercialization - Nair, Pranav; Navale, Govinda R.; Dharne, Mahesh S. (Biomass Conversion and Biorefinery, 2023)
Poly-gamma-glutamic acid (gamma-PGA) is a biodegradable, non-toxic, ecofriendly, and non-immunogenic biopolymer. Its phenomenal properties have gained immense attention in the field of regenerative medicine, the food industry, wastewater treatment, and even in 3D printing bio-ink. The gamma-PGA has the potential to replace synthetic non-degradable counterparts, but the main obstacle is the high production cost and lower productivity. Extensive research has been carried out to reduce the production cost by using different waste; however, it is unable to match the commercialization needs. This review focuses on the biosynthetic mechanism of gamma-PGA, its production using the synthetic medium as well as different wastes by L-glutamic acid-dependent and independent microbial strains. Furthermore, various metabolic engineering strategies and the recovery processes for gamma-PGA and their possible applications are discussed. Finally, highlights on the challenges and unique approaches to reduce the production cost and to increase the productivity for commercialization of gamma-PGA are also summarized.
Keywords: Commercialization; Multi-nutritious; Poly-gamma-glutamic acid; Waste valorization

Polymerizable solvent-free organic liquids: a new approach for large area flexible and foldable luminescent films - Wakchaure, Vivek Chandrakant; Veer, Sairam Dnyaneshwar; Nidhankar, Aakash D.; Kumar, Viksit; Narayanan, Aswini; Babu, Sukumaran Santhosh (Angewandte chemie-international editon, 2023)
The high demand for light-emitting and display devices made luminescent organic materials as attractive candidates. Solvent-free organic liquids are one of the promising emitters among them due to the salient features. However, the inherent limitations of forming sticky and noncurable surfaces must be addressed to become an alternate emitter for large-area device applications. Herein, we functionalized solvent-free organic liquids having monomeric emission in bulk with polymerizable groups to improve the processability. The polymerizable group on carbazole, naphthalene monoimide, and diketopyrrolopyrrole-based solvent-free liquid emitters enabled on-surface polymerization. These emitters alone and in combinations can be directly coated on a glass substrate without the help of solvents. Subsequent photo or thermal polymerization leads to stable, non-sticky, flexible, foldable, and free-standing large-area films with reasonably high quantum yield. Our demonstration of the tunable and white light-emitting films using polymerizable solvent-free liquids might be a potential candidate in flexible/foldable/stretchable electronics. The new concept of polymerizable liquid can be extended to other functional features suitable for futuristic applications.
Keywords: Energy Transfer; polymerization; Solvent-Free Organic Liquids; Thin-Film; White Light

Polymorph II of hydroxyurea 150 years after its first synthesis - Rai, Sunil K.; Tothadi, Srinu; Arhangelskis, Mihails; George, Christy P.; Gonnade, Rajesh G.; Nangia, Ashwini K. (Crystengcomm, 2023)
A new polymorph of hydroxyurea (HU) was crystallized 150 years after its first synthesis. Due to its medicinal use in neoplastic diseases and sickle cell anemia, a high throughput screen of HU binary cocrystals was attempted. Instead of a cocrystal, an isoenergetic form II crystallized concomitantly with urea in methanol.

Possible handle for broadening the catalysis regime towards low temperatures: proof of concept and mechanistic studies with CO oxidation on surface modified Pd-TiO2 - Mhamane, Nitin B. B.; Panchal, Suresh; Kolekar, Sadhu K. K.; Ranjan, Ravi; Salgaonkar, Kranti N. N.; Burange, Anand S. S.; Nalajala, Naresh; Datar, Suwarna; Gopinath, Chinnakonda S. S. (Physical Chemistry Chemical Physics, 2023)
The present work demonstrates the effect of temperature-dependent surface modification (SM) treatment and its influence in broadening the catalysis regime with Pd-TiO2 catalysts prepared by various methods. Due to SM induced changes, a shift in the onset of CO oxidation activity as well as broadening of the oxidation catalysis regime by 30 to 65 K to lower temperatures is observed compared to the temperature required for virgin counterparts. SM carried out at 523 K for Pd-Photo-TiO2 exhibits the lowest onset (10% CO2 production - T-10) and T-100 for CO oxidation at 360 and 392 K, respectively, while its virgin counterpart shows T-10 and T-100 at 393 and 433 K, respectively. The SMd Pd-TiO2 catalysts were investigated using X-ray photoelectron spectroscopy (XPS), ultra-violet photoelectron spectroscopy (UPS) and atomic force microscopy (AFM). It is observed that diffusion of atomic oxygen into Pd-subsurfaces leads to SM and changes the nature of the surface significantly. These changes are demonstrated by work function (& phi;), surface potential, catalytic activity, and correlation among them. UPS results demonstrate the maximum increase in & phi; by 0.5 eV for Pd-Photo-TiO2 after SM, compared to all other catalysts. XPS study shows a moderate to severe change in the oxidation states of Pd due to atomic oxygen diffusion into the subsurface layers of Pd. Kelvin probe force microscopy (KPFM) study also reveals corroborating evidence that the surface potential increases linearly with increasing temperature deployed for SM up to 523 K, followed by a marginal decrease at 573 K. The & phi; measured by KPFM and UPS shows a similar trend and correlates well with the changes in catalysis observed. Our results indicate that there is a strong correlation between surface physical and chemical properties, and & phi; changes could be considered as a global marker for chemical reactivity.

Post-refolding stability considerations for optimization of in-vitro refolding: L-asparaginase as a case study - Mihooliya, Kanti Nandan; Nitika, Nitika; Bhambure, Rahul; Rathore, Anurag S. S. (Biotechnology Journal, 2023)
BackgroundL-Asparaginase is an essential enzyme for the food and biopharmaceutical industry. The stability, however, of L-asparaginase is widely known to be an issue. Commercial manufacturing of any biopharmaceutical involves hold-ups during processing, and can result in product loss if stability is an issue, as is the case with L-asparaginase. This interplay of product intermediate stability and process design is the focus of this investigation. Methods and ResultsIn this study, we propose a strategy to simultaneously increase the refolding yield and stability of refolded L-asparaginase so as to improve overall process yield. Using one variable at a time (OVAT) experiments, urea (6 M), solubilized inclusion bodies (15 mg/ml), refolding method (step dilution), and pH (8.6) were identified as significant process parameters. A design of experiment (DOE)-based optimization was then performed for the refolding step. The net outcome was more than a three-fold increase in enzyme recovery (i.e., 4.90 IU/ml) compared to unoptimized conditions (i.e., 1.26 IU/ml). Further, the L-asparaginase process intermediate was found to be stable for more than a week at room temperature and 2-8 degrees C, while the unoptimized sample was stable at 2-8 degrees C but did not show any activity at room temperature after 72 h. ConclusionsThe current study elucidates how process intermediate stability needs to be given due consideration during process optimization, particularly for products such as L-asparaginase which are labile.
Keywords: design of experiment; L-asparaginase; refolding; stability

Relativistic coupled-cluster study of SrF for low-energy precision tests of fundamental physics - Talukdar, Kaushik; Buragohain, Haimyapriya; Nayak, Malaya K. K.; Vaval, Nayana; Pal, Sourav (Theoretical Chemistry Accounts, 2023)
SrF, being a laser-coolable molecule, can be an interesting system for spectroscopic tests of fundamental physics. We present an electronic structure study of this molecule within the four-component relativistic coupled-cluster singles and doubles (RCCSD) framework and employ the RCCSD-based methods to compute its molecular-frame dipole moment and core properties such as hyperfine structure coupling constant and molecular P, T-odd electronic structure parameters that are of great importance for the high-precision tests of fundamental physics. The impact of basis set size, Hamiltonian and nuclear model on the property calculation of SrF is also investigated. The computed results are in good agreement with the available experimental values. The present study shows that the SrF molecule could be useful for high-precision molecular experiments to explore physics beyond the Standard Model of elementary particles.
Keywords: Coupled cluster theory; CP violation; Hyperfine structure; Molecular spectroscopy; Relativistic effects

Rheology and processing study on controlling material and process defects in polymer melt extrusion film casting using polymer blends - Rokade, Dhammaraj; Patil, Prashant; Nandimath, Sheetal; Pol, Harshawardhan (Journal of Plastic Film & Sheeting, 2023)
The primary objective of this research paper is to control the material and process defects in polymer melt extrusion film casting (EFC) process for linear chain architecture polyethylene (PE) resins through polymer blending methodology. Extrusion film casting is a well-known industrially important manufacturing process that is used to manufacture thousands of tons of polymer/plastic films/sheets and coated products. In this research, the necking defect in an EFC process has been studied experimentally for a linear low density polyethylene (LLDPE) resin and attempts have been made to control its necking by blending in a long chain branched (LCB) low density polyethylene (LDPE) resin. The blending methodology is based on the understanding that a LDPE resin displays enhanced resistance to necking as compared to the LLDPE resin. It is found that added LDPE resin enhances necking resistance for the primary LLDPE resin. Further, as the LDPE concentration increases in the blend formulation, the necking is further reduced as compared to pure LLDPE. Analogous to past studies on EFC of linear and long chain branched architecture containing PEs, it is observed that as the LDPE is increased in the blend formulations, the formulations displayed enhanced melt elasticity and extensional strain hardening in rheological studies. It is concluded from this study that polyethylene resins having linear chain architecture can be made amenable to enhanced resistance to necking using appropriate amount of a long chain branched resins. Finally, process defects such as the draw resonance onset could be shifted to higher draw ratios as the LDPE level is increased in the LLDPE-LDPE blend formulation.
Keywords: Draw resonance; Extrusion; Film; linear chain; long-chain branched; melt elasticity; Necking; onset; strain hardening

Role of ions and their transporters in combating salt stress in Pandanus odorifer (Forssk.) Kuntze - Rashmi, Deo; Ansari, Waquar A.; Kadoo, Narendra Y.; Barvkar, Vitthal T.; Deshmukh, Rupesh; Nadaf, Altafhusain B. (Acta Physiologiae Plantarum, 2023)
Soil salinity is a major environmental constraint causing huge losses in crop production. Pandanus odorifer (Forssk.) Kuntze is an aromatic monocot plant species belonging to the family Pandanaceae, which grows naturally on the saline soils along the coasts of Asia, Southeast Asia, and Polynesia. The plants are dioecious and highly fertile, and the consistent saline sprays, strong winds, and severe soil salinity hardly affect their growth and fertility. Hence, understanding the mechanism of high salinity tolerance in P. odorifer could provide major advances in overcoming salinity stress in crop plants. In the present study, we analyzed control (0 M NaCl) and treated (1 M NaCl treatment for 3 weeks) plants of P. odorifer to understand the role of ion distribution, ion transport, and related mechanisms under salt stress. Using a combination of ionomics and transcriptomics approaches, we identified the molecular mechanisms contributing to the high salinity stress in P. odorifer. Under NaCl stress, there was a significant increase in Na, Cl, and other ions in leaves, while the concentrations of Si, Fe, Ni, and Ti decreased. Similarly, in roots, the levels of Na, Mg, Cd, and Cr were significantly high, while the levels of other ions decreased. Most of the genes related to ion transport and homeostasis, such as NHX1, CLC-C, SOS1, HAK, and ABC transporters, were upregulated in 1 M NaCl stress conditions. This study revealed that vacuolar sequestration of Na+ and the distribution of ions in the roots and shoots play significant roles in the salt-stress tolerance mechanism of P. odorifer.
Keywords: Ion transport; Ionomics; Pandanus; Salinity tolerance; Transcriptomics; Vacuolar sequestration

Scalable synthesis of silacyclohexanones and ready access to silicon building blocks - Ramesh, Eagala; Nandawadekar, Laxman D.; Rao, Ramana Sreenivasa; Reddy, D. Srinivasa (Organic Letters, 2023)
A simple and efficient two-step method for the synthesis of silacyclohexanones starting from bis(bromoethylsilanes) using TosMIC is presented. The prepared silacyclohexanones were transformed to nine different heterocycles with silicon incorporation. In addition, the developed methodology was used for the synthesis of a sila analogue of the HDAC6 inhibitor tubastatin A.

Selective and generic photocatalytic oxidation of alcohol with Pd-TiO2 thin films: butanols to butanal/butanone with different morphologies of Pd and 0.5 theta(Pt)-Pd counterparts - Salgaonkar, Kranti N.; Kale, Sandip R.; Nalajala, Naresh; Mansuri, Sayana; Gopinath, Chinnakonda S. (Chemistry-An Asian Journal, 2023)
The present study reports on the photocatalytic oxidation of butanols to butanal/butanone using thin film form of facet-dependent nano-Pd supported on commercial TiO2 under one-sun condition and demonstrates the generic nature. Pd-nanocube (Pd-NC(100)), Pd-truncated octahedron (Pd-TO (100) and (111)), polycrystalline (Pd-PC), and their counterparts with half-a-monolayer Pt-coated on Pd (0.5 theta(Pt)-Pd)) have been used as co-catalyst. A potentially scalable thin film form of Pd/TiO2 photocatalyst, prepared by drop-casting method, has been employed to study oxidation of n-butanol, 2-butanol, and iso-butanol to corresponding aldehyde/ketone. 100% selectivity is demonstrated to respective aldehyde/ketone with any catalyst used in the present study with varying degree of butanols conversion by NMR. 0.5 theta(Pt)-Pd-TO/TiO2 shows the highest conversion of 2-butanol to butanone (13.6% in 4 h). Continuous 10 h of reaction with the most active 0.5 theta(Pt)-Pd-TO/P25 catalyst demonstrates 31% conversion of 2-butanol to butanone, and catalyst recyclability has been demonstrated. The present protocol can be scalable to large scales to maximize the conversion in direct sunlight. Due to its generic nature, the current method can also be applied to many other alcohols and substrate molecules.
Keywords: energy conversion; Nanomaterials; Oxidation; Photocatalysis; Sustainability

Self-assembled amino acid microstructures as biocompatible physically unclonable functions (BPUFs) for authentication of therapeutically relevant hydrogels - Akavaram, Vishwas; Kumar, Kush; Sriram, Shreya; Narra, Saisrinath; Kumawat, Akshant; Meena, Santosh Kumar; Pushpavanam, Karthik (Macromolecular Bioscience, 2023)
Counterfeited biomedical products result in significant economic losses and pose a public health hazard for over a million people yearly. Hydrogels, a class of biomedical products, are being investigated as alternatives to conventional biomedical products and are equally susceptible to counterfeiting. Here, a biocompatible, physically unclonable function (BPUF) to verify the authenticity of therapeutically relevant hydrogels are developed. The principle of BPUF relies on the self-assembly of tyrosine into fibril-like structures which are incorporated into therapeutically relevant hydrogels resulting in their random dispersion. This unclonable arrangement leads to distinctive optical micrographs captured using an optical microscope. These optical micrographs are transformed into a unique security code through cryptographic techniques which are then used to authenticate the hydrogel. The temporal stability of the BPUFs are demonstrated and additionally, exploit the dissolution propensity of the structures upon exposure to an adulterant to identify the tampering of the hydrogel. Finally, a platform to demonstrate the translational potential of this technology in validating and detecting tampering of therapeutically relevant hydrogels is developed. The potential of BPUFs to combat hydrogel counterfeiting is exemplified by its simplicity in production, ease of use, biocompatibility, and cost-effectiveness.
Keywords: anti-counterfeiting; hydrogels; physically unclonable functions; Self-assembly; translational

Short review on recent advances in porous adsorbents for separation of oxygen from atmospheric air - Shrotri, Aadesh R. R.; Niphadkar, Prashant S. S.; Bokade, Vijay V. V.; Utgikar, Vivek P. P.; Nandanwar, Sachin U. U. (Asia-Pacific Journal of Chemical Engineering, 2023)
Pure oxygen demand is continuously increasing worldwide due to wide applications including medical and industrial. Pressure swing adsorption (PSA) is one of the promising techniques to separate O-2 from atmospheric air. The porous solid adsorbent is a key element in the PSA to trap nitrogen (N-2) and release O-2. Several adsorbents including low silica X (LSX), zeolite 5A, ion-exchanged LSX (Li-LSX, AgLi-LSX, Ca-LSX), Engelhard titanosilicate (Na-ETS-10, Ag-ETS-10), and SSZ-13 have been investigated for adsorption of N-2 from the air. This review article is a summarization of recent research work published on O-2 separation using different porous adsorbents via PSA. This review also emphasizes on the best porous sorbent for purification of O-2 by sorption of N-2 and Ar. The adsorption capacities with experimental conditions are also rigorously discussed. The review also proposed future trends and prospects for O-2 separation. This review will be helpful to choose remarkable adsorbent for the generation pure O-2.
Keywords: 13X zeolite; adsorbent; ETS-10; oxygen; Separation

Size does matter: antibacterial activities and cytotoxic evaluation of polymorphic CuO nanostructures - Desai, Dnyanada G.; Navale, Govinda R.; Late, Dattatray J.; Dharne, Mahesh S.; Walke, Pravin S. (Journal of Materials Science, 2023)
Nanostructured materials play a significant role in antibacterial activities. However, understanding the geometrical influence at the nanoscale in terms of size- and shape-correlated physical properties on antibacterial activities is very essential. Herein, we report the antibacterial influence of various copper oxide nanostructures (CuO NS) such as nanoparticles (NPs) (< 10 nm), nanospheres (NSs) (50-100 nm), and porous nanoflowers (NFs) (asymptotic to 350 nm). The XRD confirmed the crystalline nature of CuO NPs without impurities. The antibacterial activities of CuO NPs were investigated by the microplate dilution method and confocal laser scanning microscopic (CLSM) imaging. NPs having a diameter less than 10 nm exhibited significant damage to the bacterial cell membrane than NSs and NFs. Interestingly, NPs illustrated relatively low antibacterial activity against Gram-negative bacteria (Pseudomonas aeruginosa and Acinetobacter baumannii) than Gram-positive bacteria (Staphylococcus aureus and Staphylococcus epidermidis). Acinetobacter baumannii was found to be more susceptible to the NPs than other bacterial strains, attributed to its increased membrane permeability. The death phase was observed at a concentration of 15.6 mu g mL(-1) and 3.9 mu g mL(-1) for P. aeruginosa and A. baumannii, respectively, when treated with CuO NP after the 8 h of incubation. Similarly, for S. aureus and S. epidermidis, the death phase was observed at the concentration of 31.2 mu g mL(-1) and 250 mu g mL(-1), respectively. Furthermore, as the cell cytotoxicity measurements against human fibroblast L9239 cells revealed that CuO NPs were safe. The morphological and cell viability assay demonstrated 100% cell survival, when treated with NPs and NSs (5, 10, and 25 mu g mL(-1)), signifies no cytotoxicity. Therefore, CuO nanoparticles can be used for clinical and therapeutic applications.

Steric and electronic effect in unsymmetrical squaraine dyes for dye-sensitized solar cells - Nawghare, Indrajeet S.; Singh, Ambarish Kumar; Maibam, Ashakiran; Krishnamurty, Sailaja; Krishnamoorthy, Kothandam; Nithyanandhan, Jayaraj (Journal of physical chemistry C, 2023)
Functionalizing the light harvesting sensitizers with additional electron-donating or -withdrawing groups is a potential approach to modulate the photophysical and electrochemical properties which in-turn optimizes the driving force associated with the charge injection and dye-regeneration processes at the dye-TiO2/electrolyte interface and the photovoltaic device performance in dye-sensitized solar cells (DSSCs). Furthermore, modulated electronic levels of the dyes provide an opportunity to reduce the overpotential associated with the dye-regeneration process and make the dye-TiO2 interface compatible with various electrolytes. Furthermore, an in-built steric feature by means of introducing linear/branched alkyl groups in the sensitizer is important in controlling the aggregation of dyes on the TiO2 surface. Hence, to integrate both steric and electronic properties, a series of alkyl group-wrapped unsymmetrical squaraine dyes (SQ-X) with electron-donating and -withdrawing groups have been designed, synthesized, and utilized for DSSC device fabrication. These dyes are functionalized with alkyl groups at both sp(3)-C and N-atoms of the indoline donor moiety at the nonanchoring side to have a similar steric feature. Photophysical and electrochemical studies revealed that the HOMO and LUMO energy levels of the SQ-X series of dyes have been modulated systematically with sufficient driving forces for both charge injection and dye-regeneration processes with iodolyte (I-/I-3(-)) electrolyte. In the presence of electron-donating groups in SQ-X (where X = -NPh2 and -OMe), the HOMO energy levels are less positive than SQ-H, whereas the presence of electron-withdrawing groups such as -CO2Me, -CN, and -NO2 pushed the HOMO energy levels toward more positive potentials. Enhanced photovoltaic performances have been obtained for the dyes containing electron-donating groups, where the dye with the -NPh2 group showed a maximum of eta 7.03% (V-OC 708 mV, J(SC) 13.16 mA cm(-2), and ff 78%). The dye with the strong electron-withdrawing group -NO2 showed an efficiency of 1.49% (V-OC = 634 mV, J(SC) = 3.13 mA cm(-2), and ff 75%). As the dyes with the electron-withdrawing group possess deep positive HOMO energy levels, the DSSC device characterization has been investigated with the Cu+/2+ redox shuttle. The reduced device performance of electron-withdrawing-group-containing dyes is due to the unfavored charge distribution in the LUMO compared to the presence of electron-donating-group-containing dyes, and it was supported by the difference in the charge injection efficiency.
Keywords: cobalt; Donor; Dynamics; Organic dyes

Sustainable and cleaner production of poly-gamma-glutamic acid (γ-PGA) biopolymer using floral waste and its anti-staling properties - Nair, Pranav G.; Dharne, Mahesh S. (Journal of Cleaner Production, 2023)
The framework of sustainable development (SD) hinges on 17 different ideals established by the United Nations. This call for SD can be addressed by the circular bio-economy concept, which not only ensures effective waste management but also encourages its valorization and repurposing, hence fostering both ecological and economic stability. One-third of the world's floral production is in jeopardy, and because there are no potential solutions for sustaining floral waste, it inevitably ends up in landfills and riverine systems, which is detrimental to the environment. Therefore, in the present study, floral waste that was destined for landfills or water bodies was productively valorized to poly gamma glutamic acid (gamma-PGA), a high value biopolymer, with a yield of 40 g/L and productivity of 1.6 g/L/h employing an L-glutamic acid (L-GA) independent feeding approach. When gamma-PGA was coated onto Vitis vinifera grapes, it exhibited excellent moisture retention, reduced microbial contamination, and preserved the grapes' aesthetic characteristics and nutrient content. The weight loss study demonstrated that grapes coated with 1% and 2% gamma-PGA experienced significantly lower weight loss (13% and 14% respectively) compared to the control group (21.6%). Moreover, a 5-min dip coating time proved to be the most effective in reducing weight loss to 12.43%. Over a period of 14 days, the control group exhibited a remarkably high weight loss (41%) in contrast to the treated group, which showed significantly lower weight loss (16%). Our work is a fine example of how the circular bio-economy and waste valorization may be used to achieve the long-term objectives of sustainable development, economic stability, and food security.
Keywords: Bio-economy; Floral waste; L-GA independent; Poly-gamma-glutamic acid; Valorization

Synthesis, characterization and post-modification of aromatic (Co)polyesters possessing pendant maleimide groups - Jadhav, Uday A.; Nagane, Samadhan S.; Wadgaonkar, Prakash P. (High Performance Polymers, 2023)
A new series of (co)polyesters possessing pendent maleimide groups was synthesized by low temperature solution polycondensation of 4, 4’-(5-maleimidopentane-2, 2-diyl) diphenol (BPA-MA) with isophthalic acid chloride (IPC), terephthalic acid chloride (TPC) and a mixture of TPC and IPC (50:50 mol %). Copolyesters were also synthesized by polycondensation of varying compositions of BPA-MA and bisphenol-A (BPA) with IPC. The chemical structures and compositions of (co)polyesters were confirmed by NMR spectroscopy. Inherent viscosity values and number-average molecular weights of (co)polyesters were in the range 0.50–0.76 dL/g and 17,700-32,100 g/mol, respectively, indicating the formation of reasonably high molecular weight polymers. (Co)polyesters were readily soluble in common organic solvents and could be cast into tough, transparent and flexible films from chloroform solutions. (Co)polyesters exhibited 10% weight loss and glass transition temperatures in the range 464–468 and 142–178°C, respectively. A representative copolyester possessing pendant maleimide groups was chemically modified via metal-free azide-maleimide 1,3-dipolar cycloaddition click reaction with two azido compounds, namely, (azidomethyl)benzene (Bz-N3) and 1-(azidomethyl)-pyrene (Py-N3) to yield corresponding modified copolyesters in a quantitative manner.

Tale of two waves: Delineating diverse genomic and transmission landscapes driving the COVID-19 pandemic in Pune, India - Niveditha, Divya; Khan, Soumen; Khilari, Ajinkya; Nadkarni, Sanica; Bhalerao, Unnati; Kadam, Pradnya; Yadav, Ritu; Kanekar, Jugal B.; Shah, Nikita; Likhitkar, Bhagyashree; Sawant, Rutuja; Thakur, Shikha; et al. (Journal of Infection and Public Health, 2023)
Background: Modern response to pandemics, critical for effective public health measures, is shaped by the availability and integration of diverse epidemiological outbreak data. Tracking variants of concern (VOC) is integral to understanding the evolution of SARS-CoV-2 in space and time, both at the local level and global context. This potentially generates actionable information when integrated with epidemiological outbreak data.Methods: A city-wide network of researchers, clinicians, and pathology diagnostic laboratories was formed for genome surveillance of COVID-19 in Pune, India. The genomic landscapes of 10,496 sequenced samples of SARS-CoV-2 driving peaks of infection in Pune between December-2020 to March-2022, were determined. As a modern response to the pandemic, a ``band of five'' outbreak data analytics approach was used. This integrated the genomic data (Band 1) of the virus through molecular phylogenetics with key outbreak data including sample collection dates and case numbers (Band 2), demographics like age and gender (Band 3-4), and geospatial mapping (Band 5).Results: The transmission dynamics of VOCs in 10,496 sequenced samples identified B.1.617.2 (Delta) and BA(x) (Omicron formerly known as B.1.1.529) variants as drivers of the second and third peaks of infection in Pune. Spike Protein mutational profiling during pre and post-Omicron VOCs indicated differential rank ordering of high-frequency mutations in specific domains that increased the charge and binding properties of the protein. Time-resolved phylogenetic analysis of Omicron sub-lineages identified a highly divergent BA.1 from Pune in addition to recombinant X lineages, XZ, XQ, and XM. Conclusions: The band of five outbreak data analytics approach, which integrates five different types of data, highlights the importance of a strong surveillance system with high-quality meta-data for understanding the spatiotemporal evolution of the SARS-CoV-2 genome in Pune. These findings have important implica-tions for pandemic preparedness and could be critical tools for understanding and responding to future outbreaks.& COPY; 2023 Published by Elsevier Ltd on behalf of King Saud Bin Abdulaziz University for Health Sciences. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Keywords: COVID-19; Delta; Omicron; SARS-CoV-2 genomic surveillance; Variant of concern; Whole Genome Sequencing (WGS)

Thermally activated delayed fluorescent solvent-free organic liquid hybrids for tunable emission applications - Nidhankar, Aakash D. D.; Goudappagouda; Kothavade, Premkumar D.; Dongre, Sangram D.; Veer, Sairam Dnyaneshwar; Dash, Soumya Ranjan; Rajeev, Kavya; Unni, K. N. Narayanan; Shanmuganathan, Kadhiravan; Babu, Sukumaran Santhosh (Chemistry-An Asian Journal, 2023)
The synthetic feasibility and excellent luminescence features of organic molecules attracted much attention and were eventually found useful in lighting applications. In this context, a solvent-free organic liquid having attractive thermally activated delayed fluorescence features in bulk along with high processability has prime importance. Herein, we report a series of naphthalene monoimide-based solvent-free organic liquids exhibiting cyan to red thermally activated delayed fluorescence with luminescence quantum yields up to 80% and lifetimes between 10 to 45 mu s. An effective approach explored energy transfer between liquid donors with various emitters exhibiting tunable emission colors, including white. The high processability of liquid emitters improved the compatibility with polylactic acid and was used for developing multicolor emissive objects using 3D printing. Our demonstration of the thermally activated delayed fluorescence liquid will be much appreciated as a processable alternate emissive material suitable for large-area lighting, display, and related applications.
Keywords: 3D printing; Energy Transfer; OLED; Organic Liquids; TADF

Trehalose transporter-like gene diversity and dynamics enhances stress response and recovery in Helicoverpa armigera - Tellis, Meenakshi B.; Chaudhari, Bhagyashri Y.; Deshpande, Shweta V.; Nikam, Sanika V.; Barvkar, Vitthal T.; Kotkar, Hemlata M.; Joshi, Rakesh S. (Gene, 2023)
Trehalose is a primary sugar and its distribution across the insect body, regulated by trehalose transporters (TRETs), is essential for sugar metabolism and energy homeostasis. The large diversity of Tret-like sugar trans-porters (ST), belonging to SLC2A transporter family, in polyphagous insects probably contributes to their extremely adaptive nature. We aim to study spatio-temporal expression dynamics and functional relevance of ST transcript variants in the lepidopteran model organism, Helicoverpa armigera. Identification of 69 putative Tret-like HaST transcript variants from databases and their digital gene expression analysis indicated tissue and development-specific expression patterns. Phylogenetic and sequence similarity network analysis of HaSTs signify evolutionary divergence, while motif and structure analysis depicted conserved signatures. In vitro gene expression validation for selected genes depicts that HaST09 and 69 are fat body and haemolymph-specific. While, HaST06, 30, 36 and 57 are developmental stage or sex-specific. HaST69 has high expression in the haemolymph of fifth instar larvae. In the presence of trehalose metabolism inhibitors and abiotic stress, HaSTs expression show dysregulation, indicating their possible association with trehalose metabolism and stress re-covery. In vivo gene silencing of HaST69 resulted in reduced trehalose accumulation in the insect body, sug-gesting its plausible role in sugar metabolism. The overall understanding of HaST diversity and expression dynamics highlights their putative roles in sugar transport during adaptation and stress recovery of insects.
Keywords: Gene expression; Helicoverpa armigera; Stress; Transporter-like; trehalose

Ultrafast spectroscopy of plasmons and free carriers in 2D MXenes - Colin-Ulloa, Erika; Fitzgerald, Andrew; Montazeri, Kiana; Mann, Javery; Natu, Varun; Ngo, Ken; Uzarski, Joshua; Barsoum, Michel W.; Titova, Lyubov V. (Advanced Materials, 2023)
2D MXenes have diverse and chemically tunable optical properties that arise from an interplay between free carriers, interband transitions, and plasmon resonances. The nature of photoexcitations and their dynamics in three different members of the MXene family, Ti3C2, Mo2Ti2C3, and Nb2C, are investigated using two complementary pump-probe techniques, transient optical absorption, and time-resolved terahertz (THz) spectroscopy. Measurements reveal pronounced plasmonic effects in the visible and near-IR in all three. Optical excitation, with either 400 or 800 nm pulses, results in a rapid increase in lattice temperature, evidenced by a pronounced broadening of the plasmon mode that presents as a plasmon bleach in transient absorption measurements. Observed kinetics of plasmon bleach recovery provide a means to monitor lattice cooling. Remarkably slow cooling, proceeding over hundreds of picoseconds to nanoseconds time scales, implies MXenes have low thermal conductivities. The slowest recovery kinetics are observed in the MXene with the highest free carrier density, viz. Ti3C2, that supports phonon scattering by free carriers as a possible mechanism limiting thermal conductivity. These new insights into photoexcitation dynamics can facilitate their applications in photothermal solar energy conversion, plasmonic devices, and even photothermal therapy and drug delivery.
Keywords: 2D properties; MXenes; Optical properties; plasmons; ultrafast spectroscopy

Unprecedented energy storage in metal-organic complexes via constitutional isomerism - Kottaichamy, Alagar Raja; Deebansok, Siraprapha; Deng, Jie; Nazrulla, Mohammed Azeezulla; Zhu, Yachao; Bhat, Zahid Manzoor; Devendrachari, Mruthyunjayachari Chattanahalli; Vinod, Chathakudath Prabhakaran; Kotresh, Harish Makri Nimbegondi; Fontaine, Olivier; Thotiyl, Musthafa Ottakam (Chemical Science, 2023)
The essence of any electrochemical system is engraved in its electrical double layer (EDL), and we report its unprecedented reorganization by the structural isomerism of molecules, with a direct consequence on their energy storage capability. Electrochemical and spectroscopic analyses in combination with computational and modelling studies demonstrate that an attractive field-effect due to the molecule's structural-isomerism, in contrast to a repulsive field-effect, spatially screens the ion-ion coulombic repulsions in the EDL and reconfigures the local density of anions. In a laboratory-level prototype supercapacitor, those with beta-structural isomerism exhibit nearly 6-times elevated energy storage compared to the state-of-the-art electrodes, by delivering similar to 535 F g(-1) at 1 A g(-1) while maintaining high performance metrics even at a rate as high as 50 A g(-1). The elucidation of the decisive role of structural isomerism in reconfiguring the electrified interface represents a major step forward in understanding the electrodics of molecular platforms.

Visible-light-active unsymmetrical squaraine dyes with 1 V of open-circuit voltage for dye-sensitized solar cells - Singh, Amrita; Kumar Singh, Ambarish; Dixit, Ruchi; Vanka, Kumar; Krishnamoorthy, Kothandam; Nithyanandhan, Jayaraj (ChemPhotoChem, 2023)
A series of alkyl-group-functionalized, aniline- and indoline-donor-based, unsymmetrical visible-light-active squaraine dyes, AM1-3, were designed and synthesized. Dye-sensitized solar cell (DSSC) devices were fabricated with both I-/I-3(-) and [Cu(tmby)(2)](+/2+) electrolytes. DSSC devices sensitized with the AM1 and AM2 dyes showed relatively high-power conversion efficiency of 7.44 % and 7.22 %, respectively with I-/I-3(-) in the absence of chenodeoxycholic acid (CDCA) than those of the AM3 dye (5.41 %). The [Cu(tmby)(2)](+/2+) electrolyte along with poly(3,4-ethylenedioxythiophene) (PEDOT) as cathode material showed excellent open-circuit potentials (V-OC) of 1030, 1025, and 1001 mV with the DSSC efficiency of 8.05 %, 7.96 %, and 5.84 %, respectively, for the AM1, AM2, and AM3 dyes in the absence of CDCA. Here, the AM1 dye exhibited the maximum DSSC efficiency of 8.05 % and V-OC of 1030 mV, which is the highest obtained efficiency and V-OC for the visible-light active zwitterionic unsymmetrical-squaraine dye with copper-based electrolyte.
Keywords: Cu electrolytes; dihedral angle; Dye-sensitized solar cells; open circuit voltage; squaraine dyes

Visible-light-active unsymmetrical squaraine dyes with pyridyl anchoring groups for dye-sensitized solar cells - Deshmukh, Shivdeep Suresh; Maibam, Ashakiran; Krishnamurty, Sailaja; Krishnamoorthy, Kothandam; Nithyanandhan, Jayaraj (Langmuir, 2023)
Visible-light-active alkyl group-wrapped unsymmetrical squaraine dyes SD1-SD3 were synthesized, featuring an indoline donor and pyridine and carboxylic acid anchoring groups. Their photophysical, electrochemical, and photovoltaic characteristics were examined by fabricating a dye-sensitized solar cell (DSSC) device. Both carboxylic acid and pyridine anchoring groups containing squaraine dyes SD3 and SD2 possess similar photophysical and electrochemical characteristics. However, their photovoltaic performances were completely different. The SD3 dye with the carboxylic acid anchoring group displayed a DSSC device efficiency of 7.20% (V-OC 0.81 V; J(SC) 12.29 mA/cm(2)) using iodolyte (I-/I-3(-)) electrolyte, compared to SD1 (V-OC 0.659 V; J(SC) 4.97 mA/cm(2); and eta - 2.34%) and SD2 (V-OC 0.629 V; J(SC) 1.68 mA/cm(2); and eta - 0.84%), which were featured with pyridyl anchoring groups. These results were attributed to dye loading on the Lewis and Br & oslash;nsted acidic sites of TiO2 and the importance of aggregated structures for photocurrent generation. In the incident photon-to-current efficiency (IPCE) analysis, SD1 dye-sensitized devices exhibited photocurrent generation from both monomeric and aggregated dyes on the TiO2 surface. In contrast, SD2 showed photocurrent generation solely from aggregated states. Despite the introduction of long alkyl chains to reduce dye aggregation and charge recombination, the results indicated preferential charge injection from only the aggregated SD2 dye on TiO2. Fluorescence-quenching experiments indicated an efficient charge transfer from the aggregated SD2 dye to TiO2 compared to that of the monomeric dye. Cosensitization, a method to enhance the light-harvesting efficiency and photocurrent generation in DSSCs, was explored by simultaneously cosensitizing pyridyl-based dyes (SD1 and SD2) with a blue-colored carboxylic acid-based squaraine dye SD4. IPCE analysis demonstrated that both SD1 and SD4 contributed to generating a photocurrent of 9.11 mA/cm(2). The sequential cosensitization of SD1 and SD4 with the coadsorbent CDCA showed the highest performance, with a V-OC of 0.663 V, a J(SC) of 11.43 mA/cm(2), and an efficiency (eta) of 5.20%.
Keywords: co-sensitization; Design; Emmision; Fluorescent Dyes; High-Efficiency; Organic Dye; Ring

Aluminium, nitrogen-dual-doped reduced graphene oxide Co-existing with cobalt-encapsulated graphitic carbon nanotube as an activity modulated electrocatalyst for oxygen electrocatalyst for oxygen electrochemistry applications - Kharabe, Geeta Pandurang; Barik, Sidharth; Veeranmaril, Sudheesh Kumar; Nair, Aathira; Illathvalappil, Rajith; Yoyakki, Athira; Joshi, Kavita; Vinod, Chathakudath Prabhakaran; Kurungot, Sreekumar (Small, 2024)
There is a rising need to create high-performing, affordable electrocatalysts in the new field of oxygen electrochemistry. Here, a cost-effective, activity-modulated electrocatalyst with the capacity to trigger both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in an alkaline environment is presented. The catalyst (Al, Co/N-rGCNT) is made up of aluminium, nitrogen-dual-doped reduced graphene oxide sheets co-existing with cobalt-encapsulated carbon nanotube units. Based on X-ray Absorption Spectroscopy (XAS) studies, it is established that the superior reaction kinetics in Al, Co/N-rGCNT over their bulk counterparts can be attributed to their electronic regulation. The Al, Co/N-rGCNT performs as a versatile bifunctional electrocatalyst for zinc-air battery (ZAB), delivering an open circuit potential approximate to 1.35 V and peak power density of 106.3 mW cm-2, which are comparable to the system based on Pt/C. The Al, Co/N-rGCNT-based system showed a specific capacity of 737 mAh gZn-1 compared to 696 mAh gZn-1 delivered by the system based on Pt/C. The DFT calculations indicate that the adsorption of Co in the presence of Al doping in NGr improves the electronic properties favoring ORR. Thus, the Al, Co/N-rGCNT-based rechargeable ZAB (RZAB) emerges as a highly viable and affordable option for the development of RZAB for practical applications. This manuscript reports the development of a new bifunctional catalyst that exhibits high activity and stability under practical operating conditions. The catalyst (Al, Co/N-rGCNT) is made up of aluminium, nitrogen-dual-doped reduced graphene oxide sheets co-existing with the in situ formed cobalt-encapsulated CNT units is synthesized by a scalable pyrolysis method in an inert Ar atmosphere. The developed electrocatalyst achieved enhanced the oxygen reduction reaction (ORR) and the oxygen evolution reaction OER activity as a result of the favorable synergistic modulations and the system can serve as a process-friendly air-electrode for rechargeable zinc-air battery (RZAB). image
Keywords: Al; Bifunctional catalyst; DFT study; encapsulated structure; N-dual doping; Oxygen Evolution Reaction; oxygen reduction reaction; rechargeable zinc-air battery; X-ray absorption spectroscopy

Aniline and indoline donors based far-red active unsymmetrical squaraine dyes for dye sensitized solar cells - Jadhav, Avinash P.; Singh, Ambarish Kumar; Maibam, Ashakiran; Krishnamurty, Sailaja; Krishnamoorthy, Kothandam; Nithyanandhan, Jayaraj (Chemphotochem, 2024)
In dye-sensitized solar cells (DSSC), controlling the dye-aggregation on the metal-oxide surface by appending the alkyl groups around the donor or pi-spacer unit of the dye is a potential approach to enhance DSSC efficiency. Further, rigidification of the dye structures by cyclization modulates the photophysical properties of the sensitizer. Here a series of donor-acceptor-donor (D-A-D) type far-red active unsymmetrical squaraine dyes (SQA) have been designed and synthesized, where N,N-dimethylaniline, methylated- and branched-indoline have been used as donor units. These dyes showed absorption between 629-654 nm (lambda max) with the molar extinction coefficient of 1.49-1.94x105 M-1 cm-1. Systematic enhancements in DSSC device efficiency have been observed due to the cyclization and alkyl-groups incorporation in this set of dyes which were further enhanced with the addition of chenodeoxycholic acid (CDCA). The highest DSSC device efficiency of 4.78 % (Jsc of 8.77 mA/cm2 and Voc of 692 mV) has been achieved for SQA3. The IPCE profile of SQA dyes indicates the contribution of aggregated structures for the photocurrent generation. Further, co-sensitization of SQA3 dye with a complementary visible light active dye AK4 showed the enhanced device efficiency of 6.27 % with panchromatic IPCE response. Dye rigidification, and controlled aggregation of dyes on TiO2 by means of cyclization of donor unit and introducing the alkyl groups in the dye structure synergistically improve the dye-sensitized solar cell (DSSC) device performance. Donor-Acceptor-Donor (D-A-D) based unsymmetrical squaraine dye SQA3 showed the DSSC device performance of 4.78 %.image
Keywords: co-sensitization; dye-sensitized solar cell; effect of alkyl chain; molecular planarity; squaraine dye

Aqueous glycerol to glyceric acid and green hydrogen by visible-light-driven photocatalysis with Ni/Co(PO4)2-TiO2: parallel utilization of holes and electrons - Nivedhitha, Thazhath R.; Bajpai, Himanshu; Oommen, Jiffin Varghese; Abraham, Athira; Chauhan, Inderjeet; Gopinath, Chinnakonda S. (ACS Sustainable Chemistry & Engineering, 2024)
Replacing the kinetically sluggish oxygen evolution reaction (OER) with the oxidation of an abundantly available organic molecule to value-added product(s) (VAPs) at low voltage along with the hydrogen evolution reaction (HER) is a big challenge in water splitting, either by electrolysis or sunlight-driven photocatalysis. Glycerol oxidation to a VAP is kinetically fast, compared to an OER, and offers hope to enhance sunlight-driven water splitting to hydrogen by the concurrent utilization of holes and electrons. Mixed bimetal phosphates of Co and Ni (CoxNiy(PO4)(2) (CoNiP)) with different Co:Ni ratios (10:0, 7:3, 5:5, 3:7, and 0:10) were integrated with TiO2 to generate final photocatalyst composites (x wt % CoNiP with TiO2) and employed for concurrent photocatalytic HER and glycerol oxidation. Irrespective of the weight ratios of CoNiP and TiO2, any TiO2-CoNiP composite showed better photocatalytic activity for the HER and glycerol oxidation compared to virgin TiO2. The highest HER as well as selectively generated glyceric acid yield was observed to be 54 and 67 mmol/g, respectively, after 25 h of reaction under 1 sun conditions with TiO2-CoNiP-5:5. An increase in catalytic activity can be attributed to the formation of p-n heterojunctions of the constituent component along with uniform distribution of CoNiP to effectively utilize the charge carriers for redox reactions. Highly selective oxidation of glycerol to glyceric acid (85%), along with other minor products, is also demonstrated, which offers further scope to use solar light to generate VAPs in a sustainable manner. A simple comparison of H-2 yield and all oxidized products together indicates the better utilization of holes for the latter, and hence, there is scope to increase HER and possibly the whole photocatalytic activity.
Keywords: biomass component; earth-abundantmaterial; energy conversion; organicvalorisation; water splitting

architecturally rational hemostat for rapid stopping of massive bleeding on anticoagulation therapy - Lee, Vivian K.; Lee, Taewoo; Ghosh, Amrit; Saha, Tanmoy; Bais, V. Manish; Bharani, Kala Kumar; Chag, Milan; Parikh, Keyur; Bhatt, Parloop; Namgung, Bumseok; Venkataramanan, Geethapriya; Agrawal, Animesh; et al. (Proceedings of the National Academy of Sciences of the United States of America, 2024)
Hemostatic devices are critical for managing emergent severe bleeding. With the increased use of anticoagulant therapy, there is a need for next- generation hemostats. We rationalized that a hemostat with an architecture designed to increase contact with blood, and engineered from a material that activates a distinct and undrugged coagulation pathway can address the emerging need. Inspired by lung alveolar architecture, here, we describe the engineering of a next- generation single - phase chitosan hemostat with a tortuous spherical microporous design that enables rapid blood absorption and concentrated platelets and fibrin microthrombi in localized regions, a phenomenon less observed with other classical hemostats without structural optimization. The interaction between blood components and the porous hemostat was further amplified based on the charged surface of chitosan. Contrary to the dogma that chitosan does not directly affect physiological clotting mechanism, the hemostat induced coagulation via a direct activation of platelet Toll - like receptor 2. Our engineered porous hemostat effectively stopped the bleeding from murine liver wounds, swine liver and carotid artery injuries, and the human radial artery puncture site within a few minutes with significantly reduced blood loss, even under the anticoagulant treatment. The integration of engineering design principles with an understanding of the molecular mechanisms can lead to hemostats with improved functions to address emerging medical needs.
Keywords: biomaterial; clotting; hemostasis; hemostat; trauma

Aromatic (co)polycarbonates bearing pendant 2,3-dimethylmaleimido group based upon a new phthalimidine-containing "cardo" bisphenol - Talanikar, Aniket A.; Nagane, Samadhan S.; Wadgaonkar, Prakash P.; Rashinkar, Gajanan S. (Journal of Macromolecular Science Part A-Pure and Applied Chemistry, 2024)
A new ``cardo'' bisphenol viz., 1-(2-(1,1-bis(4-hydroxyphenyl)-3-oxoisoindolin-2-yl)ethyl)-3,4-dimethyl- 1H-pyrrole-2,5-dione (PPH-MA) was synthesized in a two-step reaction sequence starting from phenolphthalein. PPH-MA was utilized as a step-growth monomer for the synthesis of a homo- and fourco-polycarbonates bearing pendant 2,3-dimethylmaleimido groups (PC-MAs) via solution polycondensation of PPH-MA or various mol % compositions of PPH-MA and bisphenol-A, respectively, with triphosgene.H-1 NMR spectroscopy confirmed the chemical structure and composition of PC-MAs. Inherent viscosity and number average molecular weight values of PC-MAs were in the range 0.45-0.64 dL g(-1) and 18,300 - 36,200 g mol(-1), respectively, indicating the formation of polymers of medium to reasonably high molecular weights. Tough, transparent and flexible films of PC-MAs could be cast from chloroform solution. X-ray diffraction studies indicated the amorphous nature of PC-MAs. The 10% weight loss temperature (T-10) values of PC-MAs were in the range 373-443 degrees C indicating their good thermal stability.
Keywords: (co)polycarbonates; 2; 3-dimethylmaleimido; phenolphthalein; phthalimidine ring; ``cardo'' bisphenol

Aromatic (Co)polycarbonates bearing pendant norbornenyl groups: Synthesis, characterization and post-polymerization modification - Talanikar, Aniket A.; Nagane, Samadhan S.; Wadgaonkar, Prakash P.; Rashinkar, Gajanan S. (High Performance Polymers, 2024)
A homo- and three co-polycarbonates (PC-NBs) bearing pendant norbornenyl groups were synthesized via solution polycondensation of triphosgene with 4, 4'-(bicyclo (2.2.1) hept-5-en-2 yl methylene) bis (2-methoxyphenol) (BPA-NB) or various mol % compositions of BPA-NB and bisphenol-A, respectively. 1H-NMR spectroscopy confirmed the chemical structure and composition of PC-NBs. Inherent viscosity and number-average molecular weight (Mn) values of PC-NBs were in the range 0.44 - 0.64 dL g-1 and 21,800 - 34,100 g mol-1, respectively, indicating the formation of polymers of medium to reasonably high molecular weights. Tough, transparent, and flexible films of PC-NBs could be cast from chloroform solution. X-Ray diffraction studies indicated the amorphous nature of PC-NBs. Glass transition temperature (Tg) values, determined by DSC analysis, of PC-NBs were in the range 154 - 175 degrees C and Tg values increased with the increase in mol % of BPA-NB. The post-polymerization modification of a representative PC-NB was demonstrated using 3,6-diphenyl-1,2,4,5-tetrazine via tetrazine-ene reaction.
Keywords: (co)polycarbonates; norbornenyl groups; post-polymerization modification; tetrazine-ene click reaction; thermoplastics

Atmospheric-pressure continuous-flow methane oxidation to methanol and acetic acid using H2O2 over the Au-Fe catalyst - Jagtap, Anuradha V.; Kumar, Pawan; Gupta, Sharad; Nagendra, Abharana; Jha, Shambhu Nath; Bhattacharyya, D.; Ajithkumar, Thalasseril G.; Vinod, C. P. (ACS SUSTAINABLE CHEMISTRY & ENGINEERING, 2024)
Keywords: CO oxidation; HIGHLY SELECTIVE OXIDATION; metal-organic frameworks

Base controlled rongalite-mediated reductive aldol/cyclization and dimerization of isatylidene malononitriles/cyanoacetates - Chaudhari, Suryakant S.; Nichinde, Chandrakant B.; Patil, Baliram R.; Girase, Amardipsing S.; Rama Krishna, Gamidi; Kinage, Anil K. (Organic and biomolecular chemistry, 2024)
In this study, we developed a novel methodology involving a base-controlled, rongalite-mediated reductive/aldol reaction, followed by cyclization of isatylidene malononitriles/cyanoacetates, resulting in the synthesis of spiro[2,3-dihydrofuran-3,3 `-oxindole]. Additionally, we have disclosed a rongalite-mediated dimerization process for isatylidene malononitriles, yielding dispiro[cyclopent-3 `-ene]bisoxindole. The utilization of rongalite in this reaction serves a dual purpose, acting both as a reducing agent and a C1 synthon. The developed approach has several advantages like a simple reaction setup, a wide substrate scope, requiring less time, using water as a green solvent, no metal or catalyst is required and products can be easily isolated via filtration with excellent yields under mild reaction conditions. A novel methodology was developed for the synthesis of spiro[2,3-dihydrofuran-3,3 `-oxindole] and dispiro[cyclopent-3 `-ene]bisoxindole under mild reaction conditions using inexpensive reagents.

Biobased reusable nonisocyanate polyurethane hot-melt adhesives with potential chemical degradability - Ghuge, Gorakh Hiraman; Torris, Arun; Nair, Kiran Sukumaran (ACS Applied Polymer Materials, 2024)
Hot-melt adhesives (HMAs) derived from renewable resources are always attractive, as they promote less dependence on fossil resources and aid in developing environmentally friendly materials. However, developing sustainable HMAs exhibiting good adhesive performance and biodegradability remains challenging. Herein, reusable biobased HMAs with a high bio content of 88-90%, biodegradability, and tunable adhesive nature were developed as a possible alternative to conventional petroleum-based hot-melt adhesives. Moreover, the structure-property relationship of the product was investigated in detail. By tailoring the monomer composition, NIPU-40 HMA exhibited a good bonding ability with a superior adhesion strength of 6.39 MPa. To the best of our knowledge, this is the highest adhesion strength observed when bonding with an Al substrate among the biobased thermoplastic NIPU-HMAs. Impressively, NIPU-HMAs could display excellent reusability even after three bonding and debonding cycles without a significant drop in the adhesive strength and were found to exhibit good adhesion performance under wet conditions. More importantly, the NIPU-HMAs are prone to degradation under acid-catalyzed conditions. Considering their features, these biobased NIPU thermoplastic hot-melt adhesives offer an opportunity to create environmentally friendly, degradable adhesives that possess excellent adhesive strength and can be reused multiple times.
Keywords: acid degradability; biobased NIPUs; cyclic carbonates; hot meltadhesives; lap shearstrength; spiro-aromatic

Biodegradable and 3D printable lysine functionalized polycaprolactone scaffolds for tissue engineering applications - Naik, Sonali S.; Torris, Arun; Choudhury, Namita R.; Dutta, Naba K.; Nair, Kiran Sukumaran (Biomaterials Advances, 2024)
Tissue engineering (TE) has sparked interest in creating scaffolds with customizable properties and functional bioactive sites. However, due to limitations in medical practices and manufacturing technologies, it is challenging to replicate complex porous frameworks with appropriate architectures and bioactivity in vitro. To address these challenges, herein, we present a green approach that involves the amino acid (L-lysine) initiated polymerization of epsilon-caprolactone (CL) to produce modified polycaprolactone (PCL) with favorable active sites for TE applications. Further, to better understand the effect of morphology and porosity on cell attachment and proliferation, scaffolds of different geometries with uniform and interconnected pores are designed and fabricated, and their properties are evaluated in comparison with commercial PCL. The scaffold morphology and complex internal micro-architecture are imaged by micro-computed tomography (micro-CT), revealing pore size in the range of similar to 300-900 mu m and porosity ranging from 30 to 70 %, while based on the geometry of scaffolds the compressive strength varied from 143 +/- 19 to 214 +/- 10 MPa. Additionally, the degradation profiles of fabricated scaffolds are found to be influenced by both the chemical nature and product design, where Lys-PCL-based scaffolds with better porosity and lower crystallinity degraded faster than commercial PCL scaffolds. According to in vitro studies, Lys-PCL scaffolds have produced an environment that is better for cell adhesion and proliferation. Moreover, the scaffold design affects the way cells interact; Lys-PCL with zigzag geometry has demonstrated superior in vitro vitality (>90 %) and proliferation in comparison to other designs. This study emphasizes the importance of enhancing bioactivity while meeting morphology and porosity requirements in the design of scaffolds for tissue engineering applications.
Keywords: Additive manufacturing; Amino acid; Micro-computed tomography; Polycaprolactone

Bismuth ferrite based acetone gas sensor: evaluation of graphene oxide loading - Ghadage, Pandurang; Shinde, K. P.; Nadargi, Digambar; Nadargi, Jyoti; Shaikh, Hamid; Alam, Mohammad Asif; Mulla, Imtiaz; Tamboli, Mohaseen S.; Park, J. S.; Suryavanshi, Sharad (RSC Advances, 2024)
We report a BiFeO3/graphene oxide (BFO/GO) perovskite, synthesized using a CTAB-functionalized glycine combustion route, as a potential material for acetone gas sensing applications. The physicochemical properties of the developed perovskite were analysed using XRD, FE-SEM, TEM, HRTEM, EDAX and XPS. The gas sensing performance was analysed for various test gases, including ethanol, acetone, propanol, ammonia, nitric acid, hydrogen sulphide and trimethylamine at a concentration of 500 ppm. Among the test gases, the developed BFO showed the best selectivity towards acetone, with a response of 61% at an operating temperature of 250 degrees C. All the GO-loaded BFO samples showed an improved gas sensing performance compared with pristine BFO in terms of sensitivity, the response/recovery times, the transient response curves and the stability. The 1 wt% GO-loaded BiFeO3 sensor showed the highest sensitivity of 89% towards acetone (500 ppm) at an operating temperature of 250 degrees C. These results show that the developed perovskites have significant potential for use in acetone gas sensing applications. CTAB-functionalized glycine combustion yields BiFeO3/graphene oxide (BFO/GO) perovskite for acetone gas detection.

Bridging the gap: an investigation of biosurfactants-polymer systems - Abhyankar, Isha; Hirlekar, Swarali; Prabhune, Asmita; Nisal, Anuya (Current Opinion in Colloid & Interface Science, 2024)
Biosurfactants (BSs) have been extensively researched due to their potential applications in various fields, including textiles, cosmetics, pharmaceuticals, agriculture, and oil remediation. These BSs possess a diverse range of physical, chemical, and biological properties. In recent years, researchers have combined these biosurfactants with both natural and synthetic polymers, resulting in the development of advanced material systems that exhibit a unique combination of properties. This review focuses on highlighting the recent advancements in these biosurfactant-polymer material systems and identifies existing gaps in the literature. The combination of biosurfactants with polymers has led to the formation of interpenetrated hydrogels, films, chemically modified surfaces, vesicles, functionalized nanofiber nonwoven mats, nano-formulations, and nano-assemblies. Some studies have also investigated the interactions between biosurfactants and polymer molecules. In most cases, non-specific, non-covalent interactions, such as electrostatic interactions, hydrogen bonding, and hydrophobic interactions have been found to govern the properties of these systems. Moreover, promising results have been achieved through the covalent modification of polymer surfaces, followed by functionalization using biosurfactant molecules. The literature demonstrates that these advanced materials could find applications in various fields, including drug delivery, bioremediation, biomedical materials, and as antimicrobial agents. These findings indicate the promising potential of biosurfactant-polymer systems for future advancements in these areas.

Bronsted acid-promoted cyclodimerization of α,β-unsaturated γ-ketoesters: construction of fused pyrano-ketal-lactones and γ-ylidene-butenolides - Vinodkumar, Ramavath; Nakate, Ashwini K.; Sharma, Himanshu; Vanka, Kumar; Rama Krishna, Gamidi; Kontham, Ravindar (ACS Omega, 2024)
Unprecedented MsOH-promoted diastereoselective cascade dimerization and intramolecular lactonization of readily accessible alpha,beta-unsaturated gamma-ketoesters are presented. The results obtained in this work, control experiments, and density functional theory (DFT) calculations suggested that the initial enolization and E to Z isomerization/equilibration of olefin (C=C) of substrate alpha,beta-unsaturated gamma-ketoesters give a Z-isomer preferentially over an E-isomer. Subsequently, the Z-isomer undergoes intermolecular annulation with alpha,beta-unsaturated gamma-ketoesters via domino Michael addition/ketalization/lactonization steps to furnish fused tetracyclic pyrano-ketal-lactone. However, the Z-isomer prefers intramolecular trans-esterification in a competing pathway and gives bicyclic gamma-ylidene-butenolide. The key features of this work include simple Br & oslash;nsted acid catalysis, the formation of three bonds, two rings, and three contiguous stereogenic centers in a single step, DFT calculations, and the assignment of relative stereochemistry through X-ray diffraction (XRD) and two-dimensional (2D) nuclear magnetic resonance (NMR) analyses.

Colocasia esculenta stems for the isolation of cellulose nanofibers: a chlorine-free method for the biomass conversion - Dominic, C. D. Midhun; Maheswary, S.; Neenu, V. K.; Sajadi, S. Mohammad; Rosa, Derval dos Santos; Begum, P. M. Sabura; Mathew, Mariya; Ajithkumar, T. G.; Parameswaranpillai, Jyotishkumar; George, Tresa Sunitha; Resmi, V. C.; Ilyas, R. A.; et al. (Biomass Conversion and Biorefinery, 2024)
The reuse of waste products is the green key to sustainability. The extraction of cellulose nanofibers from Colocasia esculenta stems is presented in the paper. The study proved that the waste biomass could be effectively re-engineered into highly valued cellulose nanofibers (CNFs). Cellulose nanofibers were extracted via a chemo-mechanical route. The pre-treatments included mild alkali hydrolysis (2% NaOH) and chlorine-free bleaching (peroxide bleaching in an alkaline medium). Cellulose I-beta structure was confirmed using C-13 solid-state nuclear magnetic resonance spectroscopy and X-ray diffraction analysis. The elemental analysis of CNFs detected the elements, carbon and oxygen. The CNFs had a crystallinity and transmittance of 71.72% and 60%, respectively. Microscopic studies verified the elimination of non-cellulosic components and the fibrous nature of CNFs. Moreover, the fiber diameter of CNFs was 20-40 nm. Thermal analysis revealed good thermal stability of 335.8 degrees C (T-50) for nanofibers. Long-term aids are numerous in eco-friendly technology. Developing an eco-design will support zero waste ideals, lowers carbon dioxide emissions, and encourages a circular economy. Owing to the merits of natural fibers, they can be adopted in various sectors including packaging, automobile, aerospace, electronics, biomedical, construction, and furniture.
Keywords: acid hydrolysis; cellulose nanofibers; Colocasia esculenta stems; High crystallinity

Continuous flow synthesis of hierarchical low silica X zeolite - Adarsh, V. K.; Shrotri, Aadesh R.; Birje, Amit R.; Nandanwar, Sachin U. (Materials Today Communications, 2024)
Zeolites, renowned for their versatile applications in catalysis, adsorption, and ion exchange, have long been synthesized using conventional batch processes. However, the inherent limitations of these methods, such as resource-intensive conditions and inconsistent product quality, underscore the need for a sustainable and efficient approach. In this study, a continuous flow synthesis process was established for the synthesis of industrially important low silica X (LSX) zeolite using a tubular reactor. The synthesis gel was subjected to aging for 5 days at room temperature to facilitate nucleation and crystal growth combined with the fast-heating rate in a tubular reactor at 363 K & 1.1 atm., which in turn produces LSX after 40 min. The synthesized product was confirmed by the XRD, FE-SEM, EDS, XRF, TEM, and N2 adsorption-desorption; the data was compared with the LSX sample synthesized by batch process. The result implies that LSX prepared by continuous flow has a pure phase of LSX with the hierarchical structure, which provides better adsorption capacity of CO2 at 298 K up to 20 bar. Due to continuous flow synthesis, the crystallization time was reduced and faster kinetics which may be helpful for scale-up the process for LSX synthesis.
Keywords: Adsorption; Carbon dioxide; continuous flow; Low silica X; Tubular reactor; zeolites

Deciphering the role of chemisorbed CO in CO2 methanation: kinetic and mechanistic investigation over monometallic (Ru) and bimetallic (Ru-Ni) catalysts - Dongapure, Pavan; Tekawadia, Jyoti; Naidu, V. Satyam; Devi, R. Nandini (Catalysis Science & Technology, 2024)
Supported metal catalysts have made prominent contributions to CO2 mitigation through conversion into useful chemicals. However, intermediates and mechanisms involved in this process remain ambiguous. Herein, we present the kinetics, mechanistic route and impact of chemisorbed CO in CO2 methanation on Ru/gamma-Al2O3 and Ru-Ni/gamma-Al2O3 catalysts. Both the catalysts show minimal variation in adsorbed species on changing the duration of reduction, as confirmed through in situ IR spectroscopy. A notable observation is that the adsorbed CO exhibits a red shift at a longer reduction time and a more reactive nature on the Ru/gamma-Al2O3 surface. Conversely, stable bridged CO mode is detected on Ru-Ni/gamma-Al2O3 under similar conditions, leading to catalyst poisoning in all instances. This indicates that pre-reduction duration does not have much effect on the surface but interference of CO has more effect at lower concentrations of reactant gases. In situ XRD analysis reveals limited changes in the metallic or mixed oxide species during these conditions. Reaction kinetic analysis showed that Ru-Ni/gamma-Al2O3 has better rate performance at higher concentrations of CO2, whereas Ru/gamma-Al2O3 exhibits better rate performance at lower concentrations. The activation energy was found to be 74.07 kJ per mole for Ru/gamma-Al2O3 and 89.38 kJ per mole for Ru-Ni/gamma-Al2O3. The turnover frequency (TOF) is directly proportional to the rate of formation of methane.

Dietary supplementation of lactococcus lactis subsp. lactis BIONCL17752 on growth performance, and gut microbiota of broiler chickens - Navale, Vishwambar D.; Yadav, Rakeshkumar; Khilari, Ajinkya; Dharne, Mahesh; Shanmugam, Dhanasekaran; Vamkudoth, Koteswara Rao (Probiotics and Antimicrobial Proteins, 2024)
The rapid rise of antimicrobial resistance (AMR) is a global concern, being triggered by the overuse or misuse of antibiotics in poultry farming sector. We evaluated Lactococcus lactis subsp. lactis BIONCL17752 strain, and characterized its probiotic potential to endure hostile gastrointestinal conditions. Genome sequencing analysis revealed probiotics traits, and gene clusters involved in bacteriocins, lactococcin A, and sactipeptides production. The absence of genes for antibiotic resistance, virulence, and biogenic amine production indicates the potential of probiotic strain. The BIONCL17752 strain was explored for antibiotic-free feed supplement for growth promotor in broiler chicken. The feed supplemented with 4 x 109 CFU/kg of probiotic strain, in combination with various concentrations of fructooligosaccharides (FOS) 1.0, 2.5, and 5.0 kg/tonne in starter, grower, and finisher diets, respectively. A significant improvement of body weight 152 to 171 g/bird (p < 0.05), and a low feed conversion ratio (FCR) of 1.62, was achieved without using synthetic antibiotics for growth promotion. The results of biochemical, hematological, and histological examinations showed normal features, indicating that the treatment had no harmful effects on the bird's health. Reduced levels of cholesterol, triglycerides, high-density lipoprotein (HDL), and low-density lipoprotein (LDL) in serum are an indication of the health benefits for the treated birds. Microbial community analysis of fecal samples of poultry birds exhibited a higher abundance of Bacteroidetes, Firmicutes, Proteobacteria, Actinobacteria, and Fusobacteria. Probiotic treatment resulted in reduced Firmicutes and increased Bacteroidetes (F/B ratio) in the broiler's gut which highlights the benefits of probiotic dietary supplements. Importantly, the probiotic-fed group exhibited a high abundance of carbohydrate-active enzymes (CAZyme) such as glycoside hydrolases (GH), glycoside transferases (GT), and carbohydrate-binding module (CBM) hydrolases which are essential for the degradation of complex sugar molecules. The probiotic potential of the BIONCL17752 strain contributes to broilers' health by positively affecting intestinal microbiota, achieving optimal growth, and lowering mortality, demonstrating the economic benefits of probiotic treatment in organic poultry farming.
Keywords: Antibiotic growth promotor; Broiler chickens; Functional genome analysis; Growth performance; Gut microbiota; Lactococcus lactis subsp. lactis

Divergent access to polycyclic spiro- and fused-N,O-ketals through Bi(OTf)3-catalyzed [4+2]-annulation of cyclic N-sulfonyl ketimines and alkynols - Nakate, Ashwini K.; Kataria, Priyanka; Sambherao, Pooja I.; Krishna, Gamidi Rama; Kontham, Ravindar (Chemical Communications, 2024)
Bismuth(iii) triflate-catalyzed [4+2]-annulation of cyclic N-sulfonyl ketimines (derived from saccharin) and alkynyl alcohols (4-pentyn-1-ols and 5-hexyn-1-ols) has been reported. This cascade annulation provides a diverse array of polycyclic spiro-and-fused N,O-ketals with excellent substrate scope, good isolated yields, and diastereoselectivities under mild reaction conditions.

Durable polymer composites preparation with oxy-delignified banana fiber for automotive parts: A study on mechanical and thermal properties - Mulla, Abdul Mannan; Munagala, Chandan K.; Kesari, Aman K.; Raju, L. Yugender; Nagar, Harsha; Behara, Dilip K.; Aniya, Vineet (INDUSTRIAL CROPS AND PRODUCTS, 2024)
Keywords: Automotive parts; Banana fiber; Oxygen delignification; polypropylene; Twin-screw extruder

Early detection of KP.2 SARS-CoV-2 variant using wastewater-based genomic surveillance in Pune, Maharashtra, India - Rajput, Vinay; Das, Rashmita; Pramanik, Rinka; Nannaware, Kiran; Sushma, Y.; Taji, Nyabom; Rajput, Vishal; Rajkhowa, Riyakshi; Pacharne, Poonam; Shah, Priyanki; Gogate, Niharika; Sangwar, Poornima; et al. (Journal of Travel Medicine, 2024)

Effect of CTMABr/SiO2 molar ratio in synthesis of micro-mesoporous ZSM-5 composite and its application in 5-EMF (biofuel additive) formation - Manal, Prajakta N.; Niphadkar, Prashant S.; Nandanwar, Sachin U.; Bokade, Vijay V. (Environmental Progress and Sustainable Energy, 2024)
Synthesis of micro-mesoporous zeolite composite with optimum micro and mesoporosity is an emerging research area due to its wide applications, especially in bulk chemical or biomass transformations. It offers advantages in preserving zeolite crystallinity, creating mesoporosity and converting bulky molecules into valuable products. This work presents the process of preparing bimodal micro-mesoporous ZSM-5 using dual templates (CTMABr and TPABr). XRD, N2 adsorption-desorption, SEM, TEM, Si-29, and Al-27 NMR were used to analyze the two-dimensional micro-mesoporous ZSM-5. One-step synthesis of bimodal micro-mesoporous ZSM-5 features dual micro/mesoporosity by a marginal decrease in the crystallinity (71%). Micro-mesoporous ZSM-5 composite was found to be dependent on the optimum CTMABr/SiO2 molar ratio of 0.04 to 0.06. The micro-mesoporous ZSM-5 zeolite composite was evaluated for cascade synthesis of 5-EMF (methoxymethyl furfural- biofuel additive) from fructose and exhibited a five fold increase in 5-EMF yield to 24.2% as compared with parent ZSM-5 (4.6%).
Keywords: fructose; methoxymethyl furfural-biofuel additive; micro-meso composite; ZSM-5

Effect of position of donor units and alkyl groups on dye-sensitized solar cell device performance: indoline-aniline donor-based visible light active unsymmetrical squaraine dyes - Singh, Amrita; Singh, Ambarish Kumar; Dixit, Ruchi; Vanka, Kumar; Krishnamoorthy, Kothandam; Nithyanandhan, Jayaraj (ACS Om., 2024)
Indoline (In) and aniline (An) donor-based visible light active unsymmetrical squaraine (SQ) dyes were synthesized for dye-sensitized solar cells (DSSCs), where the position of An and In units was changed with respect to the anchoring group (carboxylic acid) to have In-SQ-An-CO2H and An-SQ-In-CO2H sensitizers, AS1-AS5. Linear or branched alkyl groups were functionalized with the N atom of either In or An units to control the aggregation of the dyes on TiO2. AS1-AS5 exhibit an isomeric pi-framework where the squaric acid unit is placed in the middle, where AS2 and AS5 dyes possess the anchoring group connected with the An donor, and AS1, AS3, and AS4 dyes having the anchoring group connected with the In donor. Hence, the conjugation between the middle squaric acid acceptor unit and the anchoring -CO2H group is short for AS2, AS5, and AK2 and longer for AS1, AS3, and AS4 dyes. AS dyes showed absorption between 501 and 535 nm with extinction coefficients of 1.46-1.61 x 10(5) M-1 cm(-1). Further, the isomeric pi-framework of An-SQ-In-CO2H and In-SQ-An-CO2H exhibited by means of changing the position of In and An units a bathochromic shift in the absorption properties of AS2 and AS5 compared to the AS1, AS3, and AS4 dyes. The DSSC device fabricated with the dyes contains short acceptor-anchoring group distance (AS2 and AS5) showed high photovoltaic performances compared to the dyes having longer distance (AS1, AS3, and AS4) with the iodolyte (I-/I-3(-)) electrolyte. DSSC device efficiencies of 5.49, 6.34, 6.16, and 5.57% have been achieved for AS1, AS2, AS3, and AS4 dyes, respectively; without chenodeoxycholic acid (CDCA), small changes have been observed in the device performance of the AS dyes with CDCA. Significant changes have been noted in the DSSC parameters (open-circuit voltage V-OC, short-circuit current J(SC), fill factor ff, and efficiency eta) for the AS5 dye while sensitized with CDCA and showed highest DSSC efficiency of 8.01% in the AS dye series. This study revealed the potential of shorter SQ acceptor-anchoring group distance over the longer one and the importance of alkyl groups on the overall DSSC device performance for the unsymmetrical squaraine dyes.

An effective, facile, and rapid synthesis of nanosized Mn3O4 using a microwave route - Yadav, Akash; Jha, Ratnesh; Bhatkar, Akash; Kamble, Aditi; Vaishnav, Vishal; Bogalera, Shivamurthy P.; Manikandan, Marimuthu; Nayaka, Girish Praveen; Umbarkar, Shubhangi; Raja, Thirumalaiswamy; Bhatte, Kushal D. (Journal of Nanoparticle Research, 2024)
Microwave-assisted one-pot, one-step, calcination-free synthesis of nanosized Mn3O4 is reported using only benzylamine and manganese acetate. Benzylamine in this protocol plays a vital role for efficient microwave synthesis. This microwave method enables the synthesis of nanosized Mn3O4 in just few hours only in a single step eliminating the need of calcinations of any intermediate. The synthesized nanosized Mn3O4 was analyzed by XRD, HRTEM, EDAX, and Raman spectroscopy. The catalytic and electrochemical properties of as-synthesized Mn3O4 were investigated. In galvanostatic charge-discharge experiments, after 800 cycles, more than 89% capacitance was retained for electrodes made by as synthesized Mn3O4 nanomaterials indicating its very good stability. In the catalytic conversion of cinnamyl alcohol to cinnamaldehyde via oxidation, using as prepared nanosized Mn3O4 as a catalyst, it displays effective catalytic properties. A probable mechanical study of its formation was also envisaged. This synthesis protocol is additive-free, occurs in a short time, is facile, is energy efficient, and eliminates the use of many chemicals. These silent features make these reported protocols economically viable and environmentally benign which adhere to the principles of Green Chemistry.
Keywords: Calcination free; Electrochemical and catalytic properties; Nanosized Mn3O4; Single-step synthesis

Efficient electrochemical synthesis of Cu 3 Si/Si hybrids as negative electrode material for lithium-ion battery - Jiang, Siwei; Cheng, Jiaxu; Nayaka, G. P.; Dong, Peng; Zhang, Yingjie; Xing, Yubo; Zhang, Xiaolei; Du, Ning; Zhou, Zhongren (Journal of Alloys and Compounds, 2024)
Nanoscaling and alloying techniques for silicon -based materials are widely recognized as vital technological approaches to effectively address the challenges associated with volume expansion and poor conductivity in silicon anodes. Developing short process, cost-effective preparation methods and shape controllable silicon -based materials is expected to improve their cyclability. Herein, utilizing the superior electrical conductivity of copper metal and its stable alloy interaction with silicon, the present study introduced a simple synthetic process by incorporating nanoscale Cu 2 O into a SiO 2 dioxide matrix under a combination of hydrothermal reaction with Cu (NO 3 ) 2 as the copper source and further sintering treatment. Under the conditions of a Cu:Si molar ratio to 3:8 under 850 degrees C by 2.6 V of constant electrolsyis for 3 h, straight silicon nanowires with a cross-sectional distribution were obtained. The Cu 3 Si alloy particles were enriched around silicon nanowires. Experimental testing was conducted to evaluate the electrochemical storage capabilities of Cu 3 Si/Si nanowires, resulting in an initial specific capacity of 2630.7 mAh g -1 and an initial coulombic efficiency of 88.94%. After 100 charge -discharge cycles, the discharge specific capacity reached 1675.4 mAh g -1 , with a capacity retention rate of 66.20%. This work demonstrates the effectiveness of constructing a Cu 3 Si conductive network for solving the volume expansion and conductivity problems of Si and the distinctive Cu 3 Si/Si architecture offers an exemplary model for the design of silicon -based composite anodes for advanced lithium -ion batteries.
Keywords: Cu3Si/Si alloy; Electrochemical storage capacity; Molten salt electrochemistry; Si nanowires

Electrochemical property of nanosphere-like MgO electrode synthesized via SILAR in asymmetric supercapacitor - Gaikwad, D. S.; Bobade, R. G.; Suryawanshi, V. B.; Nakate, U. T.; Shaikh, S. F.; Al-Enizi, Abdullah M.; Dabke, N. B.; Lokhande, B. J.; Ambare, Revanappa C. (Journal of Materials Science-Materials in Electronics, 2024)
In this research article, we synthesized nanospheres of MgO thin-film substrate using the successive ionic layer adsorption and reaction (SILAR) technique on stainless steel substrates. The final optimized sample was used for physical characterization. XRD revealed the cubic structure of the MgO electrode. Additionally, it was utilized for electrochemical supercapacitive characterization, including cyclic voltammetry (CV), chronopotentiometry, and electrochemical impedance spectroscopy (EIS). Results showed that MgO nanospheres exhibited a higher specific capacitance (SC) of 536.06 F/g. The maximum values of specific energy and specific power were 30.79 Wh/kg and 1420 W/kg, respectively, at 2 mA/cm2 in 1-M KOH. The EIS plot confirmed an internal resistance (Ri) of 0.86 omega, indicating good power performance and outstanding rate capability of MgO nanospheres. This material demonstrated excellent cycling capability, retaining 91.38% capacitance after 5000 CV cycles. The MgO//AC device displayed an SC of 210.21 F/g at 5 mV/s in a PVA-KOH solid-state electrolyte. With an energy density of 23.90 Wh/kg and a power density of 1.84 kW/kg, the asymmetric supercapacitor performance showed that the MgO-based electrode is suitable for use in actual device manufacturing. After 5000 CV cycles, the supercapacitor device exhibited exceptional capacitance retention of 92.93%. Thus, this research successfully demonstrated the usefulness of the simple and affordable SILAR method for synthesizing pure MgO nanostructures for application in supercapacitors.

Engineered PLGA core-lipid shell hybrid nanocarriers improve the efficacy and safety of irinotecan to combat colon cancer - Giram, Prabhanjan S.; Nimma, Ramakrishna; Bulbule, Anuradha; Yadav, Amit Singh; Gorain, Mahadeo; Radharani, Nalukurthi Naga Venkata; Kundu, Gopal C.; Garnaik, Baijayantimala (ACS BIOMATERIALS SCIENCE & ENGINEERING, 2024)
Keywords: BULK-POLYMERIZATION; Drug-delivery; LIPOSOMAL DOXORUBICIN

Enhanced catalytic conversion of disaccharides to propylene glycol using metal-supported graphitic carbon nitride - Kirali, Arun Arunima Balachandran; Narayanan, Hariprasad; Viswanathan, Balasubramanian; Yadav, Parmeshwar; Marimuthu, Banu (Energy and Fuels, 2024)
Propylene glycol (or) 1,2-propanediol (1,2-PD) is an important polyol widely used for pharmaceuticals, polyester resins, paints, cosmetics, antifreeze, etc. Sucrose has emerged as a promising feedstock to produce 1,2-PD, as indicated by recent research findings. Graphitic carbon nitride (g-C3N4/gCN) was synthesized by using different crucibles. Ni-Mo was loaded on different g-C3N4 supports via the wetness impregnation method for sucrose hydrogenolysis. Effects of different g-C3N4 supports were studied. Catalysts with varying Ni (x = 0-8 wt %) and Mo (y = 0-15 wt %) contents were characterized using XRD, BET, XPS, FE-SEM, Py-FTIR, HR-TEM, TPD (CO2)and Raman spectroscopy. An attempt was made on sucrose conversion into 1,2-PD using a Ni-Mo/g-C3N4 catalyst. The catalyst containing 8% Ni and 10% Mo on Gr-gCN exhibited the best performance, achieving complete sucrose conversion with a 76% yield of 1,2-PD under mild reaction conditions. The presence of highly dispersed nanoparticles and the nature of graphitic carbon nitride help improve the reactions' yield by allowing reactions at lower temperatures, reducing the occurrence of side reactions, and increasing recycling rates. A straightforward approach to material preparation, coupled with the exceptional dispersion of metal nanoparticles, paves the way for a novel platform for biomass conversion.

Entropy-driven reversible melting and recrystallization of layered hybrid perovskites - Rajput, Parikshit Kumar; Salunkhe, Parashurama; Sarma, Manmayuri; Basu, Meghasree; Gopal, Animesh; Joshi, Aprajita; Shingote, Ajinkya Sundarnath; Saha, Surajit; Rahman, Atikur; Nag, Angshuman (SMALL, 2024)
Keywords: hybrid perovskites; photodetector; reversible melting

Exploring the synthesis, characterization, electrical, and magnetic behavior of crystalline Ni1-xZnxFe2O4 nanoparticles - Adsure, Kiran T.; Jagtap, Sumant B.; Newaskar, Shivkumar R.; Kore, Kiran B.; Funde, Adinath M.; Patange, Sunil M.; Late, Dattatray J. (JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS, 2024)
Keywords: CO; DC RESISTIVITY; DIELECTRIC-PROPERTIES; FERRITE NANOPARTICLES; Ni; Substitution; ZN

Extraction, characterization, and life cycle assessment of nanosilica from millet husk: sustainable alternative with low environmental impact - Dominic, C. D. Midhun; Rosa, Derval dos Santos; Barbosa, Rennan Felix da Silva; Anagha, O. V.; Neenu, K. V.; Begum, P. M. Sabura; Kumar, V. Aswathy; Parameswaranpillai, Jyotishkumar; Siriwong, Chomsri; Ajithkumar, T. G.; Shelke, Ankita; Pasc, Andreea (Journal of Cleaner Production, 2024)
Eco-friendly approaches for silica production are highly researched to respond increasing industrial demand for bio-nanofillers. Herein, nanosilica of 10-20 nm with mesoporosity was obtained through a mild oxalic acid pre-treatment of millet husk, followed by calcination at 700 degrees C for 2 h. Compared with commercial precipitated silica (CS) and millet husk ash (MHA) directly obtained by calcination of the husk, the pre-treated silica (MHS) had higher purity, revealed using EDX spectroscopy. Moreover, FTIR and Si-29 NMR showed a higher condensation degree in MHS with 73% of Q4 siloxane bonds vs 4% in MHA. The release of the metal and organic impurities from the husk also allows to reduce the crystallinity of MHS, and to increase the specific surface area from 82 m(2)/g in MHA to 238 m(2)/g in MHS. The type II N-2 adsorption-desorption isotherms of MHA and MHS indicate aggregates of non-porous silica particles. MHS also demonstrated remarkable thermal resilience. According to the LCA analysis, MHS has a 40% lower impact on global warming, a 38% lower impact on human carcinogenic toxicity, and a 38% lower impact on terrestrial acidification compared to rice husk nanosilica. This research thus addresses sustainability challenges by repurposing millet husks, which are readily available due to continuous millet cultivation, particularly in India. By reducing the ecological impact of husk disposal through burning, this study offers an economically viable technology for high-purity silica production, aligning with global efforts to combat climate change and promote sustainable practices.
Keywords: Life cycle assessment; Millet husk; Nanosilica; Oxalic acid

Genome sequencing and analysis of penicillin V producing Penicillium rubens strain BIONCL P45 isolated from India - Sawant, Amol M.; Navale, Vishwambar D.; Vamkudoth, Koteswara Rao (International Microbiology, 2024)
Background A filamentous fungus Penicillium rubens is widely recognized for producing industrially important antibiotic, penicillin at industrial scale. Objective To better comprehend, the genetic blueprint of the wild-type P. rubens was isolated from India to identify the genetic/biosynthetic pathways for phenoxymethylpenicillin (penicillin V, PenV) and other secondary metabolites. Method Genomic DNA (gDNA) was isolated, and library was prepared as per Illumina platform. Whole genome sequencing (WGS) was performed according to Illumina NovoSeq platform. Further, SOAPdenovo was used to assemble the short reads validated by Bowtie-2 and SAMtools packages. Glimmer and GeneMark were used to dig out total genes in genome. Functional annotation of predicted proteins was performed by NCBI non-redundant (NR), UniProt, Kyoto Encyclopedia of Genes and Genomes (KEGG), and Gene Ontology (GO) databases. Moreover, secretome analysis was performed by SignalP 4.1 and TargetP v1.1 and carbohydrate-active enzymes (CAZymes) and protease families by CAZy database. Comparative genome analysis was performed by Mauve 2.4.0. software to find genomic correlation between P. rubens BIONCL P45 and Penicillium chrysogenum Wisconsin 54-1255; also phylogeny was prepared with known penicillin producing strains by ParSNP tool. Results Penicillium rubens BIONCL P45 strain was isolated from India and is producing excess PenV. The 31.09 Mb genome was assembled with 95.6% coverage of the reference genome P. chrysogenum Wis 54-1255 with 10687 protein coding genes, 3502 genes had homologs in NR, UniProt, KEGG, and GO databases. Additionally, 358 CAZymes and 911 transporter coding genes were found in genome. Genome contains complete pathways for penicillin, homogentisate pathway of phenyl acetic acid (PAA) catabolism, Andrastin A, Sorbicillin, Roquefortine C, and Meleagrin. Comparative genome analysis of BIONCL P45 and Wis 54-1255 revealed 99.89% coverage with 2952 common KEGG orthologous protein-coding genes. Phylogenetic analysis revealed that BIONCL P45 was clustered with Fleming's original isolate P. rubens IMI 15378. Conclusion This genome can be a helpful resource for further research in developing fermentation processes and strain engineering approaches for high titer penicillin production.
Keywords: comparative genomics; Illumina NovoSeq; Penicillin biosynthesis; Penicillium rubens; Secondary metabolites; whole genome sequencing

Genome sequencing and protein modeling unraveled the 2AP biosynthesis in Bacillus cereus DB25 - Dhondge, Harshal V.; Barvkar, Vitthal T.; Dastager, Syed G.; Dharne, Mahesh S.; Rajput, Vinay; Pable, Anupama A.; Henry, Robert J.; Nadaf, Altafhusain B. (International Journal of Food Microbiology, 2024)
2-Acetyl-1-pyrroline (2AP) is an important and major flavor aroma compound responsible for the fragrance of basmati rice, cheese, wine, and several other food products. Biosynthesis of 2AP in aromatic rice and a few other plant species is associated with a recessive Betaine aldehyde dehydrogenase 2 (BADH2) gene. However, the literature is scant on the relationship between the functional BADH2 gene and 2AP biosynthesis in prokaryotic systems. Therefore, in the present study, we aimed to explore the functionality of the BADH2 gene for 2AP biosynthesis in 2AP synthesizing rice rhizobacterial isolate Bacillus cereus DB25 isolated from the rhizosphere of basmati rice (Oryza sativa L.). Full-length BcBADH2 sequence was obtained through whole genome sequencing (WGS) and further confirmed through traditional PCR and Sanger sequencing. Then the functionality of the BcBADH2 gene was evaluated in-silico through bioinformatics analysis and protein docking studies and further experimentally validated through enzyme assay. The sequencing and bioinformatics analysis results revealed a full-length 1485 bp BcBADH2 coding sequence without any deletion or premature stop codons. Full-length BcBADH2 was found to encode a fully functional protein of 54.08 kDa with pI of 5.22 and showed the presence of the conserved amino acids responsible for enzyme activity. The docking studies confirmed a good affinity between the protein and its substrate whereas the presence of BcBADH2 enzyme activity confirmed the functionality of BADH2 enzyme in B. cereus DB25. In conclusion, the findings of the present study suggest that B. cereus DB25 is able to synthesize 2AP despite a functional BADH2 gene and there may be a different molecular mechanism responsible for 2AP biosynthesis in bacterial systems, unlike that found in aromatic rice and other eukaryotic plant species.
Keywords: 2-Acetyl-1-pyrroline; Basmati rice flavor; Betaine aldehyde dehydrogenase 2; Protein-ligand docking; Rhizobacteria; Whole-genome sequence

Immunogenicity of SARS-CoV-2 vaccines BBV152 (COVAXIN®) and ChAdOx1 nCoV-19 (COVISHIELD™) in seronegative and seropositive individuals in India: a multicentre, nonrandomised observational study - Asokan, Mangaiarkarasi S.; Joan, Roshni Florina; Babji, Sudhir; Dayma, Girish; Nadukkandy, Prajitha; Subrahmanyam, Vinutha; Pandey, Archana; Malagi, Girish; Arya, Pooja; Mahajan, Vibhuti; Bhavikatti, Jayateerth; Pawar, Ketakee; et al. (Lancet Regional Health - Southeast Asia, 2024)
<p style="box-sizing: inherit; line-height: 1.5; margin: 1.2rem 0px; color: rgb(33, 33, 33); font-family: BlinkMacSystemFont, -apple-system, "Segoe UI", Roboto, Oxygen, Ubuntu, Cantarell, "Fira Sans", "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px;"> Background: There are limited global data on head-to-head comparisons of vaccine platforms assessing both humoral and cellular immune responses, stratified by pre-vaccination serostatus. The COVID-19 vaccination drive for the Indian population in the age group 18-45 years began in April 2021 when seropositivity rates in the general population were rising due to the delta wave of COVID-19 pandemic during April-May 2021. <p style="box-sizing: inherit; line-height: 1.5; margin: 1.2rem 0px; color: rgb(33, 33, 33); font-family: BlinkMacSystemFont, -apple-system, "Segoe UI", Roboto, Oxygen, Ubuntu, Cantarell, "Fira Sans", "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px;"> Methods: Between June 30, 2021, and Jan 28, 2022, we enrolled 691 participants in the age group 18-45 years across four clinical sites in India. In this non-randomised and laboratory blinded study, participants received either two doses of Covaxin® (4 weeks apart) or two doses of Covishield™ (12 weeks apart) as per the national vaccination policy. The primary outcome was the seroconversion rate and the geometric mean titre (GMT) of antibodies against the SARS-CoV-2 spike and nucleocapsid proteins post two doses. The secondary outcome was the frequency of cellular immune responses pre- and post-vaccination. <p style="box-sizing: inherit; line-height: 1.5; margin: 1.2rem 0px; color: rgb(33, 33, 33); font-family: BlinkMacSystemFont, -apple-system, "Segoe UI", Roboto, Oxygen, Ubuntu, Cantarell, "Fira Sans", "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px;"> Findings: When compared to pre-vaccination baseline, both vaccines elicited statistically significant seroconversion and binding antibody levels in both seronegative and seropositive individuals. In the per-protocol cohort, Covishield™ elicited higher antibody responses than Covaxin® as measured by seroconversion rate (98.3% vs 74.4%, p < 0.0001 in seronegative individuals; 91.7% vs 66.9%, p < 0.0001 in seropositive individuals) as well as by anti-spike antibody levels against the ancestral strain (GMT 1272.1 vs 75.4 binding antibody units/ml [BAU/ml], p < 0.0001 in seronegative individuals; 2089.07 vs 585.7 BAU/ml, p < 0.0001 in seropositive individuals). As participants at all clinical sites were not recruited at the same time, site-specific immunogenicity was impacted by the timing of vaccination relative to the delta and omicron waves. Surrogate neutralising antibody responses against variants-of-concern including delta and omicron was higher in Covishield™ recipients than in Covaxin® recipients; and in seropositive than in seronegative individuals after both vaccination and asymptomatic infection (omicron variant). T cell responses are reported from only one of the four site cohorts where the vaccination schedule preceded the omicron wave. In seronegative individuals, Covishield™ elicited both CD4+ and CD8+ spike-specific cytokine-producing T cells whereas Covaxin® elicited mainly CD4+ spike-specific T cells. Neither vaccine showed significant post-vaccination expansion of spike-specific T cells in seropositive individuals.

Influence of the crystal plane orientation in enhancing the electrochemical performance of a trication-substituted cathode for Li-ion batteries - Shivamurthy, Bogalera Papaiah; Thripuranthaka, Marulasiddappa; Shelke, Manjusha V.; Nayaka, Girish Praveen (Energy and Fuels, 2024)
High-voltage spinel cathodes with low nickel are promising candidates for Li-ion batteries owing to their high energy and power density, thermal stability, and eco-friendliness. However, the high operating voltage (similar to 4.7 V) leads to the decomposition of electrolytes, structural disorder, and deterioration of the cathode-electrolyte interphase (CEI) as well as hinders practical capability. We have synthesized trication-substituted spinel cathode materials with exposed (111) crystal planes and truncated octahedral shapes. These materials have demonstrated high specific discharge capacity and high rate capability up to 1000 cycles with a voltage window of 3.5-5 V. The crystal plane orientation of these materials has been investigated using X-ray diffraction of electrodes and electron microscopic studies and correlated with the electrochemical performance of the surface plane of exposed cathode materials. Among the three synthesized materials, the LMNFA2 cathode has shown a specific discharge capacity of 109.29 mAh g(-1) at 1 C after 1000 cycles with a capacity retention of 76.3%, which is nearly equal to the previously reported dual-phase material with the same metal compositions.

Inhibition of trehalose synthesis in lepidoptera reduces larval fitness - Tellis, Meenakshi B.; Mohite, Sharada D.; Nair, Vineetkumar S.; Chaudhari, Bhagyashri Y.; Ahmed, Shadab; Kotkar, Hemlata M.; Joshi, Rakesh S. (Advanced Biology, 2024)
Trehalose is synthesized in insects through the trehalose 6-phosphate synthase and phosphatase (TPS/TPP) pathway. TPP dephosphorylates trehalose 6-phosphate to release trehalose. Trehalose is involved in metamorphosis, but its relation with body weight, size, and developmental timing is unexplored. The expression and activity of TPS/TPP fluctuate depending on trehalose demand. Thus, TPS/TPP inhibition can highlight the significance of trehalose in insect physiology. TPS/TPP transcript levels are elevated in the pre-pupal and pupal stages in Helicoverpa armigera. The inhibition of recombinantly expressed TPP by N-(phenylthio)phthalimide (NPP), is validated by in vitro assays. In vivo inhibition of trehalose synthesis reduces larval weight and size, hampers metamorphosis, and reduces its overall fitness. Insufficient trehalose leads to a shift in glucose flux, reduced energy, and dysregulated fatty acid oxidation. Metabolomics reaffirms the depletion of trehalose, glucose, glucose 6-phosphate, and suppressed tricarboxylic acid cycle. Reduced trehalose hampers the energy level affecting larval vitality. Through trehalose synthesis inhibition, the importance of trehalose in insect physiology and development is investigated. Also, in two other lepidopterans, TPP inhibition impedes physiology and survival. NPP is also found to be effective as an insecticidal formulation. Overall, trehalose levels affect the larval size, weight, and metabolic homeostasis for larval-pupal transition in lepidoptera. Inhibition of trehalose synthesis enzyme TPS/TPP is a good model to study the contribution of trehalose in attaining body weight and in larval-pupal transition. Transcriptomics and metabolomics studies reveal overall reduced energy and dysregulated glucose, protein, and fatty acid metabolism.image
Keywords: Lepidoptera; metabolic homeostasis; trehalose; trehalose 6-phosphate phosphatase

Insights on prussian blue analogue cathode material engineered with polypyrrole surface protection layer for aqueous rechargeable zinc metal battery - Puthiyaveetil, Priyanka Pandinhare; Nair, Aathira; Dilwale, Swati; Kurian, Maria; Joshi, Kavita; Kurungot, Sreekumar (Small, 2024)
One of the key intricacies against using Prussian blue analogues (PBAs) in aqueous batteries is their gradual dissolution in aqueous electrolytes, resulting in inadequate cycling stability. Besides, the rate capability of PBAs is limited due to their poor electrical conductivity. To overcome these challenges, it is essential to tune the physical and chemical properties of PBAs at the nano regime without affecting the inherent charge storage properties, especially at high-voltage operating conditions. Through this work, a strategy is demonstrated to enhance the electrochemical performance of vanadium-based PBA (V-PBA) by surface engineering using a conducting polymer nano-skin (V-PBA/PPy) for aqueous zinc metal batteries. The polypyrrole (PPy) nano-skin over the V-PBA nanoparticles acts as an electron percolation path to ameliorate the poor electronic conductivity of the otherwise pristine V-PBA. Interestingly, the V-PBA with an optimized polypyrrole coating (V-PBA/PPy-2) exhibits an enhanced specific capacity (173 mAh g-1 at 0.10 A g-1) than the pristine V-PBA counterpart (80 mAh g-1) and 85% capacity retention up to 500 cycles. The DFT calculation confirms the synergistic interaction between PPy and V-PBA and the presence of PPy favors the adsorption of Zn.
Keywords: aqueous rechargeable zinc metal battery; DFT; polypyrrole coating; Prussian blue analogue; surface protection layer

Intertwining of localized (d) and delocalized (π) spins in magnetically frustrated two-dimensional metal-organic frameworks - Ugale, Ajay; Ninawe, Pranay; Jain, Anil; Sangole, Mayur; Mandal, Rimpa; Singh, Kirandeep; Ballav, Nirmalya (Inorganic Chemistry, 2024)
Two-dimensional metal-organic frameworks (2D MOFs) are emerging as a new class of multifunctional materials for diversified applications, although magnetic properties have not been widely explored. The metal ions and organic ligands in some of the 2D MOFs are arranged in the well-known Kagome lattice, leading to geometric spin frustration. Hence, such systems could be the potential candidates to exhibit an exotic quantum spin liquid (QSL) state, as was observed in Cu-3(HHTP)(2) (HHTP = hexahydroxytriphenylene), with no magnetic transition down to 38 mK. Hereto, we have investigated the spin intertwining in a bimetallic 2D MOF system, M-3(HHTP)(2) (M = Cu/Zn)(,) arising from the localized (d-electron) and delocalized (pi-electron) S = 1/2 spins from the Cu(II) ions and the HHTP radicals, respectively. The origin of the spin frustration (down to 5K) was critically examined by varying the metal composition in bimetallic systems, CuxZn3-x(HHTP)(2) (x = 1, 1.5, 2), containing both S = 1/2 and S = 0 spins. Additionally, to gain a deeper understanding, we studied the spin interaction in the pristine Zn-3(HHTP)(2) system containing only S = 0 Zn(II) ions. In view of the quantitative estimate of the localized and delocalized spins, the d-pi spin correlation appears essential in understanding the unusual magnetic and/or other physical properties of such hybrid organic-inorganic 2D crystalline solids

Investigation of structural and morphological insights of nanostructured layered double hydroxides: catalytic activity in aldol condensation - Bhagat, Shailesh K.; Nagpure, Atul S.; Lanjewar, Mamata R.; Gode, Nilesh G.; Thakare, Sanjay R. (Journal of Porous Materials, 2024)
Layered double hydroxides (LDHs) materials finds extensive applications in numerous fields such as medical science, industrial sector, agriculture and food, catalysis, polymers, nanotechnology, etc. The LDHs properties (structural, textural, morphological, spectroscopic and theoretical insights) can be design for achieving required materials for particular application in scientific areas. In the current investigation, we have synthesized mesoporous nanostructured LDHs materials via microwave, sonication and stirring method. The nanostructured LDHs was scientifically characterized by various physico-chemical techniques like XRD, N2 sorption, TGA, solid state one-dimensional 27Al magic angle spinning NMR spectroscopy, XPS, Raman Spectroscopy, FT-IR, ICP-OES, Electron Microscopy (SEM, FE-SEM, TEM and HR-TEM), EDX, elemental analysis, etc. On the basis of experimental study, it can be evidently witnessed that nanostructured LDHs materials was formed with good crystalline mesoporous nature. Solid state 27Al NMR showed single and sharp 27Al NMR signal at chemical shift value of + 1.4 ppm, strongly suggesting the presence of octahedral (Oh) AlO6 coordination site in all as-synthesized LDHs. Microwave and sonication techniques furnishes regularly dispersed well-developed flower-shaped nanocrystals however, stirring method gives mostly agglomerated nano-sized platelets. The mechanistic insights for the fabrication of nanostructures LDHs via microwave, sonication and stirring process were also highlighted. The different LDHs materials were utilized in the aldol condensation reaction of furfural with acetone for understanding structure-activity correlation. Microwave and sonication methodologies can be further exploited for the synthesis of many other inorganic-organic nanocomposites materials with stable and good dispersion of nanocrystals in addition to desired morphology and catalytic activity.
Keywords: Aldol condensation; catalysis; Flower-shaped nanocrystals; layered double hydroxides; Microwave and sonication techniques; Nanostructured materials

La-Fe-O perovskite based gas sensors: recent advances and future challenges - Patil, Suraj S.; Babar, Bapuso M.; Nadargi, Digambar Y.; Shaikh, Faiyyaj I.; Nadargi, Jyoti D.; Sankapal, Babasaheb R.; Mulla, Imtiaz S.; Tamboli, Mohaseen S.; Truong, Nguyen Tam Nguyen; Suryavanshi, Sharad S. (ACS OMEGA, 2024)
Keywords: ASSISTED SYNTHESIS; ETHANOL SENSING CHARACTERISTICS; LAFEO3 NANOPARTICLES

Ligand isomerization driven electrocatalytic switching - Kottaichamy, Alagar Raja; Nazrulla, Mohammed Azeezulla; Parmar, Muskan; Thimmappa, Ravikumar; Devendrachari, Mruthyunjayachari Chattanahalli; Vinod, Chathakudath Prabhakaran; Volokh, Michael; Kotresh, Harish Makri Nimbegondi; Shalom, Menny; Thotiyl, Musthafa Ottakam (ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2024)
Keywords: Catalysts; CO2 reduction; O-2 REDUCTION; oxygen reduction

Mechanistic modeling of size exclusion chromatography-assisted in vitro refolding of the recombinant biosimilar teriparatide (PTH-34) - Ughade, Santosh; Rana, Sunil; Nadeem, Mohd; Kumthekar, Rupali; Mahajani, Sanjay; Bhambure, Rahul (ACS Omega, 2024)
In vitro protein refolding is one of the critical unit operations in manufacturing recombinant peptides expressed using Escherichia coli as host cells. This study is focused on designing size exclusion chromatography-assisted in vitro refolding process for biosimilar recombinant parathyroid hormone. Inclusion bodies (IBs) of recombinant parathyroid hormone were solubilized at higher pH, and in vitro refolding was performed using size exclusion chromatography. In the first part of the investigation, DoE-based empirical optimization was performed to achieve a higher refolding yield for a biosimilar recombinant parathyroid hormone. The effect of solubilized inclusion body (IB) feed volume, concentration of IBs, and residence time on in vitro refolding of recombinant teriparatide was studied using the Box-Behnken design. Size exclusion chromatography (SEC)-assisted in vitro refolding was performed at 8 C-degrees at pH 10.5 by using 20 mM Tris buffer. The maximum refolding yield of 98.12% was achieved at feed volume (12.5% of CV) and 20 mg/mL inclusion body (IB) concentration with a residence time of 50 min and a purity of 66.1% based on densitometric analysis using SDS-PAGE. In the latter part of the investigation, the general rate mechanistic model framework for size exclusion chromatography was developed and validated with the experimental results. The developed model helped in the accurate prediction of the elution volumes and product yield. The developed model also helps to predict the elution performance of a scalable column a priori. Post in vitro refolding, the formation of the native peptide structure was examined using various orthogonal analytical tools to study the protein's primary, secondary, and tertiary structures. The developed hybrid process development approach is a valuable tool toachieve high-yield, scalable refolding conditions for recombinant proteins without disulfide bonds.

Modular synthesis of unsymmetrical indolyl diketones from ynediones via sequential aza-Michael addition/C-H functionalization - Naveed, Abdul; Bag, Debojyoti; Sawant, Sanghapal D. (Organic & Biomolecular Chemistry, 2024)
Herein, we disclose an efficient approach for the synthesis of unsymmetrical indolyl diketones from easily accessible 1,2-alkynediones involving a sequential aza-Michael addition/C-H Functionalization process. The two-step, one-pot strategy involves the aza-Michael addition of an aniline generating the N-aryl enaminones followed by iodine-mediated C-H functionalization.

Morphology tuning via linker modulation: metal-free covalent organic nanostructures with exceptional chemical stability for electrocatalytic water splitting - Karak, Shayan; Koner, Kalipada; Karmakar, Arun; Mohata, Shibani; Nishiyama, Yusuke; Duong, Nghia Tuan; Thomas, Neethu; Ajithkumar, Thalasseril Govindankuttykaimal; Hossain, Munshi Sahid; Bandyopadhyay, Subhajit; Kundu, Subrata; Banerjee, Rahul (Advanced Materials, 2024)
The development of synthetic routes for the formation of robust porous organic polymers (POPs) with well-defined nanoscale morphology is fundamentally significant for their practical applications. The thermodynamic characteristics that arise from reversible covalent bonding impart intrinsic chemical instability in the polymers, thereby impeding their overall potential. Herein, a unique strategy is reported to overcome the stability issue by designing robust imidazole-linked POPs via tandem reversible/irreversible bond formation. Incorporating inherent rigidity into the secondary building units leads to robust microporous polymeric nanostructures with hollow-spherical morphologies. An in-depth analysis by extensive solid-state NMR (1D and 2D) study on H-1, C-13, and N-14 nuclei elucidates the bonding and reveals the high purity of the newly designed imidazole-based POPs. The nitrogen-rich polymeric nanostructures are further used as metal-free electrocatalysts for water splitting. In particular, the rigid POPs show excellent catalytic activity toward the oxygen evolution reaction (OER) with long-term durability. Among them, the most efficient OER electrocatalyst (TAT-TFBE) requires 314 mV of overpotential to drive 10 mA cm(-2) current density, demonstrating its superiority over state-of-the-art catalysts (RuO2 and IrO2).
Keywords: bi-functional electrocatalysts; chemically robust; hollow-spherical morphologies; imidazole-linked; inherent rigidity; metal-free; water splitting

Multi-dimensional impact of captopril modification on human serum albumin - Ghosh, Amrita; Jani, Vinod; Sonavane, Uddhavesh; Naphade, Anvi N.; Joshi, Rajendra; Kulkarni, Mahesh J.; Giri, Ashok P. (International Journal of Biological Macromolecules, 2024)
Captopril is a thiol drug, widely used for the management of hypertension and cardiovascular diseases. Reactive thiols are found to covalently modify the cysteines of plasma proteins and affect their structure and function. Human serum albumin (HSA) is prone to undergo modification by various low molecular weight compounds, including drugs. Cysteine34 (Cys34) in HSA has a free thiol group with antioxidant properties, considered to be the most redox-sensitive amino acid in plasma. Through mass-spectrometric analysis, we demonstrate for the first time that captopril forms a disulfide adduct at Cys34 residue and increases the protease susceptibility of HSA to trypsin. As evidenced by our biophysical and electron microscopy studies, HSA undergoes structural alteration, aggregation and morphological changes when treated with different captopril concentrations. Molecular dynamics studies further revealed the regions of secondary structural changes in HSA due to disulfide adduct formation by captopril at Cys34. It also elucidated the residues involved in the noncovalent interactions with captopril. It is envisaged that structural change in HSA may influence the efficacy of drug delivery as well as its own biological function. These findings may thus provide significant insights into the field of pharmacology intriguing further investigation into the effects of long-term captopril treatment.
Keywords: Captopril; Electron microscopy; Human serum albumin; Mass spectrometry; Molecular dynamic simulation; Spectrophotometry

Nonedible thevetia peruviana oil for the synthesis of biobased thermosets and vitrimers with tunable mechanical properties - Olosho, Adebayo Isaac; Alam, Md Shafi; Sukumaran Nair, Kiran; Ambade, Ashootosh V.; Adekola, Folahan Amoo (ACS Applied Polymer Materials, 2024)
Current attempts to replace fossil-derived materials with vegetable oils for polymer production mainly rely on edible oils. This approach raises sustainability concerns due to potential food security risks. This report introduces the first in-depth examination of Thevetia peruviana oil (TPO) epoxidation, an easily accessible nonedible vegetable oil, utilizing diverse acidic ion-exchange resins as catalysts. It is followed by the development of vitrimers based on epoxidized oil (ETPO) with various dicarboxylic acid hardeners. Amberlite IRC120H emerged as the most effective catalyst for the epoxidation of the oil, allowing for repeated catalyst reusability for up to five cycles. An impressive relative oxirane conversion of 98.9% was achieved after optimization. DSC analysis revealed that among the diacids, 2,2'-dithiodibenzoic acid (DTBZ) has the lowest activation energy with ETPO. Additionally, the ETPO-DTBZ-based thermosets displayed exceptional solvent resistance and thermal stability, indicative of a high degree of cross-linked networks within the system. Mechanical analyses revealed that all aliphatic hardeners resulted in soft materials, while DTBZ resulted in thermosets with tensile stress and modulus of 15 and 843 MPa, respectively. Consequently, DTBZ-ETPO thermosets were successfully recycled, repaired, and reshaped with minimal changes in the mechanical properties. The shape memory of the thermosets was also established.
Keywords: biobasedvitrimers; environmental sustainability; epoxidizedThevetial peruviana oil; nonedible oil; Optimization; shape memory

Novel GO hoisted SnO2-BiOBr bifunctional catalyst for the remediation of organic dyes under illumination by visible light and electrocatalytic water splitting - Dhillon, Manshu; Naskar, Abhishek; Kaushal, Neha; Bhansali, Shekhar; Saha, Avishek; Basu, Aviru Kumar (NANOSCALE, 2024)
Keywords: Chemistry; Multidisciplinary; Nanoscience & Nanotechnology

One-pot production of liquid hydrocarbons by catalytic hydrodeoxygenation of lignocellulosic biomass using nickel loaded on zeolite-based supports - Siakpebru, Odiri K.; Uchagawkar, Anoop; Gurrala, Lakshmiprasad; Bartlett, Jared; Adamson, Piersen; Gorschak, Nicholas; Hassiba, Adam; Niphadkar, Prashant; Bokade, Vijay; Morais, Ana Rita C. (Energy & Fuels, 2024)
The synthesis of liquid hydrocarbons from lignocellulosic biomass has been achieved with notable success. However, these technologies often require multistep approaches and are energy intensive. Thus, there is a considerable economic and environmental benefit of process intensification by the synthesis of liquid hydrocarbons in a one-pot process. For the first time, we report direct conversion of raw poplar into liquid alkanes and aromatics (carbon yield of 15.6 +/- 0.6 wt %) with high selectivity toward C-7-C15 cycloalkanes (7.8 +/- 0.1 wt %) and low level of oxygenated compounds (<2.0 wt %) at 270 degrees C and 3 MPa initial H(2 )pressure for 6 h using 10% Ni/H-beta zeolite as a catalyst and cyclohexane as a solvent. The effect of temperature (250-270 degrees C), Ni loading (0-10%), and type of zeolite support (H-beta, ZSM-5, and USY) on process performance was also investigated. In addition, the 10% Ni/H-beta catalyst showed recyclability over two reactions, with a 17.6% decrease in liquid hydrocarbon yield after the first reaction. This approach has the potential to simplify the synthesis of liquid fuels from lignocellulosic biomass.