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 conversion of sucrose to 1,2-propanediol over alumina-supported Ni-Mo bimetallic catalysts - Sreekantan, Sreejith; Kirali, Arun Arunima Balachandran; Marimuthu, Banu (Sustainable Energy & Fuels, 2022)
Ni-Mo supported on gamma-Al2O3 catalysts were synthesized to test its catalytic activity towards sucrose to 1,2-propanediol (1,2-PDO) conversion. The catalyst system was characterized using various physicochemical methods, including XRD, BET, py-FTIR, XPS, FE-SEM, HR-TEM and ICP. The metal combination of 8%Ni-20%Mo/gamma-Al2O3 is found to be effective in producing a good yield of 1,2-propanediol (similar to 74%) under mild reaction conditions of 180 degrees C, 40 bar H-2 pressure and a run time of 4.5 h in a batch reaction. The activity of the active catalyst over various substrates such as cellulose, glucose, fructose and real-source biomass has also been investigated. XPS analysis of the active catalyst confirms the various oxidation states of the metals Ni and Mo in the active catalyst. The py-IR results show that the optimum Lewis to Bronsted acidic site ratio is responsible for the selective conversion of sucrose to 1,2-PDO. The presence of interparticle mesopores on gamma-Al2O3 helps in the high conversion of sucrose. Furthermore, the catalyst has been found reusable for four consecutive runs without any structural or morphological changes.

Ce promoted Cu/?-Al2O3 catalysts for the enhanced selectivity of 1,2-pro-panediol from catalytic hydrogenolysis of glucose - Kirali, Arun Arunima Balachandran; Sreekantan, Sreejith; Marimuthu, Banu (Catalysis Communications, 2022)
Ce promoted Cu/gamma-Al2O3 catalysts were prepared with varying amounts of Cu (x = 0-10 wt%) and Ce (y = 0-15 wt%). The prepared catalysts were characterized and tested for the conversion of aqueous glucose (5 wt%) to 1,2propanediol in a batch reactor. 10%Ce-8%Cu/gamma-Al2O3 & nbsp;showed the complete conversion of glucose with 62.7% selectivity of 1,2-propanediol and total glycols (1,2-propanediol, ethylene glycol & 1,2-butanediol) of 81% at milder reaction conditions. Cu facilitated the hydrogenation activity and Ce loading optimize the acid/base sites of Cu/gamma-Al2O3 which obtain high selectivity of 1, 2-propanediol. Catalyst reusability is reported.
Keywords: 2-Propanediol; 1; Cu-Ce catalyst; ethylene glycol; Gamma alumina; Glucose hydrogenolysis

C-O hydrogenolysis of C3-C4 polyols selectively to terminal diols over Pt/W/SBA-15 catalysts - Bhowmik, Susmita; Enjamuri, Nagasuresh; Marimuthu, Banu; Darbha, Srinivas (Catalysts, 2022)
Pt/W/SBA-15 catalysts (with Pt-loading = 0.5-4 wt% and W-loading = 1 wt%) prepared by the sequential impregnation method were evaluated for selective C-O cleavage of erythritol and glycerol in an aqueous medium. The Pt and W particles dispersed on SBA-15 approached close proximity at higher Pt loadings and afforded synergistic enhancement in C-O hydrogenolysis activity/selectivity. 1,4-Butanediol yields of 30.9% (at 190 degrees C, 50 bar H-2 and 24 h) and 1,3-propanediol yields of 34.4% (at 190 degrees C, 50 bar H-2 and 12 h of reaction) were obtained over these catalysts. Pt nanoparticles (facilitating dissociative H-2 adsorption and spillover) and W (present as acidic oligomeric WOx species; activating and coordinating the polyol via 1 degrees-OH group) worked in tandem for the selective hydrogenolysis of polyols yielding terminal diols of industrial demand.
Keywords: diol; Erythritol; Glycerol; Hydrodeoxygenation; Pt; SBA-15; W

Comparative investigation on the catalytic performance of HT/SBA-15 and SBA-15/HT composites for the isomerization of glucose to fructose - Manikandan, Marimuthu; Arjunan, Ayyappan; Prabu, Marimuthu; Raja, Thirumalaiswamy; Sangeetha, Palanivelu (Materials Science and Engineering B-Advanced Functional Solid-State Materials, 2022)
Hydrotalcites (HT) have a broad spectrum of applications as prosperous heterogeneous catalysts for diverse chemical transformations. The catalytic activity of HT-based materials can be tailored by introducing siliceous material into the internal or external framework. The surface modification of the HT framework with silica mesostructures leads to the formation of versatile Lewis base, Bronsted base and redox catalytic active sites. This work presents the comparative evaluation of the catalytic performance of HT/SBA-15 and SBA-15/HT composites for the isomerization of glucose to fructose using 1-butanol as a solvent. The composites with different external morphology were prepared by a modified template-assisted hydrothermal method, using different HT to SBA-15 proportions. The textural and morphological characterization results conferred the efficiency of the employed post-synthetic intercalation strategy to achieve the successful formation of HT/SBA-15 and SBA-15/HT composites. With optimal HT loading and surface basicity, the HTS-3 composite demonstrated the highest catalytic performance, resulting in good glucose conversions (54 %) with improved selectivity (>83 %). The observed high reactivity could be mainly attributed to the extensive dispersion of HT particles on the SBA-15 component, which contributes to a significant increase in textural properties and surface basicity. Furthermore, special attention is devoted to addressing such reactivity phenomena as active site selectivity, catalyst multifunctionality and multisite reactivity commonly encountered in mesoporous catalysis.
Keywords: composites; glucose; hydrotalcite; isomerization; SBA-15

Concerted effect of Ni-in and S-out on ReS2 nanostructures towards high-efficiency oxygen evolution reaction - Das, Tapas K.; Ping, Tapan; Mohapatra, Manoj; Anwar, Shahid; Gopinath, Chinnakonda S.; Jena, Bikash Kumar (Chemical Communications, 2022)
Herein, a one-step hydrothermal reaction is developed to synthesize a Ni-doped ReS2 nanostructure with sulphur defects. The material exhibited excellent OER activity with a current density of 10 mA cm(-2) at an overpotential of 270 mV, a low Tafel slope of 31 mV dec(-1), and good long-term durability of 10 h in 1 M KOH. It shows high faradaic efficiency of 96%, benefiting from the rapid charge transfer caused by the concerted effect of Ni-in and S-out on the ReS2 nanostructure.

Construction of tetrahydrobenzo[f]quinoline scaffolds via polar [4+2]-Cycloaddition reaction with arynes as dienophiles - Pandya, Virat G.; Mhaske, Santosh B. (Tetrahedron Letters, 2022)
A transition-metal-free route has been developed for the direct synthesis of biologically significant tetrahydrobenzo[f]quinoline scaffolds. The reaction features polar [4 + 2] Diels-Alder cycloaddition reaction of arynes with a well-designed diene N-Boc protected vinyl tetrahydropyridine, followed by the isomerisation of the double bond leading to the formation of tetrahydrobenzo[f]quinoline scaffolds in good to moderate yields.
Keywords: Aryne; Diels-Alder; Diene; Tetrahydrobenzo[ f ]quinoline

Controlled modulation of the structure and luminescence properties of zero-dimensional manganese halide hybrids through structure-directing metal-ion (Cd2+ and Zn2+) centers - Das, Deep Kumar; Bakthavatsalam, Rangarajan; Anilkumar, Vishnu; Mali, Bhupendra P.; Ahmed, Md Soif; Raavi, Sai Santosh Kumar; Pallepogu, Raghavaiah; Kundu, Janardan (Inorganic Chemistry, 2022)
Zero-dimensional (0D) metal halide hybrids with high exciton binding energy are excellent materials for lighting applications. Controlling/modulating the structure of the con-stituent metal halide units allows tunability of their photo-luminescence properties. 0D manganese halide hybrids are currently attracting research efforts in lighting applications due to their eco-friendly and strong emission. However, structural transformation-induced tunability of their photophysical propertieshas rarely been reported. Herein, we demonstrate a rationalsynthetic strategy to modulate the structure and luminescenceproperties of 0D Mn(II) halide hybrids utilizing the structure-directing d10metal ions (Cd2+/Zn2+). 0D metal halide hybrids ofCd2+/Zn2+, which act as hosts with tunable structures, accept Mn2+ions as substitutional dopants. This structural flexibility of thehost d10metal ions is realized by optimizing the metal-to-ligand ratio (Cd/AEPip). This reaction parameter allows structuraltransformation from an octahedral (AEPipCdMnBrOh) to a tetrahedral (AEPipCdMnBrTd) 0D Mn halide hybrid with tunableluminescence (orange -> green) with high photoluminescence quantum yield. Interestingly, when Zn2+is utilized, a tetrahedralAEPipZnMnBr structure forms exclusively with strong green emission. Optical and single-crystal X-ray diffraction structural analysisof the host and the doped system supports our experimental data and confirms the structure-directing role played by Cd2+/Zn2+centers. This work demonstrates a rational strategy to modulate the structure/luminescence properties of 0D Mn(II) halide hybrids, which can further be implemented for other 0D metal halide hybrids

Conventional and microwave-assisted organic synthesis of novel antimycobacterial agents bearing furan and pyridine hybrids - Desai, Nisheeth C.; Bhatt, Kandarp; Jadeja, Dharmpalsinh J.; Mehta, Harsh K.; Khedkar, Vijay M.; Sarkar, Dhiman (Drug Development Research, 2022)
Drug resistance in tuberculosis poses a serious threat to humanity because currently available antitubercular drugs are ineffective against Mycobacterium tuberculosis (M. tuberculosis). As a result, the approval of Bedaquiline and Delamanid for the treatment of drug-resistant tuberculosis was accelerated. Still, there is an urgent need to search for new antitubercular drugs with novel mechanisms of action (MoA). Due to this, we have designed a synthetic strategy by utilizing microwave-assisted organic synthesis. We have compared our method with the conventional procedure, and the data show that our procedure is more effective in the preparation of title compounds. A unique series of 1-(2-(furan-2-yl)-5-(pyridin-4-yl)-1,3,4-oxadiazol-3(2H)-yl)-3-(aryl)-pr op-2-en-1-ones (5a-o) was synthesized utilizing conventional and microwave-assisted techniques. Synthetic compounds were investigated for antitubercular activity against Mycobacterium TB H37Ra and Mycobacterium bovis (M. bovis). Compound 5b was reported to be the most effective against M. tuberculosis H37Ra (97.69 percent inhibition at 30 mu g/ml) and M. bovis (97.09 percent inhibition at 30 mu g/ml). An in silico binding affinity study of mycobacterial enoyl-acyl carrier protein reductase (InhA) reveals the binding mechanism and thermodynamic interactions that determine these molecule's binding affinity. Compound 5b had a high glide score of -8.991 and low glide energy of -49.893 kcal/mol.
Keywords: Antitubercular activity; microwave-assisted organic synthesis; Molecular docking

Copper(II) import and reduction are dependent on His-Met clusters in the extracellular amino terminus of human copper transporter-1 - Kar, Sumanta; Sen, Samarpita; Maji, Saptarshi; Saraf, Deepashri; Ruturaj; Paul, Rupam; Dutt, Sohini; Mondal, Basudeb; Rodriguez-Boulan, Enrique; Schreiner, Ryan; Sengupta, Durba; Gupta, Arnab (Journal of Biological Chemistry, 2022)
Copper(I) is an essential metal for all life forms. Though Cu(II) is the most abundant and stable state, its reduction to Cu(I) via an unclear mechanism is prerequisite for its bioutilization. In eukaryotes, the copper transporter-1(CTR1) is the primary high-affinity copper importer, although its mechanism and role in Cu(II) reduction remain uncharacterized. Here we show that extracellular amino-terminus of human CTR1 contains two methionine-histidine clusters and neighboring aspartates that distinctly bind Cu(I) and Cu(II) preceding its import. We determined that hCTR1 localizes at the basolateral membrane of polarized MDCK-II cells and that its endocytosis to Common-Recycling-Endosomes is regulated by reduction of Cu(II) to Cu(I) and subsequent Cu(I) coordination by the methionine cluster. We demonstrate the transient binding of both Cu(II) and Cu(I) during the reduction process is facilitated by aspartates that also act as another crucial determinant of hCTR1 endocytosis. Mutating the first Methionine cluster ((7)Met-Gly-Met(9)) and Asp(13)( )abrogated copper uptake and endocytosis upon copper treatment. This phenotype could be reverted by treating the cells with reduced and nonreoxidizable Cu(I). We show that histidine clusters, on other hand, bind Cu(II) and are crucial for hCTR1 functioning at limiting copper. Finally, we show that two N-terminal His-Met-Asp clusters exhibit functional complementarity, as the second cluster is sufficient to preserve copper-induced CTR1 endocytosis upon complete deletion of the first cluster. We propose a novel and detailed mechanism by which the two His-Met-Asp residues of hCTR1 amino-terminus not only bind copper, but also maintain its reduced state, crucial for intracellular uptake.

Crystalline xylitol production from corncob biomass with oral toxicity analysis - Ahuja, Vishal; Dasgupta, Diptarka; Kshirsagar, Siddheshwar; Ghosh, Prasenjit; More, Snehal; Gupta, Piyush; Behera, Babita; Bhaskar, Thallada (Industrial Crops and Products, 2022)
Xylitol, a five-carbon sugar alcohol, has a steady global market and finds application as a natural sugar substitute in various food and confectionery products. Biocatalytic xylitol production, although touted as a greener alternative to conventional chemical catalysis, suffers from certain challenges, the primary being high cost of production. This study demonstrates a process for food-grade xylitol production from corncob biomass with energy reduction through two major process modifications. A non-conventional fermentation strategy was adopted whereby adjusting aeration without agitation, xylitol with high yield (0.86 +/- 0.015 g/g), and productivity (0.74 gL(-1)h(-1)) could be produced by a GRAS Pichia caribbica MTCC 5703 strain. Xylitol was recovered from the broth in the form of crystals using a combination of membrane-based filtration and crystallization. The crystals demonstrated similar to 98 % purity when quantified with H-1 NMR. Oral toxicity analysis of the crystals demonstrated no adverse effect in female Winstar rats (at a loading of 2000 mg/kg body weight of animals). Overall process statistics showed that 0.584 kg of food-grade xylitol crystals could be produced from 3.5 kg of corncob biomass. The two-process modifications during fermentation and xylitol recovery enabled an energy saving of similar to 20.842 kW/kg of crystals, providing tremendous advantages for biorefinery-based large-scale xylitol production from corncob biomass.
Keywords: Biomass; Fermentation; Oral toxicity analysis; Wastewater treatment; xylitol

Cyclic peptide engineered from phytocystatin inhibitory hairpin loop as an effective modulator of falcipains and potent antimalarial - Mishra, Manasi; Singh, Vigyasa; Tellis, Meenakshi B.; Joshi, Rakesh S.; Pandey, Kailash C.; Singh, Shailja (Journal of Biomolecular Structure & Dynamics, 2022)
Cystatins are classical competitive inhibitors of C1 family cysteine proteases (papain family). Phytocystatin superfamily shares high sequence homology and typical tertiary structure with conserved glutamine-valine-glycine (Q-X-V-X-G) loop blocking the active site of C1 proteases. Here, we develop a cysteine-bounded cyclic peptide (CYS-cIHL) and linear peptide (CYS-IHL), using the conserved inhibitory hairpin loop amino acid sequence. Using an in silico approach based on modeling, protein-peptide docking, molecular dynamics simulations and calculation of free energy of binding, we designed and validated inhibitory peptides against falcipain-2 (FP-2) and -3 (FP-3), cysteine proteases from the malarial parasite Plasmodium falciparum. Falcipains are critical hemoglobinases of P. falciparum that are validated targets for the development of antimalarial therapies. CYS-cIHL was able to bind with micromolar affinity to FP-2 and modulate its binding with its substrate, hemoglobin in in vitro and in vivo assays. CYS-cIHL could effectively block parasite growth and displayed antimalarial activity in culture assays with no cytotoxicity towards human cells. These results indicated that cyclization can substantially increase the peptide affinity to the target. Furthermore, this can be applied as an effective strategy for engineering peptide inhibitory potency against proteases.
Keywords: Cyclic peptide; falcipain inhibitors; falciparum; P; Phytocystatin; protein interaction mimics; protein&#8211

Deciphering the sensing of alpha-amyrin acetate with hs-DNA: a multipronged biological probe - Pansare, V. Amol; Shedge, Amol A.; Sonawale, Maryappa C.; Pansare, V. Shubham; Mahakal, Akshay D.; Khairkar, Shyam R.; Chhatre, Shraddha Y.; Kulal, Dnyaneshwar K.; Patil, Vishwanath R. (RSC Advances, 2022)
In this study, we focus on the biomimetic development of small molecules and their biological sensing with DNA. The binding of herring sperm deoxyribonucleic acid (hs-DNA) with naturally occurring bioactive small molecule alpha-amyrin acetate (alpha-AA), a biomimetic - isolated from the leaves of Ficus (F.) arnottiana is investigated. Collective information from various imaging, spectroscopic and biophysical experiments provides evidence that alpha-AA is a minor groove sensor of hs-DNA and preferentially binds to the A-T-rich regions. Interactions of different concentrations of small molecule alpha-AA with hsDNA were evaluated via various analytical techniques such as UV-Vis, circular dichroism (CD) and fluorescence emission spectroscopy. Fluorescence emission spectroscopy results suggest that alpha-AA decreases the emission level of hsDNA. DNA minor groove sensor Hoechst 33258 and intercalative sensor EB, melting transition analysis (T-M) and viscosity analysis clarified that alpha-AA binds to hs-DNA via a groove site. Biophysical chemistry and molecular docking studies show that hydrophobic interactions play a major role in this binding. The present research deals with a natural product biosynthesis-linked chemical-biology interface sensor as a biological probe for alpha-AA: hs-DNA.

Design of hydrodynamic cavitation assisted intensified tertiary treatment unit for effective degradation of organic micropollutants in pharmaceutical industrial effluent: a case study with triclosan - Mishra, Birupakshya; Mukherjee, Anupam; Mullick, Aditi; Bhandari, Vinay M.; Moulik, Siddhartha (Journal of Water Process Engineering, 2022)
Increasing occurrence of micropollutants and trace amount of persistent organic contaminants (POC's) in the wastewater streams even after the well-established conventional treatment is a threat to human health, aquatic entities, and constitute a formidable challenge for the ecological security. In this regard, hydrodynamic cavi-tation based advanced oxidation treatment has attracted extensive attention towards removal of such micro scale pollutants from wastewater streams in the present scenario. Hence, the present work demonstrates the design and application of a rotating hydrodynamic cavitation (RHC) reactor with stator-rotor arrangement for effective degradation of organic micropollutants (triclosan being taken as the target pollutant) from tertiary effluents occurring in the pharmaceutical sector. The process performance was evaluated through optimization of geo-metric parameters of the reactor, various operating parameters as well as by studying the sole and synergistic performance of the HC process combined with other AOPs. The maximum degradation of Triclosan (TCS) ach-ieved by RHC alone was found to be 35.2 % and in synergism, with ozone, a maximum of 97.6 % degradation was observed. Further, to ensure the mineralization of the components, total organic carbon (TOC) contents of the samples were measured and the degradation pathway was predicted through LC-MS analysis. The techno-economic feasibility of the process were understood through economic and energetic analysis and technology transfer was done for replicating the same study for a pilot scale reactor.
Keywords: Advanced oxidation process; Hydrodynamic cavitation; Micropollutant; Pharmaceutical effluent; Tertiary treatment

Design, synthesis of anticancer and anti-inflammatory 4-(1-methyl-1H-indol-3-yl)-6-(methylthio) pyrimidine-5-carbonitriles - Bhale, Pravin S.; Chavan, V. Hemant; Shringare, Sadanand N.; Khedkar, Vijay M.; Tigote, Radhakrishna M.; Mali, Nikita N.; Jadhav, Tukaram D.; Kamble, Nitin B.; Kolat, Swati P.; Bandgar, Babasaheb P.; Patil, Harshal S. (Synthetic Communications, 2022)
A novel series of 4-(1-methyl-1H-indol-3-yl)-6-(methylthio) pyrimidine-5-carbonitriles (4a-i) was synthesized and evaluated for anticancer potential against cell lines for breast cancer. Compounds 4b, 4e, and 4h exhibited prominent cytotoxicity against human breast carcinoma MCF-7 cell line with GI(50 )of 2.0, 0.5, and 0.5 mu M, respectively. Molecular docking study against EGFR tyrosine kinase could provide valuable insights into the plausible mechanism of action. The compounds could bind with significantly high binding affinity and their binding affinity scores could correlate well with the observed anticancer activity. Furthermore, compounds 4a, 4c, 4e, 4g, and 4i exhibited significant inflammatory activities as well which could expand the therapeutic domain of this novel series.
Keywords: Anti-inflammatory; Anticancer; Antioxidant; Indole; pyrimidine

Developing spherical activated carbons from polymeric resins for removal of contaminants from aqueous and organic streams - Mane, M. B.; Bhandari, V. M. (International Journal of Environmental Science and Technology, 2022)
Spherical activated carbons from polymer resin were developed with metal modifications, before/after carbonization using copper and nickel, for gradation of zeta potential (-5.01 to 8.64 mV) and high metal loading (up to 12.3%). The materials provide improved removal of various contaminants from aqueous and organic streams-removal of bacteria from water and sulfur removal from fuel. The metal-modified spherical activated carbons were highly effective for removal of both gram-negative E. coli and gram-positive S. aureus bacteria. The copper-modified spherical activated carbon could eliminate 99.9-100%, both bacterial content proving efficacy in water disinfection with a very high rate similar to 1.33 x 10(5) (CFU/ml.s). The zeta potential has significant impact with higher disinfection for high values; similar to 10-15% disinfection can be improved up to 100% for zeta potential changes from -5 to 8.6 mV. Kinetics of disinfection was studied by accounting for zeta potential in the conventional rate model, and the efficacy of both the models was compared. The fit of revised model was excellent. The spherical activated carbons can be useful for removal of slightly polar contaminants from organic streams and a high capacity of 12.8, 20 and 28 mgS/g for thiophene, benzothiophene and dibenzothiophene, respectively. The developed materials can provide useful applications in the area of environmental pollution control. [GRAPHICS] .
Keywords: Adsorption; Material; pollution; Sulfur removal; Water disinfection

Dimerization of SARS-CoV-2 nucleocapsid protein affects sensitivity of ELISA based diagnostics of COVID-19 - Khan, Wajihul; Khan, Nida; Mishra, Avinash; Gupta, Surbhi; Bansode, Vikrant; Mehta, Deepa; Bhambure, Rahul; Rathore, Anurag (International Journal of Biological Macromolecules, 2022)
Nucleocapsid protein (N protein) is the primary antigen of the virus for development of sensitive diagnostic assays of COVID-19. In this paper, we demonstrate the significant impact of dimerization of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) N-protein on sensitivity of enzyme-linked immunosorbent assay (ELISA) based diagnostics. The expressed purified protein from E. coli is composed of dimeric and monomeric forms, which have been further characterized using biophysical and immunological techniques. Indirect ELISA indicated elevated susceptibility of the dimeric form of the nucleocapsid protein for identification of protein-specific monoclonal antibody as compared to the monomeric form. This finding also confirmed with the modelled structure of monomeric and dimeric nucleocapsid protein via HHPred software and its solvent accessible surface area, which indicates higher stability and antigenicity of the dimeric type as compared to the monomeric form. The sensitivity and specificity of the ELISA at 95% CI are 99.0% (94.5-99.9) and 95.0% (83.0-99.4), respectively, for the highest purified dimeric form of the N protein. As a result, using the highest purified dimeric form will improve the sensitivity of the current nucleocapsid-dependent ELISA for COVID-19 diagnosis, and manufacturers should monitor and maintain the monomer-dimer composition for accurate and robust diagnostics.

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

Doped 2D VX2 (X = S, Se, Te) monolayers as electrocatalysts for ammonia production: a DFT based study - Maibam, Ashakiran; BabaRao, Ravichandar; Krishnamurty, Sailaj A. (Applied Surface Science, 2022)
Electrocatalytic nitrogen fixation under ambient conditions on vanadium dichalcogenides (VX2) with non-metal dopants has been explored herein. Understanding the interface chemistry, inherent electronic and acute synergistic nature of non-metal dopants on two unique phases of VX2 has been meticulously explored through a scrutiny of several non-metal atoms as catalytic centers. The efficacity of N-2 chemisorption and N-N bond activation has been implemented as crucial parameters to realize boron and carbon doped VX2 monolayers to be electrocatalytically active for nitrogen reduction reaction (NRR). Detailed investigation on the NRR mechanism brings out the pivotal role of thermodynamic favourability for product formation obtained from Gibbs free energy differences. The charge transfer on N and pi-pi* orbital hybridization and electron ``donor-acceptor `` mechanism between the non-metal and N-2 has been found to modulate the electrocatalytic barrier for NRR on VX2 monolayers. This study proposes boron doped VS2 as an efficient chemically feasible, earth abundant sustainable electrocatalyst for NRR with an overpotential as low as 0.06 eV.
Keywords: 1T and 2H phases; DFT; electrocatalysts; Nitrogen Reduction Reaction; Non metal dopants; Vanadium dichalcogenides

Dual nanomechanics in anisotropic porous covalent organic framework janus-type thin films - Mohata, Shibani; Dey, Kaushik; Bhunia, Surojit; Thomas, Neethu; Gowd, E. Bhoje; Ajithkumar, Thalasseril G.; Reddy, C. Malla; Banerjee, Rahul (Journal of the American Chemical Society, 2022)
Empowered by crystalline ordered structures and homogeneous fabrication techniques, covalent organic frameworks (COFs) have been realized with uniform morphologies and isotropic properties. However, such homogeneity often hinders various surface-dependent properties observed in asymmetric nanostructures. The challenge remains to induce heterogeneity in COFs by creating an asymmetric superstructure such as a Janus thin film. In this regard, we propose a versatile yet straightforward interfacial layer-grafting strategy to fabricate free-standing Janus-type COF-graphene thin films. Herein, two-dimensional graphene sheets were utilized as the suitable grafter due to the possibility of noncovalent interactions between the layers. The versatility of the approach was demonstrated by fabricating two distinct Janus-type films, with the COF surface interwoven with nanofibers and nanospheres. The Janus-type films showcase opposing surface morphologies originating from graphene sheets and COF nanofibers or nanospheres, preserving the porosity (552-600 m(2) g(-1)). The unique surface chemistries of the constituent layers further endow the films with orthogonal mechanical properties, as confirmed by the nanoindentation technique. Interestingly, the graphene sheets favor the Janus-type assembly of COF nanofibers over the nanospheres. This is reflected in the better nanomechanical properties of COFfiber-graphene films (E-gra(phene) = 300-1200 MPa; E-COF( )= 15-60 MPa) compared to the COFsphere-graphene films (E-gra(phe)ne = 11-14 MPa; E-CO(F )= 2-5 MPa). These results indicate a direct relationship between the mechanical properties and homo/heterogeneity of Janus-type COF films.

Dual-functional 3-acetyl-2,5-dimethylthiophene additive-assisted crystallization control and trap state passivation for high- performance perovskite solar cells - Saykar, Nilesh G.; Iqbal, Muzahir; Pawar, Mahendra; Chavan, Kashinath T.; Mahapatra, Santosh K. (ACS Applied Energy Materials, 2022)
Defect-mediated charge recombination and successive degradation mainly lag the performance of perovskite solar cells (PSCs). Insufficiency or evaporation of organic cations leaves behind the undercoordinated Pb2+ ions, which act as severe charge recombination centers. Herein, theoretical and experimental insights into crystallization control and defect passivation of MAPbI3 perovskite by the dual-functional 3-acetyl-2,5-dimethylthiophene (ADT) molecule are pre-sented. Density functional theory calculations show that both functional groups of ADT possessing different interaction energies could interact with PbI2. The carbonyl group in ADT shows the dominant interaction with Pb2+ forming an intermediate product that might decrease the crystallization rate. Further, the coordinate bonding between ADT and uncoordinated Pb2+ ions in perovskite leads to defect passivation. The 0.6% ADT-modified PSCs possess an average power conversion efficiency (PCE) of 18.22 +/- 0.80% and the highest PCE of 19.03%, whereas the pristine PSCs exhibit an average PCE of 16.23 +/- 1.32% and the highest PCE of 17.47%. Furthermore, the modified PSCs maintain 80% of the initial PCE up to 650 h during storage at ambient conditions (RH = 35 +/- 5%). The present study shows that the simultaneous crystalization control and defect passivation achieved via an ADT additive engineering approach could be an efficient strategy to enhance the PCE and stability of PSCs.
Keywords: 3-acetyl-2; 5-dimethylthiophene; additive engineering; crystallization control; defect passivation; Perovskite solar cells

Electrochemically tuned synergistic nano-interface of a tertiary Ni(OH)(2)-NiO(OH)/NixP heterojunction material for enhanced and durable alkaline water splitting - Manappadan, Zinoy; Selvaraj, Kaliaperumal (ChemistrySelect, 2022)
Making water splitting cheaper is the need of the hour.The present work reports a nickel-based, non-precious catalytic system, synthesized by a two-step electrodeposition (ED) process followed by a short-term heat treatment. The Ni(OH)(2)-NiO(OH)/NixP heterojunction has been synthesized and optimized through an unprecedented, energy-conserving method to achieve its best OER performance. Further, it has been carefully tuned for the first time by thoroughly optimizing the ED parameters to exhibit Hydrogen Evolution Reaction (HER). At high current regimes, the performance surpassed that of the Ru/C and Pt/C (>= 500 mA and >= 600 mA) respectively. The full cell electrolyzer configuring NOPO||NOPH further establishes the supremacy of the present electrocatalysts over the benchmark Ru/C||Pt/C. Moreover, the present electrocatalyst displayed 60 and 70 hours of HER and OER performances at -100 mA and 100 mA currents respectively. In short, this work is an example that illustrates how a single chemical system gets to exhibit two complementary catalytic behaviors that is, water oxidation and reduction when certain synthetic parameters are meticulously optimized.
Keywords: Electrodeposition; heterojunction; Ni(OH)(2)-NiO(OH); NixP; non-precious metal; water splitting

Electronic structure evolution from metallic vanadium to metallic VxOy: a nappes study for o2+v gas-solid interaction - Ranjan, Ravi; Mhamane, Nitin B.; Kolekar, Sadhu K.; Gopinath, Chinnakonda S. (Journal of Physical Chemistry C, 2022)
Gas-solid interactions between molecular oxygen and metallic vanadium surfaces and the systematic evolution in the electronic structure of vanadium oxide (VOx) surfaces have been explored in the present work by near-ambient pressure photo-electron spectroscopy (NAPPES). The current article studies the evolution of various oxides of vanadium as a function of partial pressure of O2 (ultrahigh vacuum to 1 mbar), temperature (298- 875 K), and the exposure time to oxygen (up to 18 h). Valence -band (VB) and core-level spectral measurements recorded with UV (He-I = 21.2 eV) and Al K alpha (1486.6 eV) photons, respectively, show interesting changes. (1) Oxidation is limited to the top layers of vanadium at 298 K and up to a partial pressure of 1 mbar O2. About 50% of vanadium gets oxidized, and the remaining amount exists as metal within the top 10 nm. (2) Metallic vanadium disappears above 625 K, and it is predominantly oxidized to a mixture of V4+ and V5+ oxidation states at a 0.1 mbar partial pressure of O2. Points 1 and 2 suggest the predominantly thermodynamically controlled nature of vanadium oxidation through oxygen diffusion into the subsurface and bulk layers. (3) The Fermi-level (EF) feature observed first at >= 725 K at a 0.1 mbar O2 pressure demonstrates the formation of metallic VO2; however, its metallic nature is preserved even at ambient temperature due to interweaving nanodomains of VOx with VO2. (4) Only partial conversion of surface layers to V5+ (V2O5) along with VO2 and V2O3 (within the probing depth of 8-10 nm by near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS)) was observed even after prolonged heating (18 h) in 1 mbar O2 pressure. (5) The nature of the surface changes between metal and semiconducting/ insulator oxides is substantiated by the observation of changes in work function (phi) and EF features. Typical VB features and Fermi intensity of V-metal and vanadium oxides were observed, and the results were corroborated with core-level and VB spectra. The present results extend the capabilities of NAPPES to explore the electronic structure evolution as a function of reaction conditions and underscore its relevance to areas such as heterogeneous catalysis and sensing.

Elliptically birefringent chemically tuned liquid crystalline nanocellulose composites for photonic applications - Singh, Shiva; Bhardwaj, Shakshi; Verma, Chhavi; Chhajed, Monika; Balayan, Kajal; Ghosh, Kaushik; Maji, Pradip K. (Journal of Molecular Liquids, 2022)
Cellulose nanocrystals (CNCs) based photonic materials are one of the promising materials in the recent trends. The liquid crystalline behavior of the CNCs can be tailored to different advanced applications. The proposed research investigates the potential of CNCs as an optically active material. CNCs were tuned to hydroxypropyl nano cellulose (HPNC) with the degree of substitution 1.39. The prepared liquid crystalline HPNC were dispersed in various concentrations of monomethyl ether of polyethylene glycol to get waterborne materials with specific optical anisotropy. The extraction, modification, and morphology of the CNCs were investigated using NMR (Nuclear Magnetic Resonance), TEM (Transmission Electron Microscopy), XRD (X-ray Powder Diffraction), and FESEM (Field Emission Scanning Electron Microscopy) analysis. The prepared HPNC was analyzed using a hot stage POM (Polarized Optical Microscope) for optical anisotropy. The thermal stability of prepared CNCs and HPNC was also investigated. Upon optimization using rheology and POM, it was found that at the ratio of 1:1, HPNC (5 wt%) and mPEG (40 wt%) had the most distinct optical properties. The potential of the prepared materials can be further explored in sensing, smart coating, and security materials. (C) 2022 Elsevier B.V. All rights reserved.
Keywords: bagasse; Cellulose nanocrystals; Elliptical birefringence; liquid crystals; optical anisotropy

Elucidating the influence of structure and Ag+ -Na+ ion-exchange on crack-resistance and ionic conductivity of Na3Al1.8Si1.65 P-1.8 O-12 glass electrolyte - Keshri, Shweta R.; Mandal, Indrajeet; Ganisetti, Sudheer; Kasimuthumaniyan, S.; Kumar, Rajesh; Gaddam, Anuraag; Shelke, Ankita; Ajithkumar, Thalasseril G.; Gosvami, Nitya Nand; Krishnan, N. M. Anoop; Allu, Amarnath R. (Acta Materialia, 2022)
Glasses are emerging as promising and efficient solid electrolytes for all-solid-state sodium-ion batteries. However, they still suffer from poor ionic conductivity and crack-resistance, which need to be improved for better battery performance, reliability, and service life. The current study shows a significant enhancement in crack resistance (from 11.3 N to 32.9 N) for Na3Al (1.8) Si-1.65 P1.8O12 glass (Ag-0 glass) upon Na+ -Ag+ ion-exchange (IE) due to compressive stresses generated in the glass surface while the ionic conductivity values (similar to 10(-5) S/cm at 473 K) were retained. In this study, magic angle spinning-nuclear magnetic resonance (MAS-NMR), molecular dynamics (MD) simulations, Vickers micro hardness, and impedance spectroscopic techniques were used to evaluate the intermediate-range structure, atomic structure, crack resistance and conductivity of the glass. MAS-NMR and MD simulations confirm the presence of Si-OAl-O-P groups in the glass, thus enabling formation of Na percolated channel regions. AC-conductivity analysis for Ag-0 and ion-exchanged Ag-0 glass suggests that the mobility of Na+ ion increases with increasing temperature. It is observed that the measured mean square displacement (root < R-2(t(p))>) for sodium cations using AC-conductivity isotherms is nearly constant up to 448 K and then increases with increasing temperature up to 523 K. From the impedance spectra for ion-exchanged Ag-0 glass, it is identified that the increase in root < R-2 (t(nu))> and thereby, the mobility of sodium-ions for Ag-0 glass is due to the structural variations in the Ag-0 glass with increasing the temperature. Overall, the mechanisms presented in this article helps in formulating better glass based electrolyte materials for room temperature or high temperature sodium-ion batteries. (C) 2022 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: amorphous; Ion-exchange; Ionic-conductivity; MD simulations; Mechanical property

Emerging landscape of molecular interaction networks: opportunities, challenges and prospects - Panditrao, Gauri; Bhowmick, Rupa; Meena, Chandrakala; Sarkar, Ram Rup (Journal of Biosciences, 2022)
Network biology finds application in interpreting molecular interaction networks and providing insightful inferences using graph theoretical analysis of biological systems. The integration of computational bio-modelling approaches with different hybrid network-based techniques provides additional information about the behaviour of complex systems. With increasing advances in high-throughput technologies in biological research, attempts have been made to incorporate this information into network structures, which has led to a continuous update of network biology approaches over time. The newly minted centrality measures accommodate the details of omics data and regulatory network structure information. The unification of graph network properties with classical mathematical and computational modelling approaches and technologically advanced approaches like machine-learning- and artificial intelligence-based algorithms leverages the potential application of these techniques. These computational advances prove beneficial and serve various applications such as essential gene prediction, identification of drug-disease interaction and gene prioritization. Hence, in this review, we have provided a comprehensive overview of the emerging landscape of molecular interaction networks using graph theoretical approaches. With the aim to provide information on the wide range of applications of network biology approaches in understanding the interaction and regulation of genes, proteins, enzymes and metabolites at different molecular levels, we have reviewed the methods that utilize network topological properties, emerging hybrid network-based approaches and applications that integrate machine learning techniques to analyse molecular interaction networks. Further, we have discussed the applications of these approaches in biomedical research with a note on future prospects.
Keywords: Centrality; disease mechanisms; hybrid network-based models; machine learning; molecular interaction networks; network topology; systems biology

Enantioselective Au(I)/Au(III) redox catalysis enabled by chiral (P,N)-ligands - Chintawar, Chetan C.; Bhoyare, Vivek W.; Mane, Manoj V.; Patil, Nitin T. (Journal of the American Chemical Society, 2022)
Presented herein is the first report of enantioselective Au(I)/Au(III) redox catalysis, enabled by a newly designed hemilabile chiral (P,N)-ligand (ChetPhos). The potential of this concept has been demonstrated by the development of enantioselective 1,2-oxyarylation and 1,2-aminoarylation of alkenes which provided direct access to the medicinally relevant 3-oxy- and 3-aminochromans (up to 88% yield and 99% ee). DFT studies were carried out to unravel the enantiodetermining step, which revealed that the stronger trans influence of phosphorus allows selective positioning of the substrate in the C-2-symmetric chiral environment present around nitrogen, imparting a high level of enantioselectivity.

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.

Enhanced field emission behaviour from ethylene glycol mediated synthesis of 2D hexagonal SnS2 disc with nanoparticle - Mutadak, Pallavi R.; Chaudhari, Nilima S.; Gadhave, Dattatraya C.; Rajput, Parikshit K.; Kolekar, Sadhu K.; Late, Dattatray J.; More, Mahendra A.; Warule, Sambhaji S. (Materials Science and Engineering B-Advanced Functional Solid-State Materials, 2022)
Herein, octahedron and stacked 2D hexagonal disc - like nanostructures of SnS2 were obtained by hydrothermal and ethylene glycol mediated hydrothermal methods, respectively. Attempt has been made to shade light on the plausible growth mechanism. Liquid phase exfoliation followed by centrifugation process leads to presence of tiny single crystalline SnS2 nanoparticles (similar to 5 nm) on the hexagonal discs over C substrate, characterized by preferred growth along {001} direction. The observed Raman shift and enhanced intensities of A(1g) and E-g modes infer charge interactions between the SnS2 disc and C substrate. Interestingly, the SnS2-C emitter exhibited superior field emission (FE) behaviour due to the unique morphology, excellent charge transfer, and reduced work function (similar to 4.1 eV). Here the extraction of large current density of similar to 1137 mu A/cm(2) at an applied field of 3.72 V/mu m, with good emission current stability. The present strategy is beneficial to design architectured morphology for multi-functionality.
Keywords: 2D layered materials; Field Emission (FE); SnS2; SnS2 on C

Evaluating suitability of confined impinging jet reactor for exothermic reactions: hydrodynamics, residence time distribution, and heat transfer - Khan, Muzammilanwar S.; Mane, Mayur; Kulkarni, Amol A. (AICHE Journal, 2022)
Effect of confinement (wall proximity) of a confined impinging jet reactor (CIJR) on the flow field, residence time distribution and heat transfer are explored, through experiments and CFD simulations. Hydrodynamic characteristics are evaluated for different parameters namely confinement, impinging jet velocity, temperature gradient, and so on. For 2 mm confinement, highest values of dispersion number and overall heat transfer coefficient are observed due to interaction of turbulent eddies followed by the effect of reactor wall proximity. For the CIJR having confinements above 10 mm, jet velocity need to be greater than 3 m/s to achieve both, excellent mixing efficiency and high heat removal rate. Empirical correlations for Dispersion and Nusselt numbers as a function of Re-j and L/D are obtained, over a range of 500 <= Rej <= 3000\$\$ 500\textbackslashle {\textbackslashmathit{\textbackslashoperatornameRe}}_j\text backslashle 3000 \$\$ and 5 <= L/D <= 35\$\$ 5\textbackslashle L/D\textbackslashle 35 \$\$, which correspond to jet velocity of 0.5-3 m/s. The present study gives a basis for designing CIJR suitable for rapid, homogeneous, exothermic reactions.
Keywords: confinement; exothermic reactions; heat transfer; impinging jets; residence time distribution

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

Facile synthesis of nanocomposites of CNF-Sn and C-Sn microspheres: Prospective field emitter - Badadhe, Satish S.; Yadav, Poonam; Suryawanshi, Sachin; More, Mahendra A. (Journal of Alloys and Compounds, 2022)
We report synthesis of Carbon nanofibers (CNFs) and hybrid nanocomposites namely, CNF-Sn and C-Sn microspheres using simple electrospinning technique, followed by annealing in controlled atmosphere. The as-prepared materials were characterized using X-raydiffraction (XRD), Field emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM), Ultra-violet photoelectron spectroscopy (UPS), and Raman spectroscopy to reveal their physico-chemical properties. As carbon family members are potential materials for field emission (FE) based applications, owing to their high aspect ratio FE characteristics of the synthesized materials were explored at base pressure of 1 x 10(-8) mbar. Interestingly, the hybrid nanocomposite CNF-Sn and C-Sn emitters showed improved FE behavior (with the turn-on field of 3.4 and 1.36 V/mu m, respectively) in contrast to the pristine CNFs emitter (turn-on field of 5.4 V/mu m). Furthermore, the maximum emission current density is substantially enhanced, 7.75 and 4.6 mA/cm(2) for CNF-Sn and C-Sn emitters, respectively. The improvement in the FE behavior of nanocomposite emitters is attributed to the combined effect of morphology and modulation of electronic properties at the interface of nanocomposites. The results confirm that FE characteristics of pristine nanostructures can be greatly improved upon formation of their nanocomposites and this approach can be extended to other nanostructures for improving their multi-functionalities. (c) 2022 Elsevier B.V. All rights reserved.
Keywords: carbon nanofiber; electrospinning; field emission; Nanocomposite; Tin

First synthesis of podocarflavone A and its analogs and evaluation of their antimycobacterial potential against mycobacterium tuberculosis with the support of virtual screening - Puranik, Ninad V.; Swami, Sagar; Misar, Ashwini V.; Mamgain, Ritu; Gulawani, Swapnaja S.; Dhiman, Sarkar; Srivastava, Pratibha (Natural Product Research, 2022)
The first synthetic route developed for Podocarflavone A reported from Podocarpus macrophyllus and its analogs in 7 steps. Computational analysis for binding with the pantothenate kinase (3AVO) of Mycobacterium tuberculosis showed their docking score (ds) in the range of -8.9 to -9.3 Kcal/mol. MD simulations delineated the stability of the protein-ligand complexes in the TIP3P model. MMGBSA and MMPBSA values of 8d were -42.46 Kcal/mol and -14.58 Kcal/mol, respectively. Further in-vitro antitubercular screening of compounds 8a, 8d, and 8e against M. tuberculosis H37Ra using XRMA protocol exhibited promising antimycobacterial activity with IC50 values 21.82 mu g/mL, 15.55 mu g/mL, and 16.56 mu g/mL, respectively. Compounds 8a, 8d, and 8e showed antibacterial activity with IC50 values 41.56 mu g/mL, 24.72 mu g/mL, and 72.45 mu g/mL respectively against the Staphylococcus aureus. 8a and 8d showed inhibition with IC50 values 39.6 mu g/mL and 27.64 mu g/mL, respectively, against Bacillus subtilis. The present study could help in the further development of lead molecules against tuberculosis.
Keywords: and MMGBSA; antimycobacterial activity; docking; MD simulations; MMPBSA; Podocarflavone A synthesis

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.

From molecular adsorption to decomposition of methanol on various ZnO facets: a periodic DFT study - Mehta, Shweta; Joshi, Kavita (Applied Surface Science, 2022)
Methanol is an interesting and important molecule to study because of its potential to replace existing fuels. It is also a prominent hydrogen source which can be used to generate hydrogen in-situ. ZnO is widely used as catalyst in synthesis of methanol from CO2 at industrial scale. In this work, we demonstrate that the same catalyst could be used for MeOH decomposition. We have investigated interaction of methanol with various flat and stepped facets of ZnO by employing Density Functional Theory (DFT). Two flat [(10(1)overbar 0) and (11(2)overbar 0)] and two stepped [(10(1)overbar 3) and (11(2)overbar 2)] facets are studied in detail for methanol adsorption. Chemisorption of MeOH with varying strength is common to all four facets. Most importantly spontaneous dissociation of O-H bond of methanol is observed on all facets except (11(2)overbar 0). Our DFT calculations reveal that molecular adsorption is favored on flat facets, while dissociation is favored on step facets. Also, (10(1)overbar 0) facet undergoes substantial reconstruction upon MeOH adsorption. Activation of C-H bond along with strengthening of C-O bond on ZnO facets suggest partial oxidation of methanol. With our DFT investigations, we dig deeper into the underlying electronic structure of various facets of ZnO and provide rationale for the observed facet dependent interaction of ZnO with MeOH.
Keywords: DFT; MeOH; Surface interactions; ZnO

Green synthesis of cyclohexanone to adipic acid over Fe-W oxides incorporated mesoporous carbon support - Mekala, Siva Prasad; Prabu, Marimuthu; Gawali, Sheetal Datta; Gopakumar, Karthik; Gogoi, Pranjal; Bhatkar, Akash Ravindra; Mohapatra, Gourab; Unnikrishanan, Eeswar; Raja, Thirumalaiswamy (Catalysis Communications, 2022)
We have prepared iron and tungsten oxides incorporated mesoporous carbon (MC) catalysts using a simple hydrothermal methodology with different carbon sources, and the catalytic performance was investigated for cyclohexanone oxidation. An adequate amount of metal oxide loading has displayed a key role in the selective catalyst for adipic acid (AA) synthesis. The MC catalyst has shown its prime activity under the influence of redox properties of W5+/W6+ and Fe2+/Fe3+ as promoters. The 10%Fe 90%W-MC fructose as a carbon source catalyst has provided its best selectivity of 87% for AA at 120 ?C.
Keywords: Adipic Acid; Liquid phase oxidation; mesoporous carbon; Redox center

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.

High-alkaline water-splitting activity of mesoporous 3D heterostructures: an amorphous-shell@crystalline-core nano-assembly of Co-Ni-phosphate ultrathin-nanosheets and V- doped cobalt-nitride nanowires - Singh, Thangjam Ibomcha; Maibam, Ashakiran; Cha, Dun Chan; Yoo, Sunghoon; BabaRao, Ravichandar; Lee, Sang Uck; Lee, Seunghyun (Advanced Science, 2022)
Introducing amorphous and ultrathin nanosheets of transition bimetal phosphate arrays that are highly active in the oxygen evolution reaction (OER) as shells over an electronically modulated crystalline core with low hydrogen absorption energy for an excellent hydrogen evolution reaction (HER) can boost the sluggish kinetics of the OER and HER in alkaline electrolytes. Therefore, in this study, ultrathin and amorphous cobalt-nickel-phosphate (CoNiPOx) nanosheet arrays are deposited over vanadium (V)-doped cobalt-nitride (V-3%-Co4N) crystalline core nanowires to obtain amorphous-shell@crystalline-core mesoporous 3D-heterostructures (CoNiPOx@V-Co4N/NF) as bifunctional electrocatalysts. The optimized electrocatalyst shows extremely low HER and OER overpotentials of 53 and 270 mV at 10 mA cm(-2), respectively. The CoNiPOx@V-3%-Co4N/NF (+/-) electrolyzer utilizing the electrocatalyst as both anode and cathode demonstrates remarkable overall water-splitting activity, requiring a cell potential of only 1.52 V at 10 mA cm(-2), 30 mV lower than that of the RuO2/NF (+)/20%-Pt/C/NF (-) electrolyzer. Such impressive bifunctional activities can be attributed to abundant active sites, adjusted electronic structure, lower charge-transfer resistance, enhanced electrochemically active surface area (ECSA), and surface- and volume-confined electrocatalysis resulting from the synergistic effects of the crystalline V-3%-Co4N core and amorphous CoNiPOx shells boosting water splitting in alkaline media.
Keywords: core-shell; hydrogen productions; metal nitrides; metal phosphates; synergistic effect; water-splitting

Hypervalent-iodine-mediated oxidation followed by the acetoxylation/tosylation of alpha-substituted benzylamines to obtain alpha-acyloxy/tosyloxy ketones - Rupanawar, Bapurao D.; Mane, Kishor D.; Suryavanshi, Gurunath (New Journal of Chemistry, 2022)
An efficient and metal-free method has been developed for the sequential oxidation of alpha-alkylbenzylamines followed by acetoxylation or tosylation for the synthesis of alpha-acyloxy/tosyloxy ketones using hypervalent iodine(iii). The employment of a simple starting material, broad substrate scope and operational simplicity are the key features of this protocol.

Identification and characterization of the key enzyme in the biosynthesis of the neurotoxin beta-ODAP in grass pea - Goldsmith, Moshe; Barad, Shiri; Knafo, Maor; Savidor, Alon; Ben-Dor, Shifra; Brandis, Alexander; Mehlman, Tevie; Peleg, Yoav; Albeck, Shira; Dym, Orly; Ben-Zeev, Efrat; Barbole, Ranjit S.; et al. (Journal of Biological Chemistry, 2022)
Grass pea (Lathyrus sativus L.) is a grain legume commonly grown in Asia and Africa for food and forage. It is a highly nutritious and robust crop, capable of surviving both droughts and floods. However, it produces a neurotoxic compound, beta-N- oxalyl-L-alpha,beta-diaminopropionic acid (beta-ODAP), which can cause a severe neurological disorder when consumed as a primary diet component. While the catalytic activity associated with beta-ODAP formation was demonstrated more than 50 years ago, the enzyme responsible for this activity has not been identified. Here, we report on the identity, activity, 3D structure, and phylogenesis of this enzyme-beta-ODAP synthase (BOS). We show that BOS belongs to the benzylalcohol O-acetyltransfer-ase, anthocyanin O-hydroxycinnamoyltransferase, anthranilate N-hydroxycinnamoyl/benzoyltransferase, deacetylvindoline 4-O-acetyltransferase superfamily of acyltransferases and is structurally similar to hydroxycinnamoyl transferase. Using molecular docking, we propose a mechanism for its catalytic activity, and using heterologous expression in tobacco leaves (Nicotiana benthamiana), we demonstrate that expression of BOS in the presence of its substrates is sufficient for beta-ODAP production in vivo. The identification of BOS may pave the way toward engineering beta-ODAP-free grass pea cultivars, which are safe for human and animal consumption.

Immobilization of HPW on UiO-66-NH2 MOF as efficient catalyst for synthesis of furfuryl ether and alkyl levulinate as biofuel - Mulik, Nagesh; Bokade, Vijay (Molecular Catalysis, 2022)
Phosphotungustic Acid (HPW) is an inorganic super acid, that is highly soluble in polar solvents limiting its applicability as acid catalysis. To overcome these limitations immobilization of HPW was carried out at room temperature by protonation of-NH2 group of UiO-66-NH2 MOF to UiO-66-NH2-HPW. ATR-FTIR spectroscopy and XPS results confirmed the protonation and chemical interaction between HPW and UiO-66-NH2. STEM-EDS mapping showed homogeneous distribution of HPW on UiO-66-NH2. BET and NH3-TPD confirmed the reduction in specific surface area, total pore volume, and increase in total acidity for UiO-66-NH2-HPW. Further, powder XRD, SEM, and HR-TEM prevailed that there is no change in phase and morphology after post-synthetic modification of UiO-66-NH2. The prepared catalyst is found to be effective for etherification and alcoholysis of furfuryl alcohol (FALc) to Furfuryl ether (FE) and Alkyl levulinate (AL). UiO-66-NH2-HPW has shown 97 mol % FALc conversions in ethanolic media and 31 mol% Ethyl furfuryl ether (EFE) yield and 29 mol% Ethyl lev-ulinate (EL) yield. UiO-66-NH2-HPW is also found to be efficient for the multistep conversion of Furfural (FFR) to FALc, FE, and AL.
Keywords: Alcoholysis; etherification; Immobilization; Phosphotungstic acid; UiO-66-NH2-HPW

Improved mucoadhesion, permeation and in vitro anticancer potential of synthesized thiolated acacia and karaya gum combination: a systematic study - Munot, Neha; Kandekar, Ujjwala; Rikame, Chaitali; Patil, Abhinandan; Sengupta, Poulomi; Urooj, Shabana; Bilal, Anusha (Molecules, 2022)
Thiolation of polymers is one of the most appropriate approaches to impart higher mechanical strength and mucoadhesion. Thiol modification of gum karaya and gum acacia was carried out by esterification with 80% thioglycolic acid. FTIR, DSC and XRD confirmed the completion of thiolation reaction. Anticancer potential of developed thiomer was studied on cervical cancer cell lines (HeLa) and more than 60% of human cervical cell lines (HeLa) were inhibited at concentration of 5 mu g/100 mu L. Immobilized thiol groups were found to be 0.8511 mmol/g as determined by Ellman's method. Cytotoxicity studies on L929 fibroblast cell lines indicated thiomers were biocompatible. Bilayered tablets were prepared using Ivabradine hydrochloride as the model drug and synthesized thiolated gums as mucoadhesive polymer. Tablets prepared using thiolated polymers in combination showed more swelling, mucoadhesion and residence time as compared to unmodified gums. Thiol modification controlled the release of the drug for 24 h and enhanced permeation of the drug up to 3 fold through porcine buccal mucosa as compared to tablets with unmodified gums. Thiolated polymer showed increased mucoadhesion and permeation, anticancer potential, controlled release and thus can be utilized as a novel excipient in formulation development.
Keywords: buccal tablets; enhanced permeation; ivabradine HCl; mucoadhesion; thiolated gums

Improvement in oxygen evolution performance of NiFe layered double hydroxide grown in the presence of 1T-Rich MoS2 - Chakraborty, Soumita; Marappa, Shivanna; Agarwal, Sakshi; Bagchi, Debabrata; Rao, Ankit; Vinod, Chathakudath P.; Peter, Sebastian C.; Singh, Abhishek; Eswaramoorthy, Muthusamy (ACS Applied Materials & Interfaces, 2022)
NiFe layered double hydroxide (NiFe LDH) grown in the presence of MoS2 (rich in 1T phase) shows exceptional performance metrics for alkaline oxygen evolution reaction (OER) in this class of composites. The as-prepared NiFe LDH/MoS2 composite (abbreviated as MNF) exhibits a low overpotential (eta(10)) of 190 mV; a low Tafel slope of 31 mV dec(-1); and more importantly, a high stability in its performance manifested by the delivery of current output for 45 h. It is important to note that this could be achieved with an exceedingly low loading of 0.14 mg cm(-2). The mass activity of this composite (97 A g(-1)) is about 14 times greater than that of the conventional RuO2 (7 A g(-1) ) at eta = 200 mV. When normalized with respect to the total metal content, a mass activity of 1000 A g(-1) (eta = 300 mV) was achieved. Impedance analysis further reveals that the significant reduction in charge-transfer resistance and hence high current density (5 times greater as compared to NiFe LDH at eta = 300 mV) observed for MNF is associated with interfacial adsorption kinetics of intermediates (R-1). Significant enhancement in the intrinsic activity of MNF over LDH has been observed through normalization of current with the electrochemically active surface area. Computational studies suggest that the Ni centers in the composite act as the active sites for OER, which is well-corroborated with the observed postreaction appearance of Ni3+ species.
Keywords: Impedance; LDH-MoS2 hybrid electrocatalyst; mass activity; OER; overpotential

Influence of catalyst reduction temperature on autogenous glycerol hydrogenolysis over NiAl catalyst - Pandya, Rajan; Mane, Rasika; Rode, Chandrashekhar (Asian Journal of Organic Chemistry, 2022)
Autogenous glycerol hydrogenolysis to 1,2-propanediol by aqueous phase reforming (APR) was investigated over supported nickel catalysts. Effect of reduction temperature on physico-chemical properties of catalysts played a significant role in tuning conversion and product selectivities. The formation of nickel aluminate (NiAl2O4) spinel phase during catalyst reduction led to rearrangement of Ni species to obtain small and stable Ni particles. The catalyst activation temperature alters the extent of reduction of multivalent Ni species (Ni-0, Ni+2/+3) which facilitated glycerol dehydration and hydrogenation while suppressing C-C cleavage and thus avoiding undesirable side products. Additionally, presence of moderate Bronsted/Lewis acid ratio of the catalyst promoted higher 1,2-PDO selectivity. In-situ glycerol hydrogenolysis involves glycerol dehydration to acetol with simultaneous reforming to H-2 and CO2 and this hydrogen converts acetol to 1,2-PDO.
Keywords: APR; autogenous hydrogenolysis; Glycerol; Propanediols; reduction temperature; spinel

Insights into active tungsten species on Pt/W/SBA-15 catalysts for selective hydrodeoxygenation of glycerol to 1,3-propanediol - Bhowmik, Susmita; Enjamuri, Nagasuresh; Sethia, Govind; Akula, Venugopal; Marimuthu, Banu; Darbha, Srinivas (Molecular Catalysis, 2022)
Diols are important class of industrial chemicals. Their synthesis from bio-resources (instead from fossil feed-stocks) is sustainable. In this study, we probed active tungsten species on Pt/W/SBA-15 catalysts for selective synthesis of 1,3-propanediol (1,3-PDO) from aqueous glycerol through a liquid-phase hydrodeoxygenation re-action. A synergistic enhancement in glycerol conversion and 1,3-PDO selectivity was observed when both Pt and W were present on the catalyst. A volcano-shape variation followed with a gradual increase in glycerol conversion and 1,3-PDO yield with W-loading (0.25-15 wt%) was observed. Pt dispersion and acidity of the catalyst dis-played similar variations with the W-loading confirming their critical role in the reaction. Structure-function relationships inferred that oligomeric WOx with moderate Bro center dot nsted acidity (predominant at 1 wt% W-loading) in contact with dispersed Pt are the active species for 1,3-PDO formation and crystalline WO3 with strong Bro center dot nsted acidity (prevalent above 4 wt% W-loading) in association with Pt nanoparticles lead to 1-propanol formation.
Keywords: 3-Propanediol; Active sites; Glycerol; Hydrodeoxygenation; Hydrogenolysis; Supported Pt-WO x

Instabilities as the origin of large-area self-assembled and aligned organic semiconductor nanocrystals - Venugopalan, Vijay; Jain, Bhanprakash; Mahale, Rajashree Y.; Subramani, Kumar; Krishnamoorthy, Kothandam (ACS Applied Electronic Materials, 2022)
Aligned nanocrystals of organic semiconductors (OSCs) are highly desirable for electronic devices and biomedical and photonic applications. Solution-based wet processing routes have the potential to produce aligned nanocrystals over large areas in small time frames. Herein, we demonstrate that by optimizing the hydrodynamic evaporative processes, controlled long-range crystalline assemblies of OSCs can be achieved (longest nanocrystal similar to 3 mm) purely through physical processes: namely, from fingering instabilities. Self-assembly is achieved here without strong noncovalent interactions such as hydrogen-bonding interactions. Experimentally our approach involves just placing a drop of a solution on an inclined substrate. Nanocrystals with widths of 300-800 nm and lengths of millimeters (length/width aspect ratios >10(5)) are formed in less than 2-8 s. A hydrazine chemiresistive sensor based on the aligned crystalline patterns show unprecedented responsivity (similar to 10(-6)), 2 orders greater than those of stick-slip patterns. Finally, experimental parameters that need optimization to achieve nanocrystal patterns are investigated in detail and pointers to fabricate such OSC nanocrystals are provided.
Keywords: aligned fibers; diketopyrrolopyrrole; fingering instability; nanocrystal arrays; naphthalenediimide; organic semiconductors

Interplay of anion-pi(+) and pi(+)-pi(+) interactions in novel pyrido[2,1-a]isoquinolinium-based aiegens - substituent- and counterion-dependent fluorescence modulation and applications in live cell mitochondrial imaging - Mule, Ravindra D.; Roy, Rupam; Mandal, Koushik; Chopra, Deepak; Dutta, Tanoy; Sancheti, Shashank P.; Shinde, Popat S.; Banerjee, Somsuvra; Lal Koner, Apurba; Bhowal, Rohit; Senthilkumar, Beeran; Patil, Nitin T. (Chemistry-A European Journal, 2022)
Recently, the concept of anion-pi(+) interactions has witnessed unique applications in the field of AIEgen development. In this contribution, we disclose a consolidated study of a library of N-doped ionic AIEgens accessed through silver-mediated cyclization of pyridino-alkynes. A thorough photophysical, computational and crystallographic study has been conducted to rationalize the observed substituent- and counterion-dependent fluorescence properties of these luminogens. We further elucidate the prominent role of anion-pi(+) interactions, pi(+)-pi(+) interactions and other non-covalent interactions, in inhibiting the undesired ACQ effect. Finally, we have also demonstrated the application of selected AIEgens for imaging of mitochondria in live cells.
Keywords: 1-a]isoquinolinium; AIEgens; anion-pi(+); crystal structure; mitochondrial imaging; pyrido[2

Iridium-catalyzed synthesis of pyrazolone fused 1,4-dihydrocinnolin-3-one employing alpha-diazotized Meldrum's acid - Kulkarni, Anand M.; Mullapudi, Venkannababu; Ramana, Chepuri Venkata (ARKIVOC, 2022)
The [Iri-catalysed carbenoid insertion and cyclization of N-arylpyrazolones has been carried out with alpha-diazotized Meldrum's acid to access tricyclic pyrazolone fused 1,4-dihydrocinnolin-3-one derivatives. Further, the selective reduction of these tricyclic derivatives has been studied under Birch reduction conditions.
Keywords: ?-diazotized Meldrum's acid; C-H activation; carbene Insertion; cinnoline derivatives; N-arylpyrazolones; [Iri-Catalysis

Isolation and characterization of chitosans from different fungi with special emphasis on zygomycetous dimorphic fungus benjaminiella poitrasii: evaluation of its chitosan nanoparticles for the inhibition of human pathogenic fungi - Mane, Shamala; Pathan, Ejaj; Tupe, Santosh; Deshmukh, Sneha; Kale, Deepika; Ghormade, Vandana; Chaudhari, Bhushan; Deshpande, Mukund (Biomacromolecules, 2022)
The cell wall chitosan was extracted from fungi belonging to different taxonomic classes, namely, Benjaminiella poitrasii (Zygomycetes, dimorphic), Hanseniaspora guilliermondii, Issatchenkia orientalis, Pichia membranifaciens, and Saccharomyces cerevisiae (Ascomycetes, yeasts), and Agaricus bisporus and Pleurotus sajor-caju (Basidiomycetes). The maximum yield of chitosan was 60.89 ± 2.30 mg/g of dry mycelial biomass of B. poitrasii. The degree of deacetylation (DDA) of chitosan extracted from different fungi, as observed with 1H NMR, was in the range of 70–93%. B. poitrasii chitosan exhibited the highest DDA (92.78%). The characteristic absorption bands were observed at 3450, 1650, 1420, 1320, and 1035 cm–1 by FTIR. Compared to chitosan from marine sources (molecular weight, MW, 585 kDa), fungal chitosans showed lower MW (6.21–46.33 kDa). Further, to improve the efficacy of B. poitrasii chitosan (Bp), nanoparticles (Np) were synthesized using the ionic gelation method and characterized by dynamic light scattering (DLS). For yeast and hyphal chitosan nanoparticles (BpYCNp and BpHCNp), the average particle size was <200 nm with polydispersity index of 0.341 ± 0.03 and 0.388 ± 0.002, respectively, and the zeta potential values were 21.64 ± 0.34 and 24.48 ± 1.58 mV, respectively. The B. poitrasii chitosans and their nanoparticles were further evaluated for antifungal activity against human pathogenic Candida albicans ATCC 10231, Candida glabrata NCYC 388, Candida tropicalis ATCC 750, Cryptococcus neoformans ATCC 34664, and Aspergillus niger ATCC 10578. BpHCNps showed lower MIC90 values (0.025–0.4 mg/mL) than the chitosan polymer against the tested human pathogens. The study suggested that nanoformulation of fungal chitosan, which has low molecular weight and high % DDA, is desirable for antifungal applications against human pathogens. Moreover, chitosans as well as their nanoparticles were found to be hemocompatible and are therefore safe for healthcare applications.

Janus cross-links in supramolecular networks - Mondal, Swagata; Lessard, Jacob J.; Meena, Chhuttan L.; Sanjayan, Gangadhar J.; Sumerlin, Brent S. (Journal of the American Chemical Society, 2022)
Thermosets composed of cross-linked polymers demonstrate enhanced thermal, solvent, chemical, and dimensional stability as compared to their non-cross-linked counterparts. However, these often-desirable material properties typically come at the expense of reprocessability, recyclability, and healability. One solution to this challenge comes from the construction of polymers that are reversibly cross-linked. We relied on lessons from Nature to present supramolecular polymer networks comprised of cooperative Janus-faced hydrogen bonded cross-links. A triazine-based guanine-cytosine base (GCB) with two complementary faces capable of self-assembly through three hydrogen bonding sites was incorporated into poly(butyl acrylate) to create a reprocessable and recyclable network. Rheological experiments and dynamic mechanical analysis (DMA) were employed to investigate the flow behavior of copolymers with randomly distributed GCB units of varying incorporation. Our studies revealed that the cooperativity of multiple hydrogen bonding faces yields excellent network integrity evidenced by a rubbery plateau that spanned the widest temperature range yet reported for any supramolecular network. To verify that each Janus-faced motif engages in multiple cross-links, we studied the effects of local concentration of the incorporated GCB units within the polymer chain. Mechanical strength improved by colocalizing the GCB within a block copolymer morphology. This enhanced performance revealed that the number of effective cross-links in the network increased with the local concentration of hydrogen bonding units. Overall, this study demonstrates that cooperative noncovalent interactions introduced through Janus-faced hydrogen bonding moieties confers excellent network stability and predictable viscoelastic flow behavior in supramolecular networks.

Kinetic model of GPCR-G protein interactions reveals allokairic modulation of signaling - Culhane, Kelly; Gupte, Tejas; Madhugiri, Indrani; Gadgil, Chetan; Sivaramakrishnan, Sivaraj (Biophysical Journal, 2022)

Kinetic study on alkylation of hydroquinone with methanol over SO3H functionalized Bronsted acidic ionic liquids - Bhongale, V. Priyanka; Amonkar, Amogh A.; Joshi, Sunil S.; Mali, Nilesh A. (Canadian Journal of Chemical Engineering, 2022)
O-alkylation of a dihydric phenol (i.e., hydroquinone) with methanol in presence of benzoquinone catalyzed by double SO3H functionalized Bronsted acidic ionic liquids (i.e., 1,3-disulphonic acid imidazolium hydrogen sulphate, 1,3-disulphonic acid benzimidazolium hydrogen sulphate, and sulphuric acid) is studied in a batch reactor. The sensitivity of activity and selectivity with reaction time, temperature, speed of agitation, and catalyst loading was examined. The plausible reaction pathways proposed based on the experimental observations and detailed kinetic investigation are performed by assuming a homogeneous reaction phase. The kinetic parameters, such as pre-exponential factor and activation energy, are estimated for both ionic liquids and sulphuric acid by considering all competitive reactions, and comparative results were presented. An extended form of the Arrhenius equation is used to estimate the kinetic parameters for the reaction which showed curvature in lnk against a 1/T plot. The model prediction with the estimated kinetic parameters is in good agreement with the experimental data, which confirmed the model validity in the experimental operating range. It was found that ionic liquid has a potential application in the synthesis of a selective monoalkylated product of hydroquinone. The kinetic analysis performed is found to be useful in the understanding of process behaviour.
Keywords: 4-Methoxyphenol; Hydroquinone; ionic liquids; Kinetic analysis; O-alkylation

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

Lewis acid triggered N-alkylation of sulfoximines through nucleophilic ring-opening of donor-acceptor cyclopropanes: synthesis of gamma-sulfoximino malonic diesters - More, Satish G.; Suryavanshi, Gurunath (Organic & Biomolecular Chemistry, 2022)
Scandium triflate (Sc(OTf)(3)) catalyzed, mild, and regioselective ring-opening reaction of donor-acceptor (D-A) cyclopropanes has been developed using sulfoximines for the synthesis of gamma-sulfoximino malonic diesters. This protocol allows the synthesis of different N-alkyl sulfoximines in good to excellent yields (up to 94%) with broad functional group tolerance. In this process, N-H and C-C bonds are cleaved to form new C-N and C-H bonds. The feasibility of this method is supported by a gram-scale reaction and synthetic elaboration of the obtained product.

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

Mapping the finite-temperature behavior of conformations to their potential energy barriers: case studies on Si6B and Si5B clusters - Maneri, Asma H.; Singh, Chandrodai Pratap; Kumar, Ravi; Maibam, Ashakiran; Krishnamurty, Sailaja (ACS Omega, 2022)
Dynamical simulations of molecules and materials have been the route to understand the rearrangement of atoms within them at different temperatures. Born-Oppenheimer molecular dynamical simulations have further helped to comprehend the reaction dynamics at various finite temperatures. We take a case study of Si6B and Si5B clusters and demonstrate that their finite-temperature behavior is rather mapped to the potential energy surface. The study further brings forth the fact that an accurate description of the dynamics is rather coupled with the accuracy of the method in defining the potential energy surface. A more precise potential energy surface generated through the coupled cluster method is finally used to identify the most accurate description of the potential energy surface and the interconnected finite-temperature behavior.

Mechanistic modeling of continuous capture step purification of biosimilar monoclonal antibody therapeutic - Deulgaonkar, Prashant; Bhambure, Rahul; Prasad, Bhaskarjyoti; Mishra, Ashok; Tiwari, Sanjay; Mody, Rustom (Journal of Chemical Technology and Biotechnology, 2022)
{BACKGROUND Continuous multicolumn Protein A chromatography offers various advantages for capture stage purification of monoclonal antibody therapeutics, like higher productivity and resin capacity utilization, lower buffer consumption, small footprint, etc. Due to the complexity of the continuous process, experimental optimization is time-consuming and cost-intensive. This investigation proposes a hybrid process development approach integrating experimental and mechanistic modeling for time- and cost-effective development and optimization of continuous Protein A affinity chromatography. RESULTS Productivity and capacity utilization of the continuous CaptureSMB process under varying operating conditions were predicted using the Chromatography Analysis and Design Toolkit (CADET) framework and validated with experimental results. Effects of critical process parameters like feed concentration (c(0)), loading breakthrough (s) and residence time (RT) on productivity and capacity utilization were evaluated. Model predictions were validated using the experimental results proving the reliability and feasibility of the modeling approach. At 15.00 +/- 0.20 mg mL(-1) feed model mAb concentration, the model-based approach predicted the best performance giving 27.56 g L-1 h(-1) productivity (RT = 2 min
Keywords: CaptureSMB; continuous chromatography; Mathematical modeling; Protein A; simulation

Metal- and light-free direct C-3 ketoalkylation of quinoxalin-2(1H)-ones with cyclopropanols in aqueous medium - More, Devidas A.; Mujahid, M.; Muthukrishnan, M. (ChemistrySelect, 2022)
Direct oxidative C-3 ketoalkylation of quinoxalin-2(1H)-ones with cyclopropanols using ammonium persulfate in an aqueous medium has been achieved in a moderate to good yield. The reaction does not require metals, light-source, or catalysts to facilitate the reaction and could be efficiently utilized to construct a wide range of biologically relevant 3-ketoalkylated quinoxalin-2(1H)-ones.
Keywords: aqueous medium; cyclopropanols; ketoalkylation; metal-free; quinoxalin-2(1H)-ones

Metal-free access to hindered N-alkyl sulfoximines via in-situ generated Aza-oxyallyl cations from functionalized alkyl bromide - More, Satish G.; Mane, Kishor D.; Suryavanshi, Gurunath (Asian Journal of Organic Chemistry, 2022)
Herein, we report a catalyst-free and mild synthetic method for the construction of hindered N-alkyl sulfoximines derivative. A wide range of hindered di-alkyl sulfoximines can be readily obtained from the reaction of alpha-bromo-hydroxamates with a variety of sulfoximines, including diaryl, aryl-alkyl, di-alkyl and heteroaryl sulfoximines.
Keywords: alpha-Bromo hydroxamates; Aza-oxyallyl cations; Di-alkyl sulfoximines; metal-free; Sulfoximines

Metal-free aminocarbonylation of p-quinone methides with isocyanides: synthesis of sterically hindered alpha-arylated acetamides - Shirsath, Sachin R.; More, Devidas A.; Muthukrishnan, M. (Chemistry-an Asian Journal, 2022)
The synthesis of sterically hindered alpha-arylated acetamides generally requires a multistep reaction sequence and is also difficult to access due to steric constraints. This protocol allows the synthesis of sterically hindered alpha-arylated acetamides in moderate to high yields via 1,6-addition of isocyanides to p-quinone methides in the presence of BF3 center dot OEt2. The present transformation features transition metal-free conditions, avoiding the use of toxic carbon monoxide, broad substrate scope, mild reaction conditions, and operational simplicity.
Keywords: Aminocarbonylation; Isocyanide; p-Quinone methide; Sterically Hindered alpha-Arylated Acetamides

MgB2/NaNO2-PVA free-standing polymer composite film as a green firework: a step towards environmental sustainability - Jeyavani, Vijayakrishnan; Kumar, Rajendra; Joy, Pattayil Alias; Mukherjee, Shatabdi Porel (Bulletin of Materials Science, 2022)
We have demonstrated a simple fabrication methodology of free-standing polymer composite film firework that sparkles, provides colour display and moderate sound, yet is less polluting. The polymer composite film fireworks are composed of magnesium boride (MgB2), sodium nitrite (NaNO2) and poly(vinyl alcohol) (PVA). This study also suggested that a flammable, explosive powder composition can be made of two very common inorganic precursors, mainly NaNO2 and MgB2 . This is the first report demonstrating composite film fireworks with new flammable composition using metal boride as a primary precursor, which can also be used in conventional fireworks fabrication, replacing the traditional fuel, mainly gunpowder. The film fireworks were free from charcoal, sulphur, metal powder and paper. Therefore, they substantially lower the odour and COx, NOx, emissions and minimize the substantial trash generated when burned. Most importantly, film firework's minimum ignition temperature and exothermic decomposition temperature are much higher than the ambient temperature; hence are safe to handle.
Keywords: Firework; free-standing film; magnesium boride (MgB2); poly(vinyl alcohol) (PVA); sodium nitrite (NaNO2)

Microwave-assisted selective N-alkylation of aniline over molybdenum supported catalyst - Bhatkar, Akash; Mane, Samruddhi; Mekala, Siva Prasad; Gogoi, Pranjal; Mohapatra, Gourab; Ramakrishnan, Archana; Marimuthu, Prabu; Thirumalaiswamy, Raja (Catalysis Communications, 2022)
Selective N-alkylation of aniline is a tough and challenging reaction due to over alkylation, therefore, catalyst with specific characteristics is needed to accomplish such transformations. In this work, a series of catalysts with molybdenum supported on alumina are prepared and subjected to various reaction conditions, out of which 30 PMA (Phosphomolybdic acid) showed the best result due to its proper combination of acidic sites. This reaction is sustainable and environmentally friendly as it is carried out with methanol as an alkylating source in the presence of microwave radiation at low temperature. The reaction data was compared with various other reactor systems too.

Molecular mechanisms underlying caveolin-1 mediated membrane curvature - Prakash, Shikha; Malshikare, Hrushikesh; Sengupta, Durba (Journal of Membrane Biology, 2022)
Caveolin-1 is one of the main protein components of caveolae that acts as a mechanosensor at the cell membrane. The interactions of caveolin-1 with membranes have been shown to lead to complex effects such as curvature and the clustering of specific lipids. Here, we review the emerging concepts on the molecular interactions of caveolin-1, with a focus on insights from coarse-grain molecular dynamics simulations. Consensus structural models of caveolin-1 report a helix-turn-helix core motif with flanking domains of higher disorder that could be membrane composition dependent. Caveolin-1 appears to be mainly surface-bound and does not embed very deep in the membrane to which it is bound. The most interesting aspect of caveolin-1 membrane binding is the interplay of cholesterol clustering and membrane curvature. Although cholesterol has been reported to cluster in the vicinity of caveolin-1 by several approaches, simulations show that the clustering is maximal in membrane leaflet opposing the surface-bound caveolin-1. The intrinsic negative curvature of cholesterol appears to stabilize the negative curvature in the opposing leaflet. In fact, the simulations show that blocking cholesterol clustering (through artificial position restraints) blocks membrane curvature, and vice versa. Concomitant with cholesterol clustering is sphingomyelin clustering, again in the opposing leaflet, but in a concentration-dependent manner. The differential stress due to caveolin-1 binding and the inherent asymmetry of the membrane leaflets could be the determinant for membrane curvature and needs to be further probed. The review is an important step to reconcile the molecular level details emerging from simulations with the mesoscopic details provided by state of the art experimental approaches. [GRAPHICS] .
Keywords: Cholesterol clustering; Membrane curvature; Protein-lipid interactions

Morphology-tuned Pt3Ge accelerates water dissociation to industrial-standard hydrogen production over a wide pH range - Mondal, Soumi; Sarkar, Shreya; Bagchi, Debabrata; Das, Tisita; Das, Risov; Singh, Ashutosh Kumar; Prasanna, Ponnappa Kechanda; Vinod, C. P.; Chakraborty, Sudip; Peter, Sebastian C. (Advanced Materials, 2022)
The discovery of novel materials for industrial-standard hydrogen production is the present need considering the global energy infrastructure. A novel electrocatalyst, Pt3Ge, which is engineered with a desired crystallographic facet (202), accelerates hydrogen production by water electrolysis, and records industrially desired operational stability compared to the commercial catalyst platinum is introduced. Pt3Ge-(202) exhibits low overpotential of 21.7 mV (24.6 mV for Pt/C) and 92 mV for 10 and 200 mA cm(-2) current density, respectively in 0.5 m H2SO4. It also exhibits remarkable stability of 15 000 accelerated degradation tests cycles (5000 for Pt/C) and exceptional durability of 500 h (@10 mA cm(-2)) in acidic media. Pt3Ge-(202) also displays low overpotential of 96 mV for 10 mA cm(-2) current density in the alkaline medium, rationalizing its hydrogen production ability over a wide pH range required commercial operations. Long-term durability (>75 h in alkaline media) with the industrial level current density (>500 mA cm(-2)) has been demonstrated by utilizing the electrochemical flow reactor. The driving force behind this stupendous performance of Pt3Ge-(202) has been envisaged by mapping the reaction mechanism, active sites, and charge-transfer kinetics via controlled electrochemical experiments, ex situ X-ray photoelectron spectroscopy, in situ infrared spectroscopy, and in situ X-ray absorption spectroscopy further corroborated by first principles calculations.
Keywords: Electrochemistry; hydrogen production; intermetallics; water electrolysis

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

Native state conformational heterogeneity in the energy landscape of protein folding - Mishra, Prajna; Jha, Santosh Kumar (Biophysical Chemistry, 2022)
The native structure of proteins is central to various functions performed by cells. A vital part of the structure-function paradigm of proteins is their inherent flexibility and dynamics. The dynamic interconversion between the conformational substates in the heterogeneous native state basin of the energy landscape enables a single protein molecule to perform multiple functions. The dynamics among the substates are assisted by the motion of different structural elements of a protein out of which side-chains of amino acids hold a significant position due to their involvement in various functions such as molecular recognition and dynamic allostery. This review briefly describes the origin of conformational heterogeneity in the native state ensemble and the motions of different structural modules that assist the equilibrium dynamics of the conformational substates. The review then centers the discussion on conformational heterogeneity due to side-chain movements in proteins, the experimental methods to detect and characterize them and their role in performing multiple functions.
Keywords: Conformational heterogeneity; Dry molten globules; Energy landscape model; Native state; Side-chain packing

Nickel-catalyzed direct synthesis of N-substituted indoles from amino alcohols and alcohols - Yadav, Vinita; Jagtap, Sayali G.; Balaraman, Ekambaram; Mhaske, Santosh B. (Organic Letters, 2022)
A one-pot cascade approach for the synthesis of N substituted indoles from amino alcohols and alcohols under additive and base-free conditions with the liberation of water as the only stoichiometric byproduct is reported. The commercially available bench-stable Ni(OTf)2 salt in combination with 1,2-bis(dicyclohexylphosphino)ethane (dcype) is very effective for this unprecedented catalytic transformation. A broad range of substrates including aromatic and aliphatic primary alcohols, cyclic and acyclic secondary alcohols, and various substituted 2-aminophenyl ethyl alcohols are employed in the reaction conditions to provide a diverse range of N-alkylated indoles. Mechanistic studies revealed that the reaction proceeds through tandem N-alkylation via hydrogen autotransfer followed by the cyclization of N-alkylated alcohol intermediate.

Novel 3-fluoro-4-morpholinoaniline derivatives: synthesis and assessment of anti-cancer activity in breast cancer cells - More, Namita A.; Jadhao, Nitin L.; Meshram, Rohan J.; Tambe, Prajakta; Salve, Rajesh A.; Sabane, Jagjivan K.; Sawant, Sanskruti N.; Gajbhiye, Virendra; Gajbhiye, Jayant M. (Journal of Molecular Structure, 2022)
Heterocyclic morpholine compounds are well-known for their anti-cancer activity. In this study, novel morpholine and its sulfonamide derivatives were designed and synthesized as potential anti-tumor agents. The new compounds were obtained from amine derivatives via nucleophilic addition reactions, providing the desired products in 70 to 90% yield. The docking analysis was performed for all thirty-one compounds. Out of them, we represent the docking poses for compounds NAM-5 and NAM-7 as representatives. After docking analysis, compounds NAM-5 and NAM- 7 were tested for in vitro antitumor activity against breast cancer cell lines (MCF-7 and MDA-MB-231) and healthy mouse embryonic fibroblast cell line (3T3L-1). Amongst these, sulfonamide group-containing compound NAM-5 showed significant anti-proliferative activity with IC50 of 1.811 mu M and 2.143 mu M for MCF-7 and MDA-MB-231 cells, respectively. On the other hand, NAM-7 showed good anti-proliferative activity against MCF-7 (IC50 1.883 mu M) but slightly lower activity against MDA-MB-231 cells (IC50 4.688 mu M). The activity of both the compound was also tested on 3T3L-1 Cell line which showed activity similar to clinically approved anti-cancer drug doxorubicin (DOX). The cell death analysis by flow-cytometry confirmed apoptosis mediated cell death in 3T3L-1, MCF-7 and MDA-MB-231 cells when treated with the NAM-5 and NAM-7, respectively. The results demonstrated that the synthesized sulfonamide derivatives have significant potential as anti-cancer agents and have a substantial importance in cancer therapeutics with favourable safety profile. Structural analysis of docked poses of sulfonamide derivatives attempts to shed light on the structural basis of sulfonamide derivatives based anti-cancer effect. (C) 2021 Elsevier B.V. All rights reserved.
Keywords: Anticancer activity; Apoptosis; Breast cancer; Heterocyclic compounds; Morpholine; Sulfonamide

Novel lignin as natural-biodegradable binder for various sectors-A review - Mili, Medha; Hashmi, Sayed Azhar Rasheed; Ather, Madeeha; Hada, Vaishnavi; Markandeya, Nishant; Kamble, Sanjay; Mohapatra, Mamata; Rathore, Sanjai Kumar Singh; Srivastava, Avanish Kumar; Verma, Sarika (Journal of Applied Polymer Science, 2022)
Lignin functions as an essential polymer in plants that forms the plant body's structural framework. The natural glue holds the cellulosic fibers together in the plant body, thereby providing rigidity and strength. Despite this, lignin shows promising relevance for biomaterial production due to its abundance, nontoxic nature and biodegradability. Considerably, adhesive components were derived from petroleum, which is increasingly more expensive. Hence, lignin, the natural glue in plant materials, gained much popularity because of its phenolic nature, making it an attractive substitute for adhesives. Lignin-based binders are produced through phenols substitution in phenol-formaldehyde resins with lignin due to their similar structural framework. Many researchers have confirmed the multifunctional applications of lignin, such as wood adhesive in fiber board, plywood and particleboard, a binder in printed wiring boards, abrasive tools, epoxy asphalts, epoxy wood composites, 3D printing, adhesive hydrogels, soil suppressants, lignocellulosic paper and coatings. This review presents a comprehensive description of the utilization of lignin-based binders for different applications. The present work highlights the discussion on the various methods by which lignin can be used to replace synthetic binders. This review focuses on global research work introducing lignin in different chemical adhesives for a more cost-effective and less harmful alternative.
Keywords: binder; biodegradable; lignin; multifunctional

Novel pharmaceutical cocrystal of apalutamide, a nonsteroidal antiandrogen drug: synthesis, crystal structure, dissolution, stress, and excipient compatibility - Saladi, Venkata Narasayya; Kammari, Bal Raju; Mandad, Pratap Reddy; Krishna, Gamidi Rama; Sajja, Eswaraiah; Thirumali, Rajan S.; Marutapilli, Arthanareeswari; Mathad, Vijayavitthal T. (Crystal Growth & Design, 2022)
Apalutamide (APA), a second-generation nonsteroidal antiandrogen BCS Class II drug with poor solubility and high permeability. A novel 1:1 cocrystal of Apalutamide (APA) with methylparaben (MP) was identified by cooling crystallization during the cocrystal screening and characterized by various solid-state techniques, such as PXRD, DSC, TGA, FT-IR, and 13C solid-state CP-MAS NMR spectroscopy. The crystal structures of APA and its cocrystal (APA-MP) were determined by the SC-XRD technique. The crystal structure analysis of the APA-MP cocrystal revealed that the APA and MP molecules are connected through strong O–H···O hydrogen bonds. The novel cocrystal improves the solubility and dissolution rate in different physiological conditions compared to poorly soluble APA due to strong hydrogen bond between the drug and the coformer. The cocrystal is stable (physically and chemically) under stress conditions, such as exposure to the relative humidity, mechanical grinding, open exposure to atmosphere at cRT (critical room temperature) and compression pressure of 10 tons. In addition, the compatibility of the cocrystal with excipients used in the drug product of APA (ERLEADA) was also investigated, and no disproportionation of cocrystal was observed.

One-pot concurrent biosynthesis of biphasic CuxO (cuprous and cupric oxide) nanoparticles using leaf extract of Eichhornia crassipes and investigation of their potent healthcare applications - Moudgil, Aliesha; Varma, Sanjana; Shinde, Manish D.; Vamkudoth, Koteswara Rao; Sarkar, Dhiman M.; Shende, Rajnigandha A.; Amalnerkar, Dinesh; Chaudhari, Bhushan P. (Emergent Materials, 2022)
Eichhornia crassipes, an aquatic weed, has been used for the one-pot quick synthesis of cuprous and cupric oxide nanoparticles in this report. The identification and validation of the formed nanoparticles were successfully done by sophisticated characterization techniques such as UV–visible spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectroscopy. Their biomedical interventions were assessed by their antioxidant and anticancer activities. The synthesized nanoparticles have a spherical morphology with an average diameter of 10 nm. Antioxidant assay performed showed an increasing trend in a dose-dependent manner with the percentage radical scavenging activity up to 94.70% at a much higher concentration of 1000 µg/ml. The antioxidant potential at such higher concentration is suspected to invoke a change in the cytotoxic potential of the nanoparticles which is then verified by the MTT assay. A significant cytotoxic activity against HeLa (cervical cancer) and HCT 116 (colorectal carcinoma) cell lines was detected with noted IC50 values of 17.17 and 13.70 µg/ml respectively. The conclusive findings obtained are enough to substantiate the use of these nanoparticles in biomedical areas specifically in anticancer treatment due to their high toxicities. The hazards imposed by Eichhornia crassipes can be alleviated by using them as biofactories for the synthesis of a variety of nanomaterials. This helps in curbing the water pollution issues as well as the developing synthesis protocols for robust and stable nanoparticles.

Palladium mediated selective cleavage of benzyl and allyl phosphates: a convenient non-hydrogenolytic method for the synthesis of phosphates and phospholipids. - Mart, Alson; Sarkar, Nitai N.; Shashidhar, Mysore S. (ChemistrySelect, 2022)
Palladium(II) hydroxide on carbon is a catalyst routinely used for the cleavage of O-benzyl groups by hydrogenolysis to obtain the corresponding parent organic compound. The work described in this article shows that allyl and benzyl phosphates, can be cleaved efficiently and selectively using palladium(II) hydroxide on carbon, under non-hydrogenolytic and neutral conditions, precluding the migration of acyl groups. The utility of these cleavage reactions for the synthesis of diacylglycerol and phosphatidic acid, containing unsaturation, is demonstrated. These methods have high potential for the synthesis of a variety of phosphates and natural phospholipids.
Keywords: Carbohydrate; Ether cleavage; Palladium; Phosphate; Phospholipid; Protecting group

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

Polymorphs of green fluorescence protein chromophore analogue: fluorescence switching with thermal stimuli - Mali, Bhupendra P.; Dash, Soumya Ranjan; Biswas, Anupam; Vanka, Kumar; Manoj, Kochunnoonny; Gonnade, Rajesh G. (Crystal Growth & Design, 2022)
Polymorphs of fluorescent organic materials offer significant implications in optoelectronics and advanced materials as they modulate photoluminescence properties. A slight alteration in the conformation/packing of molecules in the crystals shows variation in photoluminescence. This necessitates the polymorph screening of these materials to develop novel crystalline forms with distinct fluorescence emissions for broader application. In continuation of our work on the polymorph screening of Green Fluorescence Protein Chromophore (GFPc), we have synthesized a new imidazoline derivative, ethyl (Z)-2-(2-methyl-5-oxo-4-(3,4,5-trimethoxybenzylidene)-4,5-dihydro-1H-imi dazol-1- yl)acetate (1). Polymorph screening of 1 under different crystallization conditions revealed three polymorphs, Form I (needle), Form II (block), and Form III (polycrystalline material). Forms I and II are the outcome of solution crystallization, whereas Form III was produced from the melt crystallization of Forms I and II. DSC, HSM, and powder and single-crystal XRD studies indicate the conversion of Form I and Form III crystals to Form II crystals on thermal stimuli. The photoluminescence studies revealed cyan, yellow, and yellowish-green fluorescence emission for Forms I, II, and III crystals, respectively. The difference in photoluminescence could be due to the variance in aggregation modes like H-aggregation in Form I and J-aggregation in Form II crystals. Form I, Form II, and Form III crystals also showed irreversible thermal fluorescent switching from cyan-yellow-green due to polymorphic phase transitions. The study correlates the direct observation of the modulation of the excited-state transition under thermal stimuli in the crystalline phase. It will help augment the pace in the research of thermally responsive fluorescent materials.

Porous covalent organic nanotubes and their assembly in loops and toroids - Koner, Kalipada; Karak, Shayan; Kandambeth, Sharath; Karak, Suvendu; Thomas, Neethu; Leanza, Luigi; Perego, Claudio; Pesce, Luca; Capelli, Riccardo; Moun, Monika; Bhakar, Monika; Ajithkumar, Thalasseril G.; et al. (Nature Chemistry, 2022)
Carbon nanotubes, and synthetic organic nanotubes more generally, have in recent decades been widely explored for application in electronic devices, energy storage, catalysis and biosensors. Despite noteworthy progress made in the synthesis of nanotubular architectures with well-defined lengths and diameters, purely covalently bonded organic nanotubes have remained somewhat challenging to prepare. Here we report the synthesis of covalently bonded porous organic nanotubes (CONTs) by Schiff base reaction between a tetratopic amine-functionalized triptycene and a linear dialdehyde. The spatial orientation of the functional groups promotes the growth of the framework in one dimension, and the strong covalent bonds between carbon, nitrogen and oxygen impart the resulting CONTs with high thermal and chemical stability. Upon ultrasonication, the CONTs form intertwined structures that go on to coil and form toroidal superstructures. Computational studies give some insight into the effect of the solvent in this assembly process.

Possible fine-tuning of methane activation toward C2 oxygenates by 3d-transition metal-ions doped nano-ceria-zirconia - Kanungo, Subhashree S.; Mishra, Abhaya Kumar; Mhamane, Nitin B.; Marelli, Udaya Kiran; Kumar, Dharmesh; Gopinath, Chinnakonda S. (Inorganic Chemistry, 2022)
In this work, we demonstrate a simple sol-gel technique to prepare metal-ion(s)-doped ceria-zirconia solid solution for efficient catalytic methane activation. The cation -depicting formula units are Ce0.80Zr0.20 (CZ), Ce0.79Zr0.20M0.01 (CZM), and Ce0.79Zr0.20M0.005M10.005 (CZMM1) (M and M1 = V, Mn, Fe, Co, and Cu), employed for undoped, mono-metal-ion -doped, and bi-metal-ion-doped solid solutions, respectively. Methane activation with Mn, Fe, Cu mono-metal-ion-doped CZ favors the C1 product, while CZCo assists C-C coupling with the formation of acetaldehyde. On the other hand, the Co-and Fe -doped bi-metal-ion combination catalyst (CZCoFe) shows significant ethanol but predominant formic acid formation. This is further promoted by the Co + V bi-metal-ion combination (CZCoV) catalyst, and it shows ethanol as the major product along with methyl hydrogen peroxide, methanol, and formic acid as minor products. An impressive ethanol yield of 93 mu mol/g h with 76% selectivity obtained with the CZCoV catalyst is at par with that obtained with noble-metal-based catalysts under comparable reaction conditions. When Co and V content was increased two and four times from 0.005 to 0.01 and 0.02, ethanol yield increased at the expense of formic acid. The 213 mu mol/g h ethanol yield (86% selectivity) observed with Ce0.76Zr0.20Co0.02V0.02 is probably the highest observed. The partial oxidation of CH4 in Co-based bi-metal combinations (Co + V or Co + Fe) suggests the synergistic effect of doped metal ions owing to the heterogeneous near -neighbor environment. The present results are attributed to the surface heterogeneity between the host and the dopants, which selectively promotes methane activation as well as C-C coupling. This indicates a large scope to tune the activity of partial oxidation of methane and product selectivity with different metal-ion(s) combinations.

Postmodification of voxelotor (GBT 440) via [Rh]-catalyzed cross dehydrogenative coupling with olefins br - Kalshetti, Rupali G.; Rajput, Raveena; Motiwala, Zenia; Reddy, D. Srinivasa; Kulkarni, Kiran A.; V. Ramana, Chepuri (Bioorganic & Medicinal Chemistry Letters, 2022)
The directed Rh(III)-catalyzed cross dehydrogenative coupling of the pyrazole unit of the GBT-440 scaffold has been explored with simple as well as conjugated olefins to synthesize post-functionalized GBT-440 analogues. The screening of these synthesized compounds for improving the oxygen binding efficiency of the hemoglobin isolated from the sickled red blood cells revealed that some of these compounds are as good as GBT-440.
Keywords: CDC Coupling; GBT-440 (Voxelotor); Rh(III) catalysis; sickle cell anemia

Potassium phosphate catalyzed highly efficient synthesis of structurally diverse thioethers at ambient temperature - Mitragotri, Satish D.; Kulkarni, Makarand A.; Desai, V. Uday; Wadagaonkar, Prakash P. (Indian Journal of Chemistry Section B-Organic Chemistry Including Medicinal Chemistry, 2022)
Commercially available potassium phosphate has been demonstrated to be a highly efficient catalyst for the synthesis of thioethers employing two different routes viz. alkylation of thiols with alkyl/aralkyl halides and by Michael addition of thiols to conjugated alkenes.
Keywords: Alkyl halides; Potassium phosphate; thia-Michael reaction; thioethers; thiols

Process development for crystalline xylitol production from corncob biomass by Pichia caribbica - Dasgupta, Diptarka; Sidana, Arushdeep; Sarkar, Bipul; More, Snehal; Ghosh, Debashish; Bhaskar, Thallada; Ray, Anjan (Food and Bioproducts Processing, 2022)
Xylitol, a commodity chemical, is widely used in nutraceutical and pharmaceutical formulations. Microbial xylitol production is a promising alternative to mitigate current industrial practice issues and offers an environment-friendly sustainable conversion route. This study demonstrates a bioprocess for xylitol production from corncob using a mesophilic yeast Pichia caribbica. Corncob was hydrolyzed by dilute acid and steam explosion to recover fermentable xylose and used as the feed for xylitol production. Activated carbon treatment (3% w/v) completely removed the biomass-derived inhibitors furfural and hydroxymethyl furfural from the liquid hydrolysate. The fermenting yeast Pichia caribbica produced 124.1 +/- 0.45 g/L xylitol from the detoxified and concentrated corncob hydrolysate with a high yield of 0.80 +/- 0.02 g/g. The crystallized xylitol with 96.5% purity demonstrated no harmful effects on the cell line used as a control for the in-vitro toxicity studies. This proof of concept can be applied to help scale up for bio-refinery-based large-scale production of xylitol from corncob biomass.(c) 2022 Institution of Chemical Engineers. Published by Elsevier Ltd. All rights reserved.
Keywords: Biomass; Corncob; Detoxification; Fermentation; Toxicity analysis; xylitol

Process development for detoxification of corncob hydrolysate using activated charcoal for xylitol production - Ahuja, Vishal; Kshirsagar, Siddheshwar; Ghosh, Prasenjit; Sarkar, Bipul; Sutar, Ajit; More, Snehal; Dasgupta, Diptarka (Journal of Environmental Chemical Engineering, 2022)
The work describes process development for detoxification of corncob hydrolysate using activated carbon for microbial xylitol production. Activated carbon was used as an adsorbent to completely remove the major fermentation inhibitors obtained during dilute acid and steam explosion of biomass. A xylitol yield of 0.78 g/g was achieved from the detoxified hydrolysate in a 5 L fermenter by Pichia caribbica. The spent carbon was effectively regenerated and used for three consecutive cycles of operation. The successive regeneration and reuse of carbon could reduce the operational cost by similar to 38% and be used as a reference dataset for process scale-up and cost-effective xylitol production.
Keywords: Activated charcoal; Detoxification; Fermentation; Regeneration; xylitol

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.

Ready access to benzannulated [5,5]-oxaspirolactones using Au(III)-catalyzed cascade cyclizations - Mankad, Yash; Thorat, Sagar S.; Das, Pronay; Krishna, Gamidi Rama; Kontham, Ravindar; Reddy, D. Srinivasa (Journal of Organic Chemistry, 2022)
This work showcases an unprecedented Au(III)-catalyzed cascade cyclization of 2-(4-hydroxyalkynyl)benzoates to access benzannulated [5,5]-oxaspirolactones related to biologically active natural products. This reaction proceeds through an initial 5-endo-dig mode of hydroalkoxylation of the alkynol segment to give the oxocarbenium species (via cyclic enol-ether) followed by the addition of carboxylate onto the oxocarbenium that delivers the oxaspirolactone scaffold. While testing this method's scope, we found that the steric and electronic environment of the hydroxyl group could alter the reaction pathway that delivers isochromenone through a competitive 6-endo-dig mode of attack of the carboxylate onto the tethered alkyne.

Ready access to densely substituted furans using Tsuji-Wacker type cyclization - Masal, Dattatraya P.; Choudhury, Rahul; Singh, Aman; Reddy, D. Srinivasa (Journal of Organic Chemistry, 2022)
A competent method for the construction of highly substituted furans catalyzed by Pd(II) and Cu(II) chloride has been developed. The method provides easy access to di-, tri-, and tetrasubstituted furans from corresponding diols with relatively mild conditions in a unified strategy. The developed method has been successfully tested with more than 25 substrates, which resulted in furans of multiple substitution patterns with up to 84% isolated yields.

Reduction of carbon dioxide to dimethylformamide using ruthenium doped Mg/Al hydrotalcites under supercritical conditions - Chaudhary, Sagar D.; Rahatade, Shardul S.; Joshi, Sunil S.; Mali, Nilesh A. (Journal of CO2 Utilization, 2022)
The utilization of carbon dioxide is one of the developing areas due to its significant contribution to global warming. Reducing carbon dioxide (CO2) to formic acid and its derivatives has gained importance because of its thermodynamic limitations and high industrial demand. In this article, we report the synthesis of dime-thylformamide (DMF) using ruthenium doped Mg/Al calcined hydrotalcite by CO2 hydrogenation in the presence of dimethylamine (DMA). At optimized conditions, complete conversion of dimethylamine was achieved with more than 92% product yield at 170 degrees C and 13 MPa pressure with a reaction time of 6 h. Key catalyst properties were determined using X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), CO2-temper-ature programmed desorption (TPD), H-2 temperature-programmed reduction (TPR) and Fourier transform infrared (FTIR). The determination of surface morphology was carried out using field emission scanning electron microscope (FE-SEM) and high-resolution transmission electron microscopy (HR-TEM). At the same time, the chemical composition was verified by energy-dispersive X-ray (EDS). In addition, kinetic modeling is performed using the two site Langmuir-Hinshelwood-Hougen-Watson model. The regressed kinetic parameters gave an appropriate fit with experimental concentration values and activation energy is calculated as 413 kJ/mol K-1.
Keywords: Dimethylformamide; Hydrogenation; hydrotalcite; Langmuir-Hinshelwood-Hougen-Watson model; Supercritical carbon dioxide

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

Regio-isomerism directed electrocatalysis for energy efficient zinc-air battery - Mukhopadhyay, Sanchayita; Devendrachari, Mruthyunjayachari Chattanahalli; Kanade, Sandeep C.; Vinod, Chathakudath Prabhakaran; Kotresh, Harish Makri Nimbegondi; Thotiyl, Musthafa Ottakam (iScience, 2022)
We have investigated the role of ligand isomerism in modulating the mechanisms and kinetics associated with charge/ discharge chemistry of an aqueous metal-air battery. The dominant electron-withdrawing inductive effect (-I effect) and the diminished electron-withdrawing resonance effect (-R effect) in the alpha-NO2 isomer noticeably diminishes the rate of oxygen reduction (ORR) and oxygen evolution reactions (OER) on the catalytic Co-center. In their beta-counterpart, the cumulative -I and -R effects noticeably enhance the OER and ORR kinetics on the same catalytic Co-center. Therefore, the regioisomerism of the -NO2 functionality amplifies the kinetics of ORR/OER without influencing their mechanistic pathways. When isomeric electrocatalysts are integrated to aid the charge chemistry of a Zn-air battery, the overpotential could be decreased by similar to 250mV with beta-NO2 isomer leading to a round-trip efficiency as high as 60%. This work contributes to the design of novel molecular platforms to target the overall round-trip efficiency of energy storage and conversion devices.

Regioselective synthesis of 1,4,5-trisubstituted 1,2,3-triazole derivatives from alpha,beta-unsaturated carbonyls - Verma, Naimish K.; Bera, Smritilekha; Gonnade, Rajesh; Mondal, Dhananjoy (European Journal of Organic Chemistry, 2022)
The copper-catalyzed oxidative azide-olefin cycloaddition (OAOC) reaction of differently substituted alpha,beta-unsaturated carbonyls with azides provided an efficient method for preparing biologically active 1,4,5-trisubstituted 1,2,3-triazoles. In this study, the cycloaddition reaction was found to be a simple and powerful method for constructing diverse mono- and bis-(1,4,5-trisubstituted 1,2,3-triazole) functionalized heterocyclic compounds in moderate to high yields with great regioselectivity. The XRD-analysis data of one of the bis-triazole derivatives supported the regioselectivity as well as the conformity of the method in the construction of the triazole nucleus. The preliminary antifungal profile against C. albicans was observed with cinnamaldehyde-based triazole derivatives demonstrating promising results.
Keywords: alpha; antifungal; beta-Unsaturated carbonyls; Cycloaddition; Dibenzalacetone; Triazole

Regioselectivity in metalloradical catalyzed C-H bond activation: a theoretical study - Mukherjee, Anirban; Singh, Ritesh; Mane, Kishor D.; Das, Gourab Kanti (Journal of Organometallic Chemistry, 2022)
Pure quantum mechanical calculations were performed to find out the origin of regioselectivity under the metalloradical catalysis (MRC) by Co(II)-porphyrin, which showed regioselectivity is the inherent property of the aminyl radical generated from the sulfamoyl azide substrate. Different conformational analysis for the transition state from alpha-Co-III-aminyl radical to zeta-Co-III-alkyl radical formation have been studied to find out the most stable conformation for the preferable selectivity. The outcome of our study completely agrees with the reported experimental results. (C) 2021 Elsevier B.V. All rights reserved.
Keywords: C-H activation; DFT; Metalloporphyrin; Metalloradical; Regioselectivity

Reusable and efficient polystyrene immobilized ionic liquid catalyst for batch and flow methylation of hydroquinone - Bhongale, V. Priyanka; Joshi, Sunil S.; Mali, Nilesh A. (Catalysis Letters, 2022)
An environmentally benign process for synthesizing 4-methoxyphenol through methylation of hydroquinone using polystyrene immobilized Bronsted acidic ionic liquid is presented. The catalyst has been characterized by several techniques, such as solid-state NMR, FTIR, and XRD. The morphological properties were analyzed through SEM and TEM analysis. The elemental analysis was performed using EDS and XPS techniques. The catalyst was thermally stable up to 603 K, which was confirmed by TGA. The chemical interaction between ionic liquid and polystyrene was confirmed by measuring the glass transition temperature of pure polystyrene and catalyst. The BET analysis was performed to estimate the catalyst's surface area, pore size, and pore volume. The recyclability of the proposed new catalyst was established up to five recycle runs in the batch mode. In addition, continuous flow experiments were conducted to test the catalytic activity in terms of catalyst life span and showed excellent stability up to 20 h. The rapid separation, long-term stability, and efficient recycling of synthesized polymeric catalysts make an excellent alternative to the commonly used homogeneous catalysts for selective O-methylation of hydroquinone reaction. The newly developed continuous process for synthesizing 4-methoxyphenol with 100% selectivity suggests good opportunities to reduce energy consumption, which designates a cost-effective process. [GRAPHICS] .
Keywords: 4-Methoxyphenol; Hydroquinone; O-methylation; Polystyrene immobilized ionic liquid

Review on non-noble metal catalysts for glycerol hydrodeoxygenation to 1,2-propanediol with and without external hydrogen - Mane, Rasika; Jeon, Yukwon; Rode, Chandrashekhar (Green Chemistry, 2022)
The depleting petroleum oil resources, political embargos, and global warming dilemma have made it mandatory to develop alternative green technologies for energy and chemical production. Glycerol is one of the top-12 building block chemicals that can be mainly obtained as a coproduct of biodiesel production. The value addition of glycerol is only possible through its conversion to commodity and fine chemicals. Glycerol hydrogenolysis is one of the crucial pathways to produce several value-added products, among which 1,2-propanediol (1,2-PDO), 1,3-propanediol (1,3-PDO), ethylene glycol (EG) and 1-and/or 2-propanols are hydrogenolysis products. Selective glycerol hydrogenolysis to the desired product 1,2-PDO is only possible through the catalyst having an optimum combination of acid/base and metal sites (metallic and mixed oxides). The present review mainly focuses on the critical assessment of the influence of different supports, catalyst preparation methods, and/or pretreatment on structural, and electronic properties and simultaneously on the activity and product selectivity of non-noble metal catalysts. The role of reaction parameters in this industrially important reaction on catalyst performance will also be presented. A rigorous survey of patented literature on non-noble metal-catalyzed glycerol hydrogenolysis to 1,2-PDO is also discussed. Further, the review covers recent progress on non-noble metal-catalyzed autogenous glycerol hydrogenolysis through glycerol aqueous phase reforming (APR) and/or catalytic transfer hydrogenolysis (CTH), to overcome the cost and handling issues of external hydrogen. Finally, techno-economic analysis is also presented which compares the glycerol hydrogenolysis with and without external hydrogen with the conventional process of 1,2-PDO production. This analysis indicated that CTH and glycerol hydrogenolysis under ambient hydrogen pressure have the potential for commercialization, however catalyst stability and elimination of co-product formation at higher glycerol concentration need to be considered critically.

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

Screening of osmotic stress-tolerant bacteria for plant growth promotion in wheat (Triticum aestivum L.) and brinjal (Solanum melongena L.) under drought conditions - Patel, P.; Patil, T.; Maiti, S.; Paul, D.; Amaresan, N. (Letters in Applied Microbiology, 2022)
Drought stress adversely affects plant growth and productivity. Therefore, the application of plant growth-promoting bacteria is a viable option for combating drought resistance in crops. In this study, 144 bacteria were isolated from the Kutch desert soil in Gujarat. Based on osmotic stress tolerance and PGP properties, two strains, Bacillus tequilensis (KS5B) and Pseudomonas stutzeri (KS5C) were tested for their effect on wheat (Triticum aestivum L.) and brinjal (Solanum melongena L.) under drought stress conditions. Inoculation with osmotic stress-tolerant bacteria showed 15 center dot 15-29 center dot 27% enhancement in root length of wheat and 15 center dot 27-32 center dot 59% in brinjal plants. Similarly, the enhancement of shoot length ranged from 14 center dot 72 to 37 center dot 70% for wheat and 59 center dot 39-95 center dot 94% for brinjal plants. Furthermore, the inoculated plants showed significant improvement in chlorophyll content and antioxidant properties such as proline, peroxidase and polyphenol oxidase activity compared to the control. Therefore, the bacterial strains identified in this study can be used to mitigate drought stress and enhance plant biomass.
Keywords: Antioxidant; brinjal; drought; plant growth; Wheat

`Self-activating' Bi3TaO7-Bi4TaO8Br photocatalyst and its use in the sustainable production of pro-fluorophoric rhodamine-110 - Banoo, Maqsuma; Chatterjee, Kaustav; Mondal, Sanjit; Vinod, C. P.; Gautam, Ujjal K. (Green Chemistry, 2022)
We counter two common notions that (i) photocatalysts are likely to degrade during use with barely any strategy to counter it and (ii) rhodamine-B (RhB) photo-degradation lacks any useful or commercial prospects even after 53 years of its discovery by developing a photocatalyst that continues to improve its activity for similar to 300 h due to a leaching induced `self-activation' process. Rhodamine-110 (Rh110) is a widely used pro-fluorophore in biological studies. However, its commercial production is highly challenging due to the formation of various side-products originating from the presence of the two labile amino side-groups that induce the pro-fluorophore activity, leading to purification difficulties, low yield, and unusually high costs. Herein, we demonstrate a facile strategy to produce pure Rh110 using extremely inexpensive RhB and Bi3TaO7-Bi4TaO8Br heterostructures as a catalyst in sunlight. The catalyst is not just stable over 30 catalytic cycles but also gets activated continuously in successive cycles to produce a reaction yield as high as 88%. The role of the heterostructure, the origin of surface activation, and the RhB -> Rh110 transformation mechanism have been established. Based on 150 days of sunlight experiments, large-scale production prospects (similar to 4000 times scale-up) and isolation of Rh110 have also been realized, paving a novel way for its production by anyone, inexpensive biological essaying, and device fabrication. Continuously improving catalysts are unknown and compensatory leaching of metal atoms from the catalyst surface may pave the way to realize them.

Silver dependent enantiodivergent gold(i) catalysed asymmetric intramolecular hydroamination of alkenes: a theoretical study - Dixit, Ruchi; Sharma, Himanshu; Agbossou-Niedercorn, Francine; Vanka, Kumar; Michon, Christophe (Catalysts, 2022)
We report a theoretical study of the first silver-dependent enantiodivergent gold-catalysed reaction. The combination of a single chiral binuclear gold(I) chloride complex and silver perchlorate catalyses the asymmetric intramolecular hydroamination of alkenes and affords both enantiomers of the products by applying a simple solvent change from toluene to methanol. A gold-silver chloride adduct that occurs only in methanol appears to control the enantioinversion. If one gold atom coordinates and activates the alkene moiety, the other gold is included in an adduct with silver chloride, which coordinates a methanol solvent molecule and further interacts with the amine function. If the use of toluene implies free anions and affords (S)-enantiomer, methanol allows a proximal interaction with the amine, leads to an opposite stereodifferentiation of the two diastereomeric intermediates during the final protodeauration step and results in the (R)-enantiomer.
Keywords: alkene; enantiodivergent catalysis; Gold; hydroamination; Silver

Small molecule quercetin binds MALAT1 triplex and modulates its cellular function - Rakheja, Isha; Ansari, Asgar Hussain; Ray, Arjun; Joshi, Dheeraj Chandra; Maiti, Souvi (Molecular Therapy-Nucleic Acids, 2022)
The triple-helix structure at the 30 end of metastasis-associated lung adenocarcinoma transcript 1 (MALAT1), a long non -cod-ing RNA, has been considered to be a target for modulating the oncogenic functions of MALAT1. This study examines the binding of quercetin-a known triplex binding molecule-to the MALAT1 triplex. By employing UV-visible spectroscopy, circular dichroism spectroscopy, and isothermal titration calo-rimetry, we observed that quercetin binds to the MALAT1 triplex with a stoichiometry of 1:1 and Kd of 495 +/- 61 nM, along with a negative change in free energy, indicating a spontaneous interaction. Employing real-time PCR measurements, we observed around 50% downregulation of MALAT1 transcript levels in MCF7 cells, and fluorescence in situ hybridization (FISH) experiments showed concomitantly reduced levels of MALAT1 in nuclear speckles. This interaction is likely a result of a direct interaction between the molecule and the RNA, as indicated by a transcription-stop experiment. Further, tran-scriptome-wide analysis of alternative splicing changes induced by quercetin revealed modulation of MALAT1 downstream genes. Collectively, our study shows that quercetin strongly binds to the MALAT1 triplex and modulates its functions. It can thus be used as a scaffold for further development of ther-apeutics or as a chemical tool to understand MALAT1 func-tions.

SNP discovery and structural insights into OeFAD2 unravelling high oleic/linoleic ratio in olive oil - Ben Ayed, Rayda; Moreau, Fabienne; Ben Hlima, Hajer; Rebai, Ahmed; Ercisli, Sezai; Kadoo, Narendra; Hanana, Mohsen; Assouguem, Amine; Ullah, Riaz; Ali, Essam A. (Computational and Structural Biotechnology Journal, 2022)
Fatty Acid Desaturase 2 (FAD2), a key enzyme in the fatty acid biosynthesis pathway, is involved in the desaturation and conversion of oleic acid to linoleic acid. Therefore, it plays a crucial role in oleic/linoleic acid ratio and the quality of olive oil. DNA sequencing of 19 FAD2 genes from a set of olive oil varieties revealed several single-nucleotide polymorphisms (SNPs) and highlighted associations between some of the SNPs and saturated fatty acids contents. This was further confirmed by SNP-interaction and machine learning approach. Haplotype diversity analysis led to the discovery of three highly polymorphic SNPs and four haplotypes harboring differential oleic/linoleic acid ratios. Moreover, a combination of molecular modeling and docking experiments allowed a deeper and better understanding of the structure-function relationship of the FAD2 enzyme. Sequence patterns and variations involved in the regulation of the FAD2 activity were also identified. Furthermore, S82C and H213N substitutions in OeFAD2 make the Oueslati variety more interesting in terms of fatty acid profile and oleic acid level. (C) 2022 The Authors. Published by Elsevier B.V. on behalf of Research Network of Computational and Structural Biotechnology.
Keywords: docking; Fatty acid desaturase; Haplotype; machine learning; Oleic/linoleic acid ratio; Protein structure

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

Stacking herbicide detoxification and resistant genes improves glyphosate tolerance and reduces phytotoxicity in tobacco (Nicotiana tabacum L.) and rice (Oryza sativa L.) - Vennapusa, Amaranatha Reddy; Agarwal, Subham; Hm, Hanumanth Rao; Aarthy, Thiagarayaselvam; Babitha, K. C.; Thulasiram, V. Hirekodathakallu; Kulkarni, Mahesh J.; Melmaiee, Kalpalatha; Sudhakar, Chinta; Udayakumar, M.; Vemanna, Ramu S. (Plant Physiology and Biochemistry, 2022)
Glyphosate residues retained in the growing meristematic tissues or in grains of glyphosate-resistant crops affect the plants physiological functions and crop yield. Removing glyphosate residues in the plants is desirable with no penalty on crop yield and quality. We report a new combination of scientific strategy to detoxify glyphosate that reduces the residual levels and improve crop resistance. The glyphosate detoxifying enzymes Aldo-keto reductase (AKR1) and mutated glycine oxidase (mGO) with different modes of action were co-expressed with modified EPSPS, which is insensitive to glyphosate in tobacco (Nicotiana tabacum L.) and rice (Oryza sativa L.). The transgenic tobacco plants expressing individual PsAKR1, mGO, CP4-EPSPS, combinations of PsAKR1:CP4EPSPS, PsAKR1:mGO, and multigene with PsAKR1: mGO: CP4EPSPS genes were developed. The bio-efficacy studies of in-vitro leaf regeneration on different concentrations of glyphosate, seedling bioassay, and spray on transgenic tobacco plants demonstrate that glyphosate detoxification with enhanced resistance. Comparative analysis of the transgenic tobacco plants reveals that double and multigene expressing transgenics had reduced accumulation of shikimic acid, glyphosate, and its primary residue AMPA, and increased levels of sarcosine were observed in all PsAKR1 expressing transgenics. The multigene expressing rice transgenics showed improved glyphosate resis-tance with yield maintenance. In summary, results suggest that stacking genes with two different detoxification mechanisms and insensitive EPSPS is a potential approach for developing glyphosate-resistant plants with less residual content.
Keywords: Detoxification; Gene stacking; Glyphosate; Herbicide; Multigene; Residual toxicity; Resistant; rice; Tobacco; Transgenics

Steroidal alkaloids defence metabolism and plant growth are modulated by the joint action of gibberellin and jasmonate signalling - Panda, Sayantan; Jozwiak, Adam; Sonawane, Prashant D.; Szymanski, Jedrzej; Kazachkova, Yana; Vainer, Andrii; Kilambi, Himabindu Vasuki; Almekias-Siegl, Efrat; Dikaya, Varvara; Bocobza, Samuel; Shohat, Hagai; Meir, Sagit; et al. (New Phytologist, 2022)
Steroidal glycoalkaloids (SGAs) are protective metabolites constitutively produced by Solanaceae species. Genes and enzymes generating the vast structural diversity of SGAs have been largely identified. Yet, mechanisms of hormone pathways coordinating defence (jasmonate; JA) and growth (gibberellin; GA) controlling SGAs metabolism remain unclear. We used tomato to decipher the hormonal regulation of SGAs metabolism during growth vs defence tradeoff. This was performed by genetic and biochemical characterisation of different JA and GA pathways components, coupled with in vitro experiments to elucidate the crosstalk between these hormone pathways mediating SGAs metabolism. We discovered that reduced active JA results in decreased SGA production, while low levels of GA or its receptor led to elevated SGA accumulation. We showed that MYC1 and MYC2 transcription factors mediate the JA/GA crosstalk by transcriptional activation of SGA biosynthesis and GA catabolism genes. Furthermore, MYC1 and MYC2 transcriptionally regulate the GA signalling suppressor DELLA that by itself interferes in JA-mediated SGA control by modulating MYC activity through protein-protein interaction. Chemical and fungal pathogen treatments reinforced the concept of JA/GA crosstalk during SGA metabolism. These findings revealed the mechanism of JA/GA interplay in SGA biosynthesis to balance the cost of chemical defence with growth.
Keywords: alpha-tomatine; defence; gibberellin (GA); growth; jasmonate (JA); steroidal glycoalkaloids (SGAs); Tomato

Structure-tailored surface oxide on Cu-Ga intermetallics enhances CO2 reduction selectivity to methanol at ultralow potential - Bagchi, Debabrata; Raj, Jithu; Singh, Ashutosh Kumar; Cherevotan, Arjun; Roy, Soumyabrata; Manoj, Kaja Sai; Vinod, C. P.; Peter, Sebastian C. (Advanced Materials, 2022)
Electrochemical CO2 reduction reaction (eCO(2)RR) is performed on two intermetallic compounds formed by copper and gallium metals (CuGa2 and Cu9Ga4). Among them, CuGa2 selectively converts CO2 to methanol with remarkable Faradaic efficiency of 77.26% at an extremely low potential of -0.3 V vs RHE. The high performance of CuGa2 compared to Cu9Ga4 is driven by its unique 2D structure, which retains surface and subsurface oxide species (Ga2O3) even in the reduction atmosphere. The Ga2O3 species is mapped by X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) techniques and electrochemical measurements. The eCO(2)RR selectivity to methanol are decreased at higher potential due to the lattice expansion caused by the reduction of the Ga2O3, which is probed by in situ XAFS, quasi in situ powder X-ray diffraction, and ex situ XPS measurements. The mechanism of the formation of methanol is visualized by in situ infrared (IR) spectroscopy and the source of the carbon of methanol at the molecular level is confirmed from the isotope-labeling experiments in presence of (CO2)-C-13. Finally, to minimize the mass transport limitations and improve the overall eCO(2)RR performance, a poly(tetrafluoroethylene)-based gas diffusion electrode is used in the flow cell configuration.
Keywords: (2) reduction; CO; Electrochemistry; Methanol

Studies in instant water disinfection using natural oils - Dixit, Divya; Bhandari, Vinay M.; Mane, Maya B.; Balapure, Kshama (Biochemical Engineering Journal, 2022)
The present research reveals an instant and simple process for drinking water treatment by employing specific natural oils having antimicrobial properties to ensure complete elimination of harmful bacteria. The disinfection was studied for two different model bacteria, Gram-negative E. coli and Gram-positive, S. aureus. Seven natural oils, ajwain, thyme, oregano, peppermint, harsingar, cinnamon leaf and black pepper oil were evaluated and were found to yield 100% water disinfection within 1 min except for harsingar and black pepper oil. The process was also effective for the instant and 100% disinfection of real well water. The methodology for altering zeta potential, to an extent of 130%, for instant disinfection in drinking water treatment helps in selecting natural oils. Molecular docking studies indicated natural oils action as potential inhibitors of bacterial DNA gyrase. The studies indicate one of the lowest operating costs comparable to conventional chlorination. The simple meth-odology not requiring complex equipment has the potential to provide many options for implementations-from portability, household application to large scale water treatment plants.
Keywords: Bacteria removal; Natural oil; Technology; Water treatment; Zeta potential

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

Subcritical water hydrolysis of N-acetyl-D-glucosamine: hydrolysis mechanism, reaction pathways and optimization for selective production of 5-HMF and levulinic acid - Kulkarni, Sphurti Prakash; Dure, Shital N.; Joshi, Sunil S.; V. Pandare, Kiran; Mali, Nilesh A. (Carbohydrate Research, 2022)
In this study, the subcritical water hydrolysis of N-acetyl-D-glucosamine (NAG), a monomer of abundant renewable marine biopolymer chitin, for production of value-added chemicals is investigated. The enhanced ionization of water at subcritical conditions (200 degrees C; 50-100 bar), provides enough acidity for deacetylation of NAG resulting in 80% yield of acetic acid along with traces of formic acid, lactic acid, glucose, fructose, 5hydroxymethylfurfural (5-HMF),etc. The significant humin formation indicates that the self-condensation and polymerisation of 5-HMF is favored in water at subcritical conditions. A catalyst p-toluenesulfonic acid (p-TsOH) was employed to selectively convert NAG to levulinic acid (LA) via ring opening of 5-HMF previously formed during hydrolysis. The maximum yield of 27.13 +/- 1% and 53.46 +/- 1% of 5-HMF and LA, respectively, was obtained at process conditions optimized using Box-Behnken design coupled with response surface methodology. Subcritical water enables greener conversion of NAG to platform chemicals wherein the selective production can be achieved by tuning the process conditions.
Keywords: 5-Hydroxymethylfurfural; chitin; Glucosamine; levulinic acid; Response surface methodology; Subcritical water

Surface alteration driven bi-functional catalytic activity of alkali niobate-N doped graphene composite for exalted oxygen electrochemistry - Suman Kumari Jhajharia; Shashaank Gupta; Zinoy Manappadan; Kaliaperumal Selvaraj; Myoor K. Padmanabhan; Roop L. Mahajan (Applied Surface Science, 2022)
In this work, we establish that surface reconstruction, oxygen vacancies —specifically those located on the catalyst surface, and high crystallinity can be effective in tuning the catalytic activity of perovskite oxides. We report a high-performance electrocatalyst with an orthorhombic perovskite structure (NaNbO3), having an anisotropic surface layer and high crystallinity that exhibits superior activity and durability for the bi-functional oxygen electrochemistry compared to that of a similar perovskite composition with an isotropic surface layer and low crystallinity. The improvement in the electrocatalytic activity for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is mainly attributed to the formation of an easy diffusion path on the surface layer due to the ionic movements, enhanced intrinsic activity of the catalytic sites resulting from the higher crystallinity, high oxygen vacancies and a large electrochemically active surface area. The sole key parameter in achieving all the acquired characteristics is the annealing temperature. We believe that the straightforward method of bringing the desired combination of properties by just tweaking the annealing temperature is handy and energy-efficient, and hence easily adoptable.
Keywords: Bi-functionality; N-doped graphene; Oxygen Evolution Reaction; oxygen reduction reaction; perovskite; Surface reconstruction

Sustainable CO2 reduction on in (2)O(3 )with exclusive CO selectivity: catalysis and in situ valence band photoelectron spectral investigations - Mhamane, Nitin B.; Chetry, Sibo; Ranjan, Ravi; Raja, Thirumalaiswamy; Gopinath, Chinnakonda S. (ACS Sustainable Chemistry & Engineering, 2022)
This study demonstrates a sustainable catalytic CO2 conversion to near 100% CO selectivity at ambient pressure on In2O3. Critically, high CO yield could be observed at the cost of undesired methanation, using a lower than stoichiometric amount of hydrogen in the feed; 1:1 and 1:0.67 CO2:H-2 ratios exhibit 98-99.6% CO selectivity with 25-38% CO2 conversion between 773 and 873 K. CO2 and H-2 conversion under steady-state conditions at 773-873 K suggests a 1:1 ratio of adsorbed reactants (with 1:0.67 CO2:H-2 feed) on the catalyst surface, underscoring the presence of an ideal reactant composition for the reverse water-gas shift reaction, while H-2-rich feed compositions show the H-2-dominated surface. Surface electronic structure changes, under near-operating conditions, were explored with near ambient pressure photoelectron spectroscopy (NAPPES), and the interesting findings are as follows: (a) A shift in the valence band to lower binding energy, up to 0.6 eV, was observed because of electron filling at high temperatures. (b) An observation of heterogeneous nature of the catalyst surface under NAPPES measurement conditions is attributed to the generation of active oxygen vacancy (O-v) sites, which in turn changes the work function of In2O3. (c) The above changes are found to be reversible, when the reaction was stopped. Vibrational features of the reactant molecules were observed to be broadened in the active temperature window of the catalyst supporting the heterogeneous character of the catalyst surface because of dynamic O-v generation. By optimizing gas hourly space velocity, CO2:H-2 ratio, and reaction temperature, exclusive CO selectivity is possible with a H-2:CO2 ratio of similar to 0.67, which will avoid the product separation stage altogether, while minimizing the expensive H-2 in the reactant feed.
Keywords: heterogeneous catalysis; Oxygen vacancy; photoelectron spectroscopy; RWGS; Work function

Sustainable composite of SnFe2O4 conversion alloying anode for lithium-ion storage - Yadav, Poonam; Parte, Golu; Malik, Wahid; Sabri, Ylias M.; Jones, Lathe A.; Shelke, V. Manjusha (Sustainable Energy & Fuels, 2022)
The development of high-performance, low-cost electrodes using sustainable materials for Li-ion batteries is of vital importance in view of their increasing demand for use in electronics and electric vehicles, as we transition from non-renewable energy resources. Challenges associated with commercial graphite anode materials include relatively low capacity, the use of high-temperature synthesis, Li dendrite formation, and limited rate capability. In this study, we present a tin ferrite SnFe2O4 (SFO) conversion alloying material (CAM), and its synergistic composite with a scalable and low-cost waste-derived carbon (WDC), which was prepared by low-temperature pyrolysis of a waste material sustainably. The combination of SFO with the WDC in the composite boosts the conductivity, diffusion kinetics, stability, and reversibility, and accommodates volume expansion upon cycling. The first charge capacity obtained for WDC, SFO, and SFO-WDC is 595, 1269, and 1331 mA h g(-1), respectively at 100 mA g(-1) in a Li-ion half-cell. In a full cell fabricated with LFP, a stable capacity of 80 mA h g(-1) at 100 mA g(-1) could be obtained, and the corresponding energy density for the SFO-WDCIILFP full cell is 300 W h kg(-1). Kinetic studies revealed that capacitance-controlled charge storage is dominant so the capacity was higher in the composite. This composite system addresses both the low capacity issue of the carbon anode and stability issues of CAMs while being compatible for use with current Li-ion battery technology.

Synergistic and competitive lipid interactions in the serotonin1A receptor microenvironment - Mohole, Madhura; Sengupta, Durba; Chattopadhyay, Amitabha (ACS Chemical Neuroscience, 2022)
The interaction of lipids with G-protein-coupled receptors (GPCRs) has been shown to modulate and dictate several aspects of GPCR organization and function. Diverse lipid interaction sites have been identified from structural biology, bioinformatics, and molecular dynamics studies. For example, multiple cholesterol interaction sites have been identified in the serotonin1A receptor, along with distinct and overlapping sphingolipid interaction sites. How these lipids interact with each other and what is the resultant effect on the receptor is still not clear. In this work, we have analyzed lipid-lipid crosstalk at the receptor of the serotonin1A receptor embedded in a membrane bilayer that mimics the neuronal membrane composition by long coarse-grain simulations. Using a set of similarity coefficients, we classified lipids that bind at the receptor together as synergistic cobinding, and those that bind individually as competitive. Our results show that certain lipids interact with the serotonin1A receptor in synergy with each other. Not surprisingly, the ganglioside GM1 and cholesterol show a synergistic cobinding, along with the relatively uncommon GM1-phosphatidylethanolamine (PE) and cholesterol-PE synergy. In contrast, certain lipid pairs such as cholesterol and sphingomyelin appear to be in competition at several sites, despite their coexistence in lipid nanodomains. In addition, we observed intralipid competition between two lipid tails, with the receptor exhibiting increased interactions with the unsaturated lipid tails. We believe our work represents an important step in understanding the diversity of GPCR-lipid interactions and exploring synergistic cobinding and competition in natural membranes.
Keywords: GPCR; lipid crosstalk; Martini coarse-grain simulations; Membrane cholesterol; neuronal membranes

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 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 of 2D MoO3-x/N-doped-carbon nanocomposites via in situ carbonization of layered (NH4)Mo3O9-(NH4)(2)Mo4O13-organic hybrid nanomaterials for exceptionally efficient adsorption and separation of organic dyes - Gaikwad, Supriya Hanmant; Porel Mukherjee, Shatabdi (Environmental Science-Nano, 2022)
MoO3-x/N-doped-carbon (MoO3-x/N-C) nanocomposites with nanobelt structures were prepared by the in situ carbonization of the (NH4)Mo3O9-(NH4)(2)Mo4O13/oleylamine-oleic acid hybrids, and were designed using a two-step tailored nanoemulsion method followed by a solvothermal process. The MoO3-x/N-C nanocomposites possess high stability in a wide pH range of 1-11. In addition to the formation mechanism, detailed studies on adsorption properties, including adsorption isotherms, kinetics, mechanism, and reusability of the MoO3-x/N-C nanocomposites were systematically studied. The effects of various parameters on the adsorption characteristics, such as adsorbate concentration, contact time, pH, and temperature, were also evaluated. The detailed investigation of the kinetics and adsorption mechanism of MB from an aqueous solution showed that the adsorption process follows a pseudo-second-order kinetics and intraparticle diffusion model. The adsorption isotherm study demonstrated that the Langmuir isotherm model could illustrate the experimental data with a maximum adsorption capacity value of similar to 1360 mg g(-1), which turns out to be the highest among the previously reported adsorbents based on MoO3 nanomaterials, and is attributed to multiple adsorption mechanisms including electrostatic, pi-pi stacking, and H-bonding interactions between the MB dye and the MoO3-x/N-C nanocomposites. Thermodynamic analysis suggested that MB adsorption onto the MoO3-x/N-C nanocomposites was spontaneous and endothermic. Additionally, the adsorption and desorption cycles were examined for 100 ppm aqueous MB solution, where the removal efficiency by the MoO3-x/N-C nanocomposites remained at similar to 99% even after four regeneration cycles. Furthermore, the MoO3-x/N-C nanocomposites could selectively adsorb MB from a binary solution mixture containing two times higher concentrations of an anionic dye, methyl orange (MO), and the separation efficiency obtained was similar to 99% at neutral pH. More significantly, the MoO3-x/N-C nanocomposites could successfully and simultaneously adsorb several cationic dyes, including MB, malachite green (MG), crystal violet (CV), safranin O (SO), and separate an anionic dye, MO, from quaternary and pentanary dye mixture solutions with a separation efficiency of similar to 75% and 62%, respectively, at neutral pH. To the best of our knowledge, the effective separation of a single component by molybdenum oxide-based nanomaterials via a simple batch separation technique from a four/five-component mixed interfering analyte, close to a real matrix system, in an aqueous medium at neutral pH has not been reported so far. Therefore, the MoO3-x-based nanocomposite could be a new promising material for application in dye wastewater treatment.

Synthesis of a highly electron-deficient, water-stable, large ionic box: multielectron accumulation and proton conductivity - Shukla, Jyoti; Illathvalappil, Rajith; Kumar, Sharvan; Chorol, Sonam; Pandikassala, Ajmal; Kurungot, Sreekumar; Mukhopadhyay, Pritam (Organic Letters, 2022)
pi-acidic boxes exhibiting electron reservoir and proton conduction are unprecedented because of their instability in water. We present the synthesis of one of the strongest electron-deficient ionic boxes showing e(-) uptake as well as proton conductivity. Two large anions fit in the box to form anion-pi interactions and form infinite anion-solvent wires. The box with NO3-center dot center dot center dot water wires confers high proton conductivity and presents the first example that manifests redox and ionic functionality in an organic electron-deficient macrocycle.

Synthesis of new thiazole and pyrazole clubbed 1,2,3-triazol derivatives as potential antimycobacterial and antibacterial agents - Jagadale, Shivaji M.; Abhale, Yogita K.; Pawar, Hari R.; Shinde, Abhijit; Bobade, Vivek D.; Chavan, Abhijit P.; Sarkar, Dhiman; Mhaske, Pravin C. (Polycyclic Aromatic Compounds, 2022)
New series of 4-methyl-2-(4-substituted phenyl)-5-(4-((4-(4-substituted phenyl)-1H-1,2,3-triazol-1-yl)methyl)-1-phenyl-1H-pyrazol-3-yl)thiazole, 6a-t and 4-(1,3-diphenyl-1H-pyrazol-4-yl)-1-((1,3-diphenyl-1H-pyrazol-4-yl)methyl )-1H-1,2,3-triazole, 11a-o derivatives have been synthesized by applying copper-catalyzed [3 + 2] cycloaddition reaction. The newly synthesized 1,3-thiazolyl-pyrazolyl-1,2,3-triazole (6a-t) and bis-pyrazolyl-1,2,3-triazole (11a-o) derivatives were screened for in vitro antimycobacterial activity against M. Tuberculosis H37Ra dormant and active and antibacterial activity against four pathogenic bacteria, E. coli (NCIM 2576), P. flurescence (NCIM 2059), S. aureus (NCIM 2602) and B. subtilis (NCIM 2162). Compounds 6a, 6f, 6j, 11e and 11m showed good activity against M tuberculosis H37Ra Active strain, also compounds 6g, 6h, 11f, 11n and 11o showed good activity against M tuberculosis H37Ra Dormant strain. Compounds 6b, 6i, 6l, 6o, 6r, 11k, 11l and 11m showed good activity against B. subtilis with IC50 1.99-2.96 mu g/mL. The antibacterial activity of thiazolyl-pyrazolyl-1,2,3-triazole and bis-pyrazolyl-1,2,3-triazole derivatives suggested that, these derivatives could lead to new compounds for treatment against bacterial infection.
Keywords: 123-Triazole; antibacterial activity; antimycobacterial activity; Pyrazole; Thiazole

Tailored synthesis of ultra-stable Au@Pd nanoflowers with enhanced catalytic properties using cellulose nanocrystals - Hakkeem, Hasna M. Abdul; Babu, Aswathy; Shilpa, Nagaraju; Venugopal, Adithya A.; Mohamed, A. P.; Kurungot, Sreekumar; Pillai, Saju (Carbohydrate Polymers, 2022)
A green strategy for the synthesis of bimetallic core-shell Au@Pd nanoflowers (NFs) employing banana pseudostem-derived TEMPO-oxidized cellulose nanocrystals (TCNC) as both capping and shape-directing agent via seed-mediated method is presented. Flower-like nanostructures of Au@Pd bound to TEMPO-oxidized cellulose nanocrystals (TCNC-Au@Pd) were decorated on amino-functionalized graphene (NH2-RGO) without losing their unique structure, allowing them to be deployed as an efficient, reusable and a green alternative heterogeneous catalyst. The decisive role of TCNC in the structural metamorphosis of nanoparticle morphology were inferred from the structural and morphology analyses. According to our study, the presence of -OH rich TCNC appears to play a pivotal role in the structured evolution of intricate nanostructure morphology. The feasibility of the bio-supported catalyst has been investigated in two concurrently prevalent model catalytic reactions, namely the oxygen reduction reaction (ORR) and the reduction of 4-nitrophenol, the best model reactions in fuel cell and industrial catalytic applications, respectively.
Keywords: Au@Pd; catalysis; Cellulose nanocrystals; Nanoflowers; oxygen reduction reaction

Tantalum based single, double, and triple atom catalysts supported on g-C2N monolayer for effective nitrogen reduction reaction: a comparative DFT investigation - Rasool, Anjumun; Anis, Insha; Dixit, Mudit; Maibam, Ashakiran; Hassan, Afshana; Krishnamurty, Sailaja; Dar, Manzoor Ahmad (Catalysis Science & Technology, 2022)
Design of efficient and low cost electrocatalysts for the reduction of N-2 molecule to NH3 in a green manner remains a great challenge in the 21st century. Herein, we have used density functional theory based first principle simulations to systematically investigate the nitrogen reduction reaction (NRR) ability of single, double, and triple Ta-atom catalysts anchored to C2N monolayer. Our results demonstrate that the single and triple Ta-atom catalysts anchored to C2N monolayer act as superior catalysts for the NRR via alternating and distal pathways as compared to the Ru(0001) stepped surface. In particular, the triple Ta-atom catalyst anchored to C2N shows enhanced NRR performance with a limiting potential of -0.72 V which is comparable to the experimentally reported Ru based single atom catalyst. Further, all the three catalysts were found to be highly selective for NRR with an enhanced ability to suppress the competitive hydrogen evolution reaction. Electronic structure analysis revealed that the enhanced ability of Ta-3@C2N catalyst to effectively capture and reduce N-2 molecule could be attributed to the built up of localized d states near the fermi level, thereby aiding in strong electron transfer into the antibonding orbitals of N-2. Thus, our findings propose a highly active catalyst for the NRR with an emphasis on the importance of triple atom-based catalysts for electrocatalytic applications.

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.

Thallium(III) p-tosylate (TTS) mediated oxidative rearrangement of 2-naphthyl and 2-heteroarylchromanones - Kurapati, Chidvilas; Muthukrishnan, M.; Singh, V. Om; Gundla, Rambabu (Indian Journal of Chemistry, 2022)
A practical and effective approach towards the synthesis of 3-hetroaryl-4H-chromen-4-ones by the oxidative rearrangement of the respective 2-hetroaryl chroman-4-ones using thallium(III) p-tosylate is described. The oxidative rearrangement of alpha and beta-naphthyl and thiophene behave like aryl groups. However, pyridyl groups give only the dehydrogenated product.
Keywords: 2-(3-pyridyl)chromones; 2-(4-pyridyl)chromones; 2-and 3-(2-theinyl)chromones; 2-and 3-(3-theinyl)chromones; 2-and 3-(?-naphthyl) chromones; Dehydrogenation; Oxidative rearrangements; thallium(III) acetate; thallium(III) p-tosylate

Thallium(III) p-tosylate-mediated oxidative [1,2] rearrangement of 2-naphthyl and 2-heteroarylchromanones - Kurapati, Chidvilas; Muthukrishnan, Murugan; Singh, V. Om; Gundla, Rambabu (Journal of Heterocyclic Chemistry, 2022)
A practical and effective approach towards the synthesis of 3-heteroaryl-4H-chromen-4-ones by the oxidative [1,2] rearrangement of the respective 2-heteroaryl chroman-4-ones using thallium(III) p-tosylate is presented. The oxidative rearrangement of alpha- and beta-naphthyl and thiophene substituents behaves like aryl groups; However, pyridyl substituents gave only dehydrogenated products.

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.

Thiocyanate- and thiol-functionalized p-doped quantum dot colloids for the development of bulk homojunction solar cells - Dambhare, V. Neha; Sharma, Ashish; Mahajan, Chandan; Rath, Arup K. (Energy Technology, 2022)
Progress in device engineering and surface passivation strategies has led to steady progress in colloidal quantum dot (QD) solar cells. Bulk homojunction (BHJ) device architecture has several advantages over the conventional planar junction in developing QD solar cells. Herein, surface ligand chemistry is utilized to control the doping type and dispersibility of oppositely doped PbS QDs to develop BHJ solar cells. Thiocyanate and thiol ligand combination is introduced to develop p-PbS QD ink, which is blended with halide-passivated n-PbS QDs to build BHJ solar cells. It is shown that BHJ solar cells are benefited from high energy offset and higher hole mobility. This leads to the superior carrier extraction from a thicker active layer without compromising fill factor and open circuit voltage. Power conversion efficiency has reached 10.7% in 530 nm-thick BHJ solar cells, a 24% improvement over the best performing planar solar cells. With the help of the 1D solar cell capacitance simulator, it is shown that a 15% efficient QD solar cell can be realized by further improving the hole mobility above 0.1 cm(2) V-1 s(-1).
Keywords: bulk homojunctions; Doping; quantum dots; solar cells; surface functionalization

Transcriptional and translational perturbation in abiotic stress induced physiological activities and metabolic pathway networks in spongy tissue disorder of mango fruit - Oak, Pranjali; Jha, Vineet; Deshpande, Ashish; Tanpure, Rahul; Dawkar, Vishal; Mundhe, Swapnil; Ghuge, Sandeep; Prabhudesai, Shrikant; Krishanpal, Anamika; Jere, Abhay; Giri, Ashok; Gupta, Vidya (Postharvest Biology and Technology, 2022)
Spongy tissue formation is economically the most detrimental but agriculturally less focused physiological disorder in mango. `Alphonso' cultivar is highly prone to oxidative stress induced spongy tissue disorder impacting biochemical and metabolic profile, thereby affecting pulp quality and nutritional value of the fruit. In the present study, comparative analysis of spongy and healthy mesocarp tissues of `Alphonso' mango by transcriptomics using Illumina sequencing and proteomics using LC-MS approaches, respectively identified and quantified many genes and proteins in the metabolic pathways responsible for the spongy tissue development. The table green and the mid ripe stages of `Alphonso' fruit ripening were evaluated by the transcriptomic study and outcomes were validated using proteomic investigations for all the four ripening stages. Colossal amount of data including 30,582 transcripts, 10,800 gene ontologies and 387 putative proteins was generated from this analysis. Current multi-omics exploration revealed the development of abiotic stress (mainly oxidative stress) induced perturbations in various metabolic pathways and their interconnections, leading to the spongy tissue formation in mango. This further unfolded the altered cell wall degradation, ethylene and flavonoid biosynthesis, fruit ripening and flavor formation, thus hampering the fruit specific characteristics in mango with spongy tissue disorder.
Keywords: Oxidative stress; Proteome; spongy tissue disorder; Transcriptome; ` Alphonso ` mango

Trap inlaid cationic hybrid composite material for efficient segregation of toxic chemicals from water (vol 61, e202203385, 2022) - Fajal, Sahel; Mandal, Writakshi; Mollick, Samraj; More, Yogeshwer D.; Torris, Arun; Saurabh, Satyam; Shirolkar, Mandar M.; Ghosh, Sujit K. (Angewandte Chemie-International Edition, 2022)

Trap inlaid cationic hybrid composite material for efficient segregation of toxic chemicals from water - Fajal, Sahel; Mandal, Writakshi; Mollick, Samraj; More, Yogeshwer D.; Torris, Arun; Saurabh, Satyam; Shirolkar, Mandar M.; Ghosh, Sujit K. (Angewandte Chemie-International Edition, 2022)
Metal-based oxoanions are potentially toxic pollutants that can cause serious water pollution. Therefore, the segregation of such species has recently received significant research attention. Even though several adsorbents have been employed for effective management of chemicals, their limited microporous nature along with non-monolithic applicability has thwarted their large-scale real-time application. Herein, we developed a unique anion exchangeable hybrid composite aerogel material (IPcomp-6), integrating a stable cationic metal-organic polyhedron with a hierarchically porous metal-organic gel. The composite scavenger demonstrated a highly selective and very fast segregation efficiency for various hazardous oxoanions such as, HAsO42-, SeO42-, ReO4-, CrO42-, MnO4-, in water, in the presence of 100-fold excess of other coexisting anions. The material was able to selectively eliminate trace HAsO42- even at low concentration to well below the As-v limit in drinking water defined by WHO.
Keywords: Aerogel; Chemical Separation; Hybrid composite; Metal-Organic Gel; Metal-Organic Polyhedra

Tridentate NacNac stabilized tin and nickel complexes: access to a monomeric nickel hydride and its catalytic application - Pahar, Sanjukta; Sharma, Vishal; Mahata, Biplab; George, Christy P.; Sharma, Himanshu; Vanka, Kumar; Sen, Sakya S. (Inorganic Chemistry, 2022)
The transmetalation reaction of picolyl-supported tridentate nacnac germylene monochloride [2,6-iPr2-C6H3NC-(Me)CHC(Me)NH(CH2py)]GeCl (1) (py = pyridine) with SnCl2 results in an analogous stannylene chloride (2). The three -coordinated stannylenium cation [{2,6-iPr2-C6H3NC(Me)CHC-(Me)NH(CH2py)}Sn]+ with SnCl3- as a counteranion (3) has been generated through the abstraction of chloride ligand from 2 using an additional equivalent of SnCl2. Instead of forming a donor-acceptor complex, 2 undergoes a facile redox trans-metalation reaction with Ni(COD)2 (COD = cyclooctadiene) and CuCl to afford analogous nickel and copper complexes [2,6-iPr2-C6H3NC(Me)CHC(Me)NH(CH2py)]MCl [M = Ni (4) and Cu (5)]. The reactions of 4 with potassium tri-sec-butylborohydride (commonly known as K-selectride) and AgSbF6 provide access to monomeric Ni(II) hydride, [2,6-iPr2-C6H3NC(Me)CHC(Me)NH(CH2py)]NiH (6) and a Ni(II) cation, [{2,6-iPr2- C6H3NC(Me)CHC(Me)NH(CH2py)}Ni][SbF6] (7), respectively. 6 was found to be an effective catalyst for the hydroboration of amides.

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.

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%.

Visible light-promoted, photocatalyst-free C(sp(2))-H bond functionalization of indolizines via EDA complexes - Mane, Kishor D.; Rupanawar, Bapurao D.; Suryavanshi, Gurunath (European Journal of Organic Chemistry, 2022)
The catalyst and additive-free, photo-driven cross dehydrogenative coupling (CDC) reaction initiated by electron donor-acceptor (EDA) complexes between electron rich indolizines and electron poor quinones has been demonstrated. This green transformation reveals the advantages of operational simplicity, mild reaction conditions and good functional group tolerances.
Keywords: Blue LED; CDC; EDA; Indolizine; Quinone

Water-controlled keto-enol tautomerization of a prebiotic nucleobase - Datar, Avdhoot; Paithankar, Harshad; Deb, Pranab; Chugh, Jeetender; Bagchi, Sayan; Mukherjee, Arnab; Hazra, Anirban (Journal of Physical Chemistry B, 2022)
Barbituric acid is believed to be a proto-RNA nucleobase that was used for biological information transfer on prebiotic earth before DNA and RNA in their present forms evolved. Nucleobases have various tautomeric forms and the relative stability of these forms is critical to their biological function. It has been shown that barbituric acid has a tri-keto form in the gas phase and an enol form in the solid state. However, its dominant tautomeric form in aqueous medium that is most relevant for biology has been investigated only to a limited extent and the findings are inconclusive. We have used multiple approaches, namely, molecular dynamics, quantum chemistry, NMR, and IR spectroscopy to determine the most stable tautomer of barbituric acid in solution. We find a delicate balance in the stability of the two tautomers, tri-keto and enol, which is tipped toward the enol as the extent of solvation by water increases.

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

Accelerated Rauhut-Currier dimerization enabled the synthesis of (+/-)-incarvilleatone and anticancer studies - Kotammagari, Tharun K.; Misra, Sweta; Paul, Sayantan; Kunte, Sunita; Gonnade, Rajesh G.; Santra, Manas K.; Bhattacharya, Asish K. (Beilstein Journal of Organic Chemistry, 2023)
The total synthesis of racemic incarvilleatone has been achieved by utilizing unexplored accelerated Rauhut-Currier (RC) dimeriza-tion. The other key steps of the synthesis are oxa-Michael and aldol reactions in a tandem sequence. Racemic incarvilleatone was separated by chiral HPLC and the configuration of each enantiomer was determined by single-crystal X-ray analysis. In addition, a one-pot synthesis of (+/-)-incarviditone has been achieved from rac-rengyolone by using KHMDS as a base. We have also assessed the anticancer activity of all the synthesized compounds in breast cancer cells nonetheless, they exhibited very limited growth suppression activity.
Keywords: dimerization; incarviditone; incarvilleatone; oxa-Michael; Rauhut-Currier

Antibacterial and anti-HIV metabolites from marine streptomyces albus MAB56 isolated from Andaman and Nicobar Islands, India - Manikkam, Radhakrishnan; Murthy, Sangeetha; Palaniappan, Sivasankar; Kaari, Manigundan; Sahu, Amit Kumar; Said, Madhukar; Ganesan, Vijayalakshmi; Kannan, Sivakumar; Ramasamy, Balagurunathan; Thirugnanasambandan, Somasundaram; Dastager, Syed G.; Hanna, Luke Elizabeth; et al. (Applied Biochemistry and Biotechnology, 2023)
Marine-derived actinobacteria have tremendous potential to produce novel metabolites with diverse biological activities. The Andaman coast of India has a lot of microbial diversity, but it is still a relatively unknown ecology for isolating novel actinobacteria with beneficial bioactive compounds. We have isolated 568 actinobacterial strains from mangrove rhizosphere sediments and sponge samples. Crude extracts from 75 distinct strains were produced by agar surface fermentation and extracted using ethyl acetate. In the disc diffusion method, 25 actinobacterial strains showed antimicrobial activity; notably, the strain MAB56 demonstrated promising broad-spectrum activity. Strain MAB56 was identified as Streptomyces albus by cultural, microscopic, and molecular methods. Conditions for bioactive metabolites from MAB56 were optimized and produced in a lab-scale fermenter. Three active metabolites (C1, C2, and C3) that showed promising broad-spectrum antimicrobial activity were isolated through HPLC-based purification. Based on the UV, FT-IR, NMR, and LC-MS analysis, the chemical nature of the active compounds was confirmed as 12-methyltetradecanoic acid (C1), palmitic acid (C2), and tridecanoic acid (C3) with molecular formulae C14H28O2, C16H32O2, and C13H26O2, respectively. Interestingly, palmitic acid (C2) also exhibited anti-HIV activity with an IC50 value of < 1 mu g/ml. Our findings reveal that the actinobacteria from the Andaman marine ecosystems are promising for isolating anti-infective metabolites.
Keywords: actinobacteria; Andaman Islands; anti-HIV; Antibacterial; Bioactive metabolites

Antimalarial activity of anacardium occidentale leaf extracts against plasmodium falciparum transketolase (PfTK) - Kaushik, Meenakshi; Hoti, Sugeerappa L.; Saxena, Jitendra Kumar; Hingamire, Tejashri; Shanmugam, Dhanasekaran; Joshi, Rajesh K.; Metgud, Sharada C.; Ungar, Banappa; Singh, Ishwar; Hegde, Harsha V. (Acta Parasitologica, 2023)
BackgroundAs per estimates by WHO in 2021 almost half of the world's population was at risk of malaria and > 0.6 million deaths were attributed to malaria. Therefore, the present study was aimed to explore the antimalarial activity of extracts derived from the leaves of the plant Anacardium occidentale L., which has been used traditionally for the treatment of malaria. Different extracts of A.occidentale leaves were prepared and tested for their inhibitory activity against recombinant P. falciparum transketolase (rPfTK) enzyme, in vitro. Further, growth inhibitory activity against cultivated blood stage P. falciparum parasites (3D7 strain), was studied using SYBR Green fluorescence-based in vitro assays. Acute toxicity of the hydro alcoholic extracts of leaves of A. occidentale (HELA) at different concentrations was evaluated on mice and Zebra fish embryos. HELA showed 75.45 +/- 0.35% inhibitory activity against the recombinant PfTk and 99.31 +/- 0.08% growth inhibition against intra-erythrocytic stages of P. falciparum at the maximum concentration (50 mu g/ml) with IC50 of 4.17 +/- 0.22 mu g/ml. The toxicity test results showed that the heartbeat, somite formation, tail detachment and hatching of embryos were not affected when Zebra fish embryos were treated with 0.1 to 10 mu g/ml of the extract. However, at higher concentrations of the extract, at 48 h (1000 mu g/ml) and 96 h (100 mu g/ml and 1000 mu g/ml, respectively) there was no heartbeat in the fish embryos. In the acute oral toxicity tests performed on mice, the extract showed no toxicity up to 300 mg/kg body weight in mice.ConclusionThe hydro-alcoholic extract of leaves of A. occidentale L. showed potent antimalarial activity against blood stage P. falciparum. Based on the observed inhibitory activity on the transketolase enzyme of P. falciparum it is likely that this enzyme is the target for the development of bioactive molecules present in the plant extracts. The promising anti-malarial activity of purified compounds from leaves of A. occidentale needs to be further explored for development of new anti-malarial therapy.
Keywords: Anacardium occidentale L; Antimalarial activity; malaria; Plasmodium falciparum; Transketolase

Antiviral and ROS scavenging potential of Carica papaya Linn and Psidium guajava leaves extract against HIV-1 infection - Jadaun, Pratiksha; Shah, Prachibahen; Harshithkumar, R.; Said, Madhukar S.; Bhoite, Shubhangi P.; Bokuri, Sowmya; Ravindran, Selvan; Mishra, Neetu; Mukherjee, Anupam (BMC Complementary Medicine and Therapies, 2023)
Antiretroviral therapy is the only treatment option for HIV-infected patients; however, it has certain drawbacks in terms of developing multiple toxic side effects. Thus, there is a continuous need to explore safe and efficacious anti-retroviral agents. Carica papaya Linn and Psidium guajava are known for their various biological activities. In this study, we characterized the bioactive fractions of methanolic leaves extract from both plants using the High-resolution electrospray ionization mass spectrometry (HR-ESI-MS) technique, followed by the investigation of their potential as anti-HIV-1 and antioxidant agents through in vitro mechanistic assays. The anti-HIV-1 activity was examined in TZM-bl cells through luciferase gene assay against two different clades of HIV-1 strains, whereas the intracellular ROS generation was analyzed by Fluorescence-Activated Cell Sorting. Additionally, the mechanisms of action of these phyto-extracts were determined through the Time-of-addition assay. The characterization of Carica papaya Linn and Psidium guajava leaves extract through HR-ESI-MS fragmentation showed high enrichment of various alkaloids, glycosides, lipids, phenolic compounds, terpenes, and fatty acids like bioactive constituents. Both the phyto-extracts were found to be less toxic and exhibited potent antiviral activity against HIV-1 strains. Furthermore, the phyto-extracts also showed a decreased intracellular ROS in HIV-1 infected cells due to their high antioxidant potential. Overall, our study suggests the anti-HIV-1 potential of Carica papaya Linn and Psidium guajava leaves extract due to the synergistic action of multiple bioactive constituents.
Keywords: anti-HIV-1 activity; Anti-retroviral; Bioactive constituents; Carica papaya Linn; Cytotoxicity; HR-ESI-MS; Psidium guajava; reactive oxygen species

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.

BAHD-type acyltransferase concludes the biosynthetic pathway of non-bitter glycoalkaloids in ripe tomato fruit - Sonawane, Prashant D.; Gharat, Sachin A.; Jozwiak, Adam; Barbole, Ranjit; Heinicke, Sarah; Almekias-Siegl, Efrat; Meir, Sagit; Rogachev, Ilana; O'Connor, Sarah E.; Giri, Ashok P.; Aharoni, Asaph (Nature Communications, 2023)
During tomato fruit ripening, bitter and toxic steroidal glycoalkaloids (SGAs) are converted to nonbitter and less toxic forms, but proposed acylating enzyme in pathway remain unknown. Here, authors report BAHD-type acyltransferase that catalyze acylation step in biosynthesis of non-bitter SGAs in tomato. Tomato is the highest value fruit and vegetable crop worldwide, yet produces & alpha;-tomatine, a renowned toxic and bitter-tasting anti-nutritional steroidal glycoalkaloid (SGA) involved in plant defense. A suite of modifications during tomato fruit maturation and ripening converts & alpha;-tomatine to the non-bitter and less toxic Esculeoside A. This important metabolic shift prevents bitterness and toxicity in ripe tomato fruit. While the enzymes catalyzing glycosylation and hydroxylation reactions in the Esculeoside A pathway have been resolved, the proposed acetylating step remains, to date, elusive. Here, we discovered that GAME36 (GLYCOALKALOID METABOLISM36), a BAHD-type acyltransferase catalyzes SGA-acetylation in cultivated and wild tomatoes. This finding completes the elucidation of the core Esculeoside A biosynthetic pathway in ripe tomato, allowing reconstitution of Esculeoside A production in heterologous microbial and plant hosts. The involvement of GAME36 in bitter SGA detoxification pathway points to a key role in the evolution of sweet-tasting tomato as well as in the domestication and breeding of modern cultivated tomato fruit.

Benign strategy toward mesoporous carbon coated Sb nanoparticles: a high-performance Li-ion/Na-ion batteries anode - Dashairya, Love; Chaturvedi, Vikash; Kumar, Abhishek; Mohanta, Tandra Rani; Shelke, Manjusha; Saha, Partha (Solid State Ionics, 2023)
Antimony (Sb)-based anodes can offer excellent gravimetric capacity (-660 mAhg(1)) in lithium-ion/sodium-ion batteries (LIBs/SIBs) fabricated using carbonate-based electrolytes complexed with lithium/sodium salt. However, high first-cycle irreversible loss (35-40%) and gradual capacity fade (25-30%/cycle) originate from solid electrolyte interphase (SEI), and severe volumetric stress (-300%) associated with alloyed phase(s) impede reallife applications. Herein, we devise a benign strategy to develop mesoporous carbon coating onto antimony nanoparticles (Sb@C) based core-shell architecture for LIBs/SIBs anode. In particular, -30-50 nm thick mesoporous carbon spheres (-1 +/- 0.5 mu m) were obtained from resorcinol-formaldehyde (RF)-based polycondensation reaction by sol-gel chemistry engulfing Sb nanoparticles by suitably controlling Cetyltrimethylammonium bromide (CTAB)-induced steric stabilization and pH modulation during synthesis. The core-shell Sb@C helps faster Li+/Na+-ion migration preventing the structural collapse of Sb during electrochemical cycling and thereby improving the capacity fade. Electrochemical results demonstrate Sb@C can deliver a specific capacity of -536 mAhg(-1) and - 291 mAhg(-1) at 0.1C current rate in LIBs and SIBs, respectively, up to 200 cycles. Electrochemical impedance spectroscopy (EIS) indicates lower charge transfer (Rct) and SEI resistance (RSEI) of Sb@C cycled electrode than the bare Sb-NPs was the probable reason for improved Li/Na-ion storage in Sb@C anode. A detailed galvanostatic intermittent titration technique (GITT) and internal resistance measurements during 1st and 2nd cycles shed light on distinguishably different Li-ion/Na-ion storage behavior. The bulk Li+/Na+-ion diffusion coefficients found diminishes at reaction voltages (0.9 V/0.6 V for lithiation and 0.6 V/0.4 V for sodiation) corresponding with alloyed phase(s) concurrent with a drop in internal resistance at the quasi-opencircuit voltage (QOCV) during 1st and 2nd discharge cycle. On the contrary, de-alloying phenomena from the fully lithiated/sodiated phase(s) display an entirely opposite trend. The Li+ diffusion coefficient reaches minima at -1.1 V with a sudden jump in the internal resistance at QOCV during 1st and 2nd charge cycle. However, Na+ diffusion coefficient gradually drops along with a steep increase in the internal resistance, indicating partial Naion trapping and irreversible capacity loss.
Keywords: anode; Antimony; lithium-ion batteries; mesoporous carbon; Sodium-ion batteries

BF3.Et2O-catalyzed selective C-4 alkylation of isoquinolin1(2H)-ones employing p-quinone methides - More, Devidas A.; Ghotekar, Ganesh S.; Muthukrishnan, M. (Chemistry-an Asian Journal, 2023)
The direct C-4 alkylation of isoquinolin-1(2H)-one moiety is a challenging transformation in organic synthesis. Here we present a practical and efficient synthesis of C-4 alkylated isoquinolin-1(2H)-ones through conjugate addition of isoquinolin-1(2H)-ones to p-quinone methides for the first time. The process is facilitated by Lewis acid catalysis and this operationally straightforward, mild, metal-free and one-pot transformation provides a wide range of C-4 alkylated isoquinolin-1(2H)ones at ambient temperature in good to excellent yields.

Bimetallic quantum dots (Cu-Pd, Ni-Pd) catalyzed reaction of bromo arenes with alkenes and aryl boronic acids - Raut, Pallavi K.; Meroliya, Heena K.; Dumbre, Swapnil R.; Patil, Vaishali N.; Solanki, Bhanupratap S.; Waghmode, Shobha A.; Iyer, Suresh (Indian Journal of Chemistry, 2023)
Bimetallic quantum dots (Cu-Pd and Ni-Pd) are active ligand-free catalysts for the alkenylation and arylation of aryl bromides. The catalysts are easy to synthesize by benign green protocols and characterized by various techniques. The bimetallic QD catalysts synthesized thus are superior to Pd(OAc)2 or other Pd NP catalysis of alkenylation reactions of aryl bromides with similar E-selectivity. The reaction of aryl bromide with aryl boronic acid is facile with high yields.
Keywords: Aryl bromides; Bimetallic QDs catalysis; Cu-Pd; Mizoroki-Heck; Ni-Pd; Suzuki coupling

Carbamate-Protected (BOC and O-NB) 2-Aminopyrimidinedione-based janus G-C nucleobase motifs as building blocks for supramolecular assembly and smart polymers - Singh, Dharmendra; Lakshmi, Durga; Meena, Chhuttan L.; Krishna, Gamidi Rama; Sanjayan, Gangadhar J. (Journal of organic chemistry, 2023)
In this paper, we report ``carbamate protected'' 2-aminopyrimidinedione-based Janus G-C nucleobases (2-APD Janus G-C nucleobases) featuring polymerizable groups and self-complementary triple H-bonding motifs DDA and AAD as building blocks for developing smart polymers and self-healing materials. The carbamate-masked H-bonding motif, cleavable under acidic (BOC group) or photocleavable (O-nitrobenzyl group) conditions, would facilitate the synthesis of smart polymers by alleviating aggregation during polymerization which in turn would exclude self-assembly-assisted solubility issues. Ready accessibility in excellent yields coupled with the possibility for facile introduction of polymerizable groups would make these building blocks excellent candidates for diverse polymerization applications.

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

Catalyst-assisted selective vinylation and methylallylation of a quaternary carbon center using tert-butyl acetate - Mohanta, Nirmala; Samal, Pragnya Paramita; Pandey, Akanksha M.; Mondal, Shankhajit; Krishnamurty, Sailaja; Gnanaprakasam, Boopathy (Journal of Organic Chemistry, 2023)
The In-(OTf)(3)-catalyzed & alpha;-vinylationof varioushydroxy-functionalized quaternary carbon centers using in situ generatedisobutylene from tert-butyl acetate is presentedas a novel synthetic methodology. Moreover, tert-butylacetate is a nonflammable feed stock and is a readily available sourcefor the in situ production of vinyl substituents, as demonstratedby the vinylation reaction with quaternary hydroxy/methoxy compounds.Moreover, an excellent selectivity for methylallylation over vinylationwas obtained with Ni-(OTf)(2) as a catalyst. In the case ofperoxyoxindole, methylallyl-functionalized 1,4-benzoxazin-3-one derivativeswere formed through the sequential rearrangement of peroxyoxindolefollowed by the nucleophilic attack by isobutylene. The detailed mechanismfor this reaction and rationalization for the selectivity are providedusing kinetics and density functional theory studies.

Cerebrospinal fluid protein profiles in alzheimer's dementia patients: a bioinformatic approach - Misra, Anamika; Chakrabarti, Sankha S.; Gambhir, Indrajeet S.; Baghel, Meghraj S.; Patil, Yugendra R. (Annals of Indian Academy of Neurology, 2023)

C-H functionalization of pyridines - Maity, Susmita; Bera, Asish; Bhattacharjya, Ayantika; Maity, Pradip (Organic & Biomolecular Chemistry, 2023)
Pyridine and its reduced form (piperidine) are the most common nitrogen heterocycles in FDA-approved drugs. Additionally, their presence in alkaloids, ligands for transition metals, catalysts, and organic materials with various properties makes them among the most important structural cores. Despite its importance, direct and selective functionalization of pyridine remains scarce due to its electron-poor nature and nitrogen coordination power. Instead, functionalized pyridine rings were primarily constructed from suitably substituted acyclic precursors. The focus on sustainable chemistry with minimum waste generation encourages chemists to develop direct C-H functionalization. This review summarizes different approaches to tackle the reactivity and regio- and stereoselectivity aspects for direct pyridine C-H functionalization.

Challenges and emerging strategies for next generation liposomal based drug delivery: an account of the breast cancer conundrum - Moudgil, Aliesha; Salve, Rajesh; Gajbhiye, Virendra; Chaudhari, Bhushan P. (Chemistry and Physics of Lipids, 2023)
The global cancer burden is witnessing an upsurge with breast cancer surpassing other cancers worldwide. Furthermore, an escalation in the breast cancer caseload is also expected in the coming years. The conventional therapeutic regimens practiced routinely are associated with many drawbacks to which nanotechnological in-terventions offer a great advantage. But how eminent could liposomes and their advantages be in superseding these existing therapeutic modalities? A solution is reflected in this review that draws attention to a decade-long journey embarked upon by researchers in this wake. This text is a comprehensive discussion of liposomes, the front runners of the drug delivery systems, and their active and passive targeting approaches for breast cancer management. Active targeting has been studied over the decade by many receptors overexpressed on the breast cancer cells and passive targeting with many drug combinations. The results converge on the fact that the actively targeted formulations exhibit a superior efficacy over their non-targeted counterparts and the all lipo-somal formulations are efficacious over the free drugs. This undoubtedly underlines the dominion of liposomal formulations over conventional chemotherapy. These investigations have led to the development of different liposomal formulations with active and passive targeting capacities that could be explored in depth. Acknowl-edging and getting a deeper insight into the liposomal evolution through time also unveiled many imperfections and unchartered territories that can be explored to deliver dexterous liposomal formulations against breast cancer and more in the clinical trial pipeline.
Keywords: Breast cancer; Liposomal metamorphosis; Receptor-ligand dynamics; Targeted Drug Delivery

Challenges and opportunities for production of C5 sugar fatty acid esters (SFAEs) from renewable resources - Tracy, Preetanshika; Dasgupta, Diptarka; More, Snehal (Industrial Crops and Products, 2023)
Sugar fatty acid esters represent a billion-dollar market with huge global demand. Although glucose and sucrose-based surfactants have prevailed in the chemical industry for decades, C-5-based esters are relatively unknown and have recently started to gain attention owing to their multifunctional properties. These molecules can be derived from cheap and inexpensive biomass/renewable resources and present promising potential with diverse applications as additives in various nutraceutical, pharmaceutical, and cosmeceutical formulations. However, large-scale production of C-5 sugar esters is limited, with one or two commercial plants operating worldwide. This review highlights the major challenges and prospects of biotechnological production of the C-5 sugar esters, considering the possible advancements over existing technology with various aspects of industrial bioprocessing and product recovery.
Keywords: Bioprocess; C-5-fatty acid esters; Lipase; solvent; xylitol

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

Chemically gradient hydrogen-bonded organic framework crystal film - Mohammed, Abdul Khayum; Raya, Jesus; Pandikassala, Ajmal; Addicoat, Matthew A.; Gaber, Safa; Aslam, Mohamed; Ali, Liaqat; Kurungot, Sreekumar; Shetty, Dinesh (Angewandte Chemie-International Edition, 2023)
Hydrogen-bonded organic frameworks (HOFs) are ordered supramolecular solid structures, however, nothing much explored as centimetre-scale self-standing films. The fabrication of such crystals comprising self-supported films is challenging due to the limited flexibility and interaction of the crystals, and therefore studies on two-dimensional macrostructures of HOFs are limited to external supports. Herein, we introduce a novel chemical gradient strategy to fabricate a crystal-deposited HOF film on an in situ-formed covalent organic polymer film (Tam-Bdca-CGHOF). The fabricated film showed versatility in chemical bonding along its thickness from covalent to hydrogen-bonded network. The kinetic-controlled Tam-Bdca-CGHOF showed enhanced proton conductivity (8.3x10(-5) S cm(-1)) compared to its rapid kinetic analogue, Tam-Bdca-COP (2.1x10(-5) S cm(-1)), which signifies the advantage of bonding-engineering in the same system.
Keywords: Chemical Gradience; Crystal Films; Free-Standing Films; hydrogen-bonded organic framework; Interfacial Chemistry; proton conductivity

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

Co3O4 for sustainable CO2 reduction and possible fine-tuning towards selective CO production - Ranjan, Ravi; Tekawadia, Jyoti; Jain, Ruchi; Mhamane, Nitin B.; Raja, Thirumalaiswamy; Gopinath, Chinnakonda S. (Chemical Engineering Journal, 2023)
Two main challenges involved in heterogeneous catalytic CO2 reduction are: (a) decreasing the consumption of H2 to the minimum required level with possibly the maximum CO2 conversion, and (b) concurrently enhancing the selectivity of the desired CO, at the cost of methane. Towards meeting these two challenges, Co3O4 spinel has been identified as a potential catalyst and it exhibits predominant CO selectivity > 673 K at atmospheric pressure. CO2 conversion begins > 523 K, with 100% CO selectivity observed > 673 K with CO2:H2 = 3:2. Current work shows a sustainable catalytic CO2 conversion to 100% CO selectivity with Co3O4-Nanocube (NC). Critically, CO selectivity and yield is observed to increase at the cost of methane with smaller amount of H2. 1:1 and 3:2 CO2:H2 ratio exhibits 88-100% CO selectivity with 24-32.5% CO2 conversion between 623 and 823 K. Irrespective of the input CO2:H2, ratio of CO2:H2 uptake changes from around 1:3 at 523 K to 1:1-1.5 at 823 K with concurrent production of significant methane to predominant CO, respectively. Surface electronic state changes was explored by near ambient pressure photoelectron spectroscopy, and the results suggests that Co3O4 is the active phase that promotes CO2 reduction selectively to CO. Broadening observed with the vibrational feature of the CO2 molecules at high temperature underscores the heterogeneous character of the catalyst surface, under operating conditions, due to changing electron density. By optimizing the gas hourly space velocity (GHSV), H2-lean CO2:H2 ratio, and the reaction temperature/pressure, 100% CO selectivity could be broadened to a range of operating conditions.
Keywords: Carbon neutral economy; heterogeneous catalysis; RWGS; SDG; Surface Science

Cocrystal approach to modulate the photoluminescent properties of a GFP chromophore analogue: role of halogen/hydrogen bonding in achieving a wide range of solid-state fluorescence emissions - Mali, Bhupendra P.; Dash, Soumya Ranjan; Annadhasan, Mari; Biswas, Anupam; Manoj, Kochunnoonny; Vanka, Kumar; Gonnade, Rajesh G. (Crystal Growth & Design, 2023)
Fine-tuning the photophysical properties of fluorescentorganicsolids is essential to attain multicolor displays and meet the demandfor futuristic light-emitting materials. Here, we report the tunableluminescence of a green fluorescent protein (GFP) chromophore analogue,3,4,5-TIA (A), based on the formation of two-component molecular cocrystalswith six different coformers. Coformers selected to synthesize thebinary cocrystals include 1,4-diiodotetrafluorobenzene (B), perfluoronaphthalene(C), 1,4-dibromotetrafluorobenzene (D), 2,3,5,6-tetrafluoroterephthalicacid (E), benzene-1,2,4,5-tetracarbonitrile (F), and benzene-1,2,4,5-tetracarboxylicacid (G). Interestingly, the cocrystals A center dot C and A center dot Fshowed molecular crystal polymorphism with a slight variation in fluorescence,revealing an aggregation-induced emission (AIE). A crystal structureanalysis showed the interplay of hydrogen bonding, halogen bonding,and aromatic pi-stacking interactions in associating neutralsolid components in the cocrystal. All of the novel cocrystals displayeda wide range of photoluminescence ranging from blue to dark orange.The time-dependent density functional theory (TD-DFT) calculationsindicate the changes in the energy level structures (HOMO to LUMO)in cocrystals that resulted in variations in fluorescence emission.The study aims to further understand the structure-propertyrelationship between molecular arrangement and photoluminescence. Cocrystals of a GFPc analogue with differentcoformers displayeda wide range of fluorescence emissions ranging from blue to dark orangewith varying quantum yields. With similar geometries of pi-stackinginteractions, hydrogen and halogen bonding have played a vital rolein fine-tuning the photoluminescence; halogen bonding leads to a blueshift, and hydrogen bonding results in a red shift.

COF-supported zirconium oxyhydroxide as a versatile heterogeneous catalyst for Knoevenagel condensation and nerve agent hydrolysis - Shekhar, Pragalbh; Devulapalli, Venkata Swaroopa Datta; Reji, Reshma; Singh, Himan Dev; Jose, Aleena; Singh, Piyush; Torris, Arun; Vinod, Chatakudath P.; Tokarz III, John A.; Mahle, John J.; Peterson, Gregory W.; Borguet, Eric; et al. (iScience, 2023)
A composite of catalytic Lewis acidic zirconium oxyhydroxides (8 wt %) and a covalent organic framework (COF) was synthesized. X-ray diffraction and infrared (IR) spectroscopy reveal that COF's structure is pre-served after loading with zirconium oxyhydroxides. Electron microscopy confirms a homogeneous distri-bution of nano-to sub-micron-sized zirconium clusters in the COF. 3D X-ray tomography captures the micron-sized channels connecting the well-dispersed zirconium clusters on the COF. The crystalline ZrOx(OH)(y)@COF's nanostructure was model-optimized via simulated annealing methods. Using 0.8 mol % of the catalyst yielded a turnover number of 100-120 and a turnover frequency of 160-360 h(-1) for Knoevenagel condensation in aqueous medium. Additionally, 2.2 mol % of catalyst catalyzes the hy-drolysis of dimethyl nitrophenyl phosphate, a simulant of nerve agent Soman, with a conversion rate of 37% in 180 min. The hydrolytic detoxification of the live agent Soman is also achieved. Our study unveils COF-stabilized ZrOx(OH)(y) as a new class of zirconium-based Lewis + Bronsted-acid catalysts.

Comparative studies of the influence of particle size on various pretreatments of rice husk by assessment of chemical and structural components and wastewater characteristics of liquid fraction - Shahabazuddin, Mohmmad; Banuvalli, Bhavana Karibasappa; Mulik, Nagesh; Pande, Ashwini; Bokade, Vijay; Mudliar, Sandeep Narayan (Biomass Conversion and Biorefinery, 2023)
The dilute acid (DA), steam explosion (SE), and a 2-step: steam explosion followed by alkali (SEA) were evaluated for pretreatment of rice husk. The maximum hemicellulose and lignin removal via degradation and dissolution was observed for SEA pretreatment, enabling higher cellulose enrichment (up to 44% w/w) and recovery (up to 78%). The hemicellulose solubilization was >90% for all the pretreatments, while maximum lignin removal (up to 62%) was observed for SEA pretreatment. The particle size in the range of 0.3-0.6 mm enabled higher pretreatment efficiencies in terms of cellulose enrichment. The liquid fraction obtained after DA pretreatment indicated higher COD values (20800-24440 mg/L) as compared to SEA (7800-11400 mg/L) due to lower cellulose recoveries in DAP (54-68%). SEM analysis of the biomass indicated disrupted regions with multiple pores. FTIR analysis revealed cleavage of lignin side chains, and XRD analysis confirmed the increase in cellulose crystallinity post-pretreatment.
Keywords: Lignocellulosic crop residues; Liquid-waste characterization; Particle size; Rice husk biomass; Steam explosion pretreatment

Comparison of the solid-state and submerged fermentation derived secretomes of hyper-cellulolytic Penicillium janthinellum NCIM 1366 reveals the changes responsible for differences in hydrolytic performance - Sankar, Meena; Mathew, Reshma M.; Puthiyamadam, Anoop; Sreeja-Raju, Athiraraj; Christopher, Meera; Gokhale, Digambar Vitthal; Sukumaran, Rajeev K. (Bioresource Technology, 2023)
better hydrolytic performance along with a higher initial rate of reaction. Secretome analyses of the SSF and SmF enzymes using LC/MS-MS, indicated that while the type of proteins secreted were similar in both modes, the abundance of specific beta glucosidases, lytic polysaccharide monooxygenases and hemicellulolytic enzymes were very high in SSF resulting in efficient initiation, low accumulation of cellobiose and high initial reaction rates. Key enzymes that catalyse lignocellulose breakdown under SSF and SmF are therefore different and the fungus may be speculated to have regulation mechanisms that aid differential expression under different culti
Keywords: Cellulase; Solid -state fermentation

Composites of HKUST-1@nanocellulose for gas-separation and dye-sorption applications - Muhamed, Shamna; Sunny, Blesson; Kunjattu, Shebeeb H.; Alagarsamy, Thirumurugan (CHEMISTRY-A EUROPEAN JOURNAL, 2023)
In this study, composites of HKUST-1 MOF with nanocellulose, HKUST-1@NCs, have been prepared and explored for CO2/N-2 gas-separation and dye-sorption based applications. Our biopolymer-MOF composites are prepared via a copper ion pre-seeding method, in which, the HKUST-1 crystallites are grown in situ on the Cu-seeded and carboxylate anchored NC fibers for a better interfacial integration between the MOF and the polymer matrices. Static gas sorption studies show the capability of one of our HKUST-1@NC composites to reach similar to 300 % enhancement in the CO2/N-2 sorption selectivity compared to the corresponding MOF alone - blank reference sample prepared at similar conditions. The same composite, C100, in the bulk powder form, shows a remarkable IAST sorption selectivity of 298 (CO2/N-2) at 298 K and 1 bar for the CO2/N-2 (15/85, v/v) gas mixture. The relative position of the C100, in the bound plot visualizations of the CO2/N-2 separation trade-off factors indicate a significant potential. The HKUST-1@NC composites have also been processed along with a polymeric cellulose acetate (CA) matrix as HKUST-1@NC@CA films to study them as free-standing mixed-matrix membranes. The CO2/N-2 sorption selectivity, at 298 K and 1 bar is 600 for one such membrane, C-120@CA, as bulk sample studied by the static gas sorption. The composite, C120, exhibits a good uptake with an enhancement of 11 % for alizarin and 70 % for Congo red in comparison to the uptakes of the corresponding blank reference HKUST-1 sample, B120.
Keywords: CO2 separation; dye sorption; MOFs; nanocellulose composites; sustainable polymers

Comprehensive analysis of physiological and metabolomic responses to drought reveals specific modulation of acquired tolerance mechanisms in rice - Doddaraju, Pushpa; Dharmappa, Prathibha M.; Thiagarayaselvam, Aarthy; Vijayaraghavareddy, Preethi; Bheemanahalli, Raju; Basavaraddi, Priyanka A.; Malagondanahalli, Mohan Kumar V.; Kambalimath, Sumanth; Thulasiram, Hirekodathakallu V.; Sreeman, Sheshshayee M. (Physiologia Plantarum, 2023)
Mild stresses induce ``acquired tolerance traits'' (ATTs) that provide tolerance when stress becomes severe. Here, we identified the genetic variability in ATTs among a panel of rice germplasm accessions and demonstrated their relevance in protecting growth and productivity under water-limited conditions. Diverse approaches, including physiological screens, association mapping and metabolomics, were adopted and revealed 43 significant marker-trait associations. Nontargeted metabolomic profiling of contrasting genotypes revealed 26 ``tolerance-related-induced'' primary and secondary metabolites in the tolerant genotypes (AC-39000 and AC-39020) compared to the susceptible one (BPT-5204) under water-limited condition. Metabolites that help maintain cellular functions, especially Calvin cycle processes, significantly accumulated more in tolerant genotypes, which resulted in superior photosynthetic capacity and hence water use efficiency. Upregulation of the glutathione cycle intermediates explains the ROS homeostasis among the tolerant genotypes, maintaining spikelet fertility, and grain yield under stress. Bioinformatic dissection of a major effect quantitative trait locus on chromosome 8 revealed genes controlling metabolic pathways leading to the production of osmolites and antioxidants, such as GABA and raffinose. The study also led to the identification of specific trait donor genotypes that can be effectively used in translational crop improvement activities.

Comprehensive review on catalytic O-alkylation of phenol and hydroquinone - Bhongale, Priyanka; Joshi, Sunil; Mali, Nilesh (Catalysis Reviews-Science and Engineering, 2023)
The alkylation process involves two competitive paths of O- and C-alkylation and achieving better selectivity for desired products is a very challenging problem. The development of new process for synthesis of O-methylated products of phenol and dihydric phenols is a subject of high industrial and academic interest. Alkyl phenyl ethers, especially anisole and 4-methoxyphenol, have captivated significant interest due to their increasing applications in pharmaceutical industries. The main emphasis of the present review is to explore the recent development in two catalytic O-alkylation processes. The first process is O-methylation of phenol into anisole and another is selective mono O-methylation of hydroquinone into 4-methoxyphenol. The present article covers O-alkylation methods with methanol and dimethyl carbonate as alkylating agent over various acidic and basic catalytic systems. The catalyst systems analyzed involves Bronsted and Lewis acidic and basic ionic liquids, conventional acids, metal oxides, solid acid and basic catalysts, hydrotalcites, various zeolites and heteropolyacids. The mechanistic behavior of alkylation reactions in presence of different catalytic system is reviewed critically which is important to design new and/or modified catalyst in order to maximize the yield of desired product. Additionally, an influence of reaction parameters, role of catalyst and their active sites on product distribution is described. The review paper gives useful insight for researchers in the field of catalysis and reaction engineering of alkylation reactions. Understandings of the reaction pathways will help in developing reliable kinetic models necessary for process scale-up to industrial scale reactor system.
Keywords: Dimethyl carbonate; Hydroquinone; Methanol; O-alkylation; phenol

Controlled synthesis of thermosensitive tunable porous film of (pNIPAM)-b-(PCL) copolymer for sustain drug delivery - Amgoth, Chander; Patra, Sukanya; Wasnik, Kirti; Maity, Pradip; Paik, Pradip (Journal of Applied Polymer Science, 2023)
There have been reports on different types of porous polymer films for various applications. The designing of such porous films with uniform properties is a challenging task. In this work, tunable porous thin films of poly(N-isopropylacrylamide) (pNIPAM) and polycaprolactone (PCL), that is, (pNIPAM)-b-(PCL) has been fabricated and its sustained drug delivery applications have been reported. First, the (pNIPAM)-b-(PCL) has been synthesized through the addition polymerization of pNIPAM and PCL. Then the synthesized (pNIPAM)-b(PCL) has been used to design porous thin film with varying temperatures without using any external template, below and above the lower critical solution temperatures (LCST) of pNIPAM. Pore size in (pNIPAM)-b-(PCL) films has been tuned by varying the temperature from similar to 10 to 40 degrees C. Then the developed thermosensitive porous film has been taken and seeded with the K562 (chronic myeloid leukemia blood cancer) and HepG2 (hepatocarcinoma) cells and the skin cancer cells (B16-F10) killing efficiency of anticancer drug (e.g., doxorubicin hydrochloride, DOX) loaded (pNIPAM)-b-(PCL) film has been studied. It is found that the DOX-loaded (pNIPAM)-b-(PCL) can efficiently kill the skin cancer cells. The porous polymer thin film reported in this work can be a versatile platform for the loading of drugs and it can be used for the various therapeutic applications.
Keywords: Biomaterials; Biomedical Applications; drug delivery systems; films; nanostructured polymers

Covalent organic framework cladding on peptide-amphiphile-based biomimetic catalysts - Kumar Mahato, Ashok; Pal, Sumit; Dey, Kaushik; Reja, Antara; Paul, Satyadip; Shelke, Ankita; Ajithkumar, Thalasseril G.; Das, Dibyendu; Banerjee, Rahul (Journal of the American Chemical Society, 2023)
Peptide-based biomimetic catalysts are promising materialsforefficient catalytic activity in various biochemical transformations.However, their lack of operational stability and fragile nature innon-aqueous media limit their practical applications. In this study,we have developed a cladding technique to stabilize biomimetic catalystswithin porous covalent organic framework (COF) scaffolds. This methodologyallows for the homogeneous distribution of peptide nanotubes insidethe COF (TpAzo and TpDPP) backbone, creating strong noncovalent interactionsthat prevent leaching. We synthesized two different peptide-amphiphiles,C10FFVK and C10FFVR, with lysine (K) and arginine(R) at the C-termini, respectively, which formed nanotubular morphologies.The C10FFVK peptide-amphiphile nanotubes exhibit enzyme-likebehavior and efficiently catalyze C-C bond cleavage in a buffermedium (pH 7.5). We produced nanotubular structures of TpAzo-C10FFVK and TpDPP-C10FFVK through COF claddingby using interfacial crystallization (IC). The peptide nanotubes encasedin the COF catalyze C-C bond cleavage in a buffer medium aswell as in different organic solvents (such as acetonitrile, acetone,and dichloromethane). The TpAzo-C10FFVK catalyst,being heterogeneous, is easily recoverable, enabling the reactionto be performed for multiple cycles. Additionally, the synthesis ofTpAzo-C10FFVK thin films facilitates catalysis inflow. As control, we synthesized another peptide-amphiphile, C10FFVR, which also forms tubular assemblies. By depositingTpAzo COF crystallites on C10FFVR nanotubes through IC,we produced TpAzo-C10FFVR nanotubular structuresthat expectedly did not show catalysis, suggesting the critical roleof the lysines in the TpAzo-C10FFVK.

Covalently interconnected layers in g-C3N4: toward high mechanical stability, catalytic efficiency and sustainability - Roy, Raj Sekhar; Mondal, Sanjit; Mishra, Samita; Banoo, Maqsuma; Sahoo, Lipipuspa; Kumar, Amit; Vinod, C. P.; De, Arijit K.; Gautam, Ujjal K. (Applied Catalysis B: Environmental, 2023)
The grim prospects for the industrial utilization of g-C3N4 nanosheets arise from multi-step processing resulting in low material yields and poor visible light response due to quantum confinement. Herein, we introduce a strategy for linking the adjacent layers of g-C3N4 covalently to realize a high surface area without excess mass loss in a one-step process by introducing diethylene glycol as a precursor that produces-(CH2)2-O-(CH2)2-linkers in-situ. Their presence increases interlayer spacing and introduces surface curvatures, discouraging the stacking of a larger number of layers to produce nanosheets with-3 times higher surface area. Interestingly, unlike other layered materials, the linkers also provide extraordinary mechanical stability against exfoliating forces. In addition, the process instills sub-bandgap states and a considerable visible light response at 500 nm to slow down the picosecond exciton recombination dynamics, resulting in-5 times enhancement in H2 generation efficiency from photocatalytic water-splitting over the bulk sample.
Keywords: Layer-linkers; Sustainable synthesis; Transient absorption spectroscopy; water-splitting

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.

Cyclohexylamine -an efficient organocatalyst for the synthesis of 2-amino-4H-chromene derivatives by multicomponent reactions of salicylaldehydes, active methylene compounds and nitroalkanes - Mitragotri, Satish D.; Khyadage, Poonam H.; Chorghade, Diksha S.; Kulkarni, Makarand A.; Wadagaonkar, Prakash P. (Arkivoc, 2023)
Cyclohexylamine was found to be an efficient organocatalyst for the synthesis of structurally diverse 2-amino4H-chromenes by multicomponent reaction of (substituted) salicylaldehydes, active methylene compounds and nitroalkanes at ambient temperature and under solvent-free conditions. The synthesis of a variety of 2amino-4H-chromenes was achieved using the reaction of (substituted) salicylaldehydes with two different C-H acids. The present protocol, which employed commercially available cyclohexylamine as an organocatalyst, offered the advantages of operational simplicity and avoidance of conventional purification methods and the obtained products were essentially pure.
Keywords: 2-Amino-4H-chromene; active methylene compound; cyclohexylamine; organocatalyst

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 development of multi-functional graphitic carbon nitride heterostructures embedded with copper and iron oxide nanoparticles as versatile sensing platforms for environmental and agricultural applications - Khasim, Syed; Pasha, Apsar; Dastager, Syed G.; Panneerselvam, Chellasamy; Hamdalla, Taymour A.; Al-Ghamdi, S. A.; Alfadhli, S.; Makandar, Mohammad Basha; Albalawi, Jalal Bassam; Darwish, A. A. A. (Ceramics International, 2023)
In the recent past, agrotechnology has witnessed a tremendous change due to the advent of technologies employed towards enhancing the yield and quality of the crops. The application of nanotechnology in agriculture is promoting sustainable practices and smart farming. Currently, nanomaterial-based sensors are gaining considerable attention in agrotechnology, such sensors can detect the environmental conditions and support for crop growth and enhances the agricultural yield. Graphiticcarbon nitride (g-C3N4), a soft polymer belongs to a class of 2-D semiconductors which are affordable, metal-free, indispensable for sensing applications due to significant changes in their conductivity upon exposure to analyte molecules in nano-regime. Further, this g-C3N4 can be combined with other nano metal oxides to form nanocomposites with remarkable properties and superior performance. In this work we report development of high-performance sensors based on graphitic carbon nitride embedded with copper and iron oxide nanoparticles. These heterostructures offers tremendous improvement in the physical and chemical properties due to the synergetic interactions between various phases. The chemiresistive sensor fabricated from these nanocomposites exhibit excellent sensitivity towards monitoring methane gas @ ppb level, relative humidity (% RH), and soil moisture content. Owing to their excellent sensitivity, stability and selectivity, this graphitic carbon nitride embedded with Cu and Fe oxide nanoparticles could be potentially used as multifunctional sensors towards environmental monitoring and greenhouse conditions in agricultural applications.
Keywords: Agricultural sensors; CuO nanoparticles; Environmental monitoring; FeO nanoparticles; Graphitic carbon nitride

Design, synthesis, and in vitro biological evaluation of ROS-generating phenanthridin-trione-epoxide conjugates as agents against mycobacterium tuberculosis - Mamgain, Ritu; Swami, Sagar; Sarkar, Dhiman; Srivastava, Pratibha (ChemistrySelect, 2023)
Tuberculosis (TB) is one of the devasting infectious diseases and continues to spread among people despite having several specific drugs. Total eradication of TB is one of the shared interests of both the World Health Organization (WHO) and India globally. A library of antitubercular 6-((1-(aryl/heteroaryl)-1H-1,2,3-triazol-4-yl)methyl)oxireno[2,3-b] phenanthridine-5,7,9(6H,7aH,8aH)-trione (6 a-e) has been prepared in five steps including click chemistry and tested against active and dormant strains of Mycobacterium tuberculosis H37Ra using XRMA protocol. The result showed the inhibitory potential of 6 d IC50 at 0.74 & mu;g/mL concentration against active strain and at 0.9 & mu;g/mL against the dormant strain of Mtb. ROS generating ability of the compounds has been confirmed by luminol, H2O2, and glutathione assays. The molecular docking with the thioredoxin protein of Mtb showed a docking score of -9.6 Kcal/mol. To understand the mechanism with the thioredoxin protein of Mtb, the adduct formation of compounds with cystine was confirmed with HPLC. The involvement of lead molecules with existing drugs can be helpful in the eradication of tuberculosis.
Keywords: antimycobacterial agents; Computational docking; Cystine adduct; Epoxy-Phenanthridinone-triazoles; ROS generation

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.

Developing a mealybug pheromone monitoring tool to enhance IPM practices in New Zealand vineyards - Sullivan, Nicola J.; Bell, Vaughn A.; Butler, Ruth C.; Wallis, Roger; Ramesh, Remya; Reddy, D. Srinivasa; Twidle, Andrew M.; Bunn, Barry; Unelius, C. Rikard; Manning, Lee-Anne M.; Suckling, David M. (Journal of Pest Science, 2023)
Mealybugs are phloem-feeding insects found on many crops worldwide. In New Zealand vineyards, they transmit the economically important Grapevine leafroll-associated virus 3 (GLRaV-3). For some mealybug species, synthetic sex pheromones have been commercialised, and are used as monitoring tools. The mealybugs Pseudococcus longispinus and Pseudococcus calceolariae are major pests in many New Zealand vineyards. We present work on the development of a combined P. longispinus and P. calceolariae pheromone lure. The optimal dose for monitoring P. longispinus was found to be 10 mu g of the (S)-(+)-enantiomer, either alone or in the racemic mixture. Addition of the corresponding alcohol did not improve trap catch of P. longispinus. Both the P. longispinus and the P. calceolariae pheromone lures remained active in the field for 90 days. Combining the 2 species' pheromones had no negative effects on male mealybug trap catch for either species. We conclude that the pheromone ester alone is the best lure for the male P. longispinus. Combining the two mealybug species' pheromones into a single lure provides the New Zealand viticultural industry with an efficient monitoring tool. Late-vintage deployment of baited lures will provide information on mealybug abundance and local distribution that will inform the scope of future insecticide programmes, to target areas based on need rather than an area-wide application by default.
Keywords: Citrophilus mealybug; Integrated pest management (IPM); Long-tailed mealybug; monitoring; Pseudococcus calceolariae; Pseudococcus longispinus

Development of multipurpose biomass-derived adsorbents using Coccinia grandis for removal of contaminants - Raj, Surabhi S.; Mane, Maya B.; Thanekar, Pooja; Balapure, Kshama; Bhandari, Vinay M. (Clean Technologies and Environmental Policies, 2023)
The present study is an attempt to develop newer multipurpose biomass-derived adsorbents for water and wastewater treatment; biomass that are easily available, renewable and most importantly, sustainable. A model adsorbent was developed using Coccinia grandis (CG, Ivy gourd) and further modified by impregnating copper nanoparticles (CG-Cu). The adsorbent characterization was done for evaluating surface morphology, surface area and metal modification. The utility of the newer adsorbents was established for the removal of different contaminants such as dyes (cationic Malachite Green, anionic Congo Red and fluorescent cationic Rhodamine B), Active Pharmaceutical Ingredient pollutant (Ciprofloxacin) and also for the removal of pathogenic bacteria, Gram-negative Escherichia coli. Both CG and CG-Cu bio-nanocomposite were highly effective in removal of different contaminants, 99% dye removal for Malachite Green, with a high adsorption capacity of 49 mg/g, higher than that for commercial activated charcoal whereas for all other dyes, the performance of CG-Cu was similar. The isotherm studies indicated multilayer adsorption, in general. A good adsorption capacity of 10.8 mg/g was also observed for the removal of ciprofloxacin. The combined effect of the bio-nanocomposite, CG-Cu was impressive and 100% disinfection was achieved within 10 min, due to the antimicrobial activity of Cu and oxidation effect of reactive oxygen species enhancing the disinfection.Graphical abstractMultipurpose biomass derived adsorbents using Coccinia grandis for removal of contaminants
Keywords: Adsorption; Biomass; Disinfection; dye removal; nanomaterial; Separation

Differential membrane curvature induced by distinct protein conformers - Malshikare, Hrushikesh; Prakash, Shikha; Sengupta, Durba (Soft Matter, 2023)
Membrane topology changes are associated with various cellular processes and are modulated by synergistic effects between lipid composition and membrane-associated proteins. However, how protein shape or conformational dynamics couples to membrane molecular properties remains unclear. In this work, we aim to investigate this coupling behavior using the curvature-inducing protein caveolin-1. We considered distinct protein conformers of the helical hairpin protein corresponding to different protein shapes, such as the wedge and the banana-shaped conformers. The different protein conformers were simulated in a coarse-grain representation in the presence of cholesterol-sphingomyelin rich membrane. We observed that membrane curvature is dependent on protein shape and is the lowest for the wedge conformer and maximal for the banana conformer. The differences in the net stress between the two membrane leaflets, calculated from the lateral pressure profile distributions in lipid bilayers for different protein conformers, show a similar trend. In conjunction, we show that cholesterol and sphingomyelin clustering in the membrane is modulated by protein shape. Overall, our results provide molecular-level insights into the coupling between membrane topology, protein shape and lipid clustering in cell membranes.

Distortion-induced interfacial charge transfer at single cobalt atom secured on ordered intermetallic surface enhances pure oxygen production - Mondal, Soumi; Riyaz, Mohd; Bagchi, Debabrata; Dutta, Nilutpal; Singh, Ashutosh Kumar; Vinod, Chathakudath P.; Peter, Sebastian C. (ACS Nano, 2023)
In this work, atomic cobalt (Co) incorporation into the Pd2Ge intermetallic lattice facilitates operando generation of a thin layer of CoO over Co-substituted Pd2Ge, with Co in the CoO surface layer functioning as single metal sites. Hence the catalyst has been titled Co-1-CoO-Pd2Ge. High-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy confirm the existence of CoO, with some of the Co bonded to Ge by substitution of Pd sites in the Pd2Ge lattice. The role of the CoO layer in the oxygen evolution reaction (OER) has been verified by its selective removal using argon sputtering and conducting the OER on the etched catalyst. In situ X-ray absorption near-edge structure and extended X-ray absorption fine structure spectroscopy demonstrate that CoO gets transformed to CoOOH (Co3+) in operando condition with faster charge transfer through Pd atoms in the core Pd2Ge lattice. In situ Raman spectroscopy depicts the emergence of a CoOOH phase on applying potential and shows that the phase is stable with increasing potential and time without getting converted to CoO2. Density functional theory calculations indicate that the Pd2Ge lattice induces distortion in the CoO phase and generates unpaired spins in a nonmagnetic CoOOH system resulting in an increase in the OER activity and durability. The existence of spin density even after electrocatalysis is verified from electron paramagnetic resonance spectroscopy. We have thus successfully synthesized intermetallic supported CoO during synthesis and rigorously verified the role played by an intermetallic Pd2Ge core in enhancing charge transfer, generating spin density, improving electrochemical durability, and imparting mechanical stability to a thin CoOOH overlayer. Differential electrochemical mass spectrometry has been explored to visualize the instantaneous generation of oxygen gas during the onset of the reaction.
Keywords: DEMS; interfacial charge transfer; Intermetallic; long-termstability; operando spectroscopic techniques; Oxygen Evolution Reaction; structuraldistortion

Dual-mode porous and highly graphitized 3D nitrogen-doped carbon network as an advance anode material for sodium-ion batteries - Dar, Mudasir; Suresh, Karthika; Majid, Kowsar; Wahid, Malik (Journal of Physical Chemistry C, 2023)
The practical application of hard carbons as the mostappealinganode material for sodium-ion batteries is hampered by their poorcycling and rate performances, emanating from poor electrochemicalstability, low electroconductivity, and sluggish Na+ transport.Designing a single remedial method for these challenges often involvescomplex and energy-intensive processes, contradicting the core conceptof cost-effectiveness for practical energy storage technology. Herein,we employed trifunctional silica (SiO2): as colloidal silicato ice template micron-sized pores, as a hard template for nanopores,and as a catalyst for the graphitization of carbon for the synthesisof a highly graphitized, efficiently nitrogen-doped, high-surface-area,three-dimensional porous carbon network (3D PNC) with dual-mode porosity(nanopores and micron-sized pores). As an anode material, the obtained3D PNC exhibits a reversible capacity of 262 mAh g(-1) at a current density of 100 mA g(-1), an ultrahighrate capability of 173 mAh g(-1) at 1 A g(-1), and a stable cycling life of 1000 cycles at a high current densityof 100 mA g(-1) with almost 100% capacity retention.The galvanostatic intermittent titration technique (GITT) revealsfacile sodium diffusion kinetics with an average diffusion coefficientof an order of & SIM;10(-9) (cm(2) s(-1)), which is fairly low compared to most reported HCanodes for SIBs. This work demonstrates how a merger of two or moresynthesis methodologies can be employed for the advanced microstructureengineering of carbon materials, opening up new avenues for the rationaldesign of anode materials in SIBs.

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 nitrogen reduction on defective graphene modulated from single atom catalyst to aluminium clusters - Maibam, Ashakiran; Krishnamurty, Sailaja; BabaRao, Ravichandar (Applied Surface Science, 2023)
Density Functional Theory (DFT) investigation on the most earth-abundant Al-based catalysts, has been conducted detailing its electronic properties and catalytic efficacy for nitrogen reduction at ambient condition. The Al-based catalysts have been modulated to perform as par a highly performing, but rare, Ru-single atom catalytic center by varying number of Al atoms, shape, and size. The coalesce of band-center, work function and electronic properties in metal atom catalysts along with N-N bond activation has been demonstrated to be responsible for an efficient nitrogen reduction reaction (NRR) with Delta Gmax of 0.78 eV in Al5 supported on N-doped double vacancy graphene (Al5@N4-DVG) catalyst. Electron localization function analysis has shown a weak physisorption of N2 in the Al-based catalysts. Projected Density of States (PDOS) illustrates the enhancement of aluminium electron density in Al5@N4-DVG led to enhanced orbital densities overlap of Alp and Np electrons. The Bader charge analysis and electronic analysis of the intermediates show efficient electron gain on the N atoms, leading to formation of NH3 from the NxHy intermediates in Al5@N4-DVG catalyst.

Electrode|electrolyte interface enhancement in quasi-solid-state zinc-air batteries through an anion conducting polymer electrolyte interlayer by in situ polymerization - Kurian, Maria; Vijayakumar, Vidyanand; Manna, Narugopal; Kanheerampockil, Fayis; Bhat, Suresh; Kurungot, Sreekumar (Journal of Materials Chemistry A, 2023)
This work introduces a novel concept of electrode|electrolyte interface enhancement using an ultraviolet (UV) light-assisted in situ polymerization strategy to improve the performance of quasi-solid-state zinc-air batteries (ZABs). The suitability of the UV polymerization strategy to process a mechanically stable OH- conducting anion exchange polymer electrolyte membrane (AEPEM) reinforced by a glass fiber (GF) separator is also reported. The in situ polymerized ionomer-skin/interlayer (a thin anion-conducting polymer coating over the air-cathode of ZAB) acts as a buffer layer to narrow down the performance gap generally observed between ZABs possessing quasi-solid-state electrolytes and standard liquid electrolytes, respectively. For instance, when combined with the in situ polymerization strategy, a rechargeable ZAB (rZAB) based on an AEPEM-GF composite membrane delivered a high power density of 140 mW cm(-2), higher than that of the one without an in situ polymerized ionomer interlayer (120 mW cm(-2)). Notably, in a flexible rZAB configuration, this new strategy resulted in enhanced rate capability and cycling stability for 14 h at an operating current density of 2 mA cm(-2).

Electronic fingerprints for diverse interactions of methanol with various Zn-based systems - Mehta, Shweta; Joshi, Kavita (Surface Science, 2023)
We have investigated various Zn-based catalysts for their interaction with methanol (MeOH). MeOH is one of the most critical molecules being studied extensively, and Zn-based catalysts are widely used in many industrially relevant reactions involving MeOH. We note that the same element (Zn and O, in the present study) exhibits different catalytic activity in different environments. The changing environment is captured in the underlying electronic structure of the catalysts. In the present work, we compared the electronic structure of Zn-based systems, i.e., ZnAl2O4 and ZnO along with oxygen preadsorbed Zn (O-Zn) and metallic Zn. We demonstrate the one-to-one correlation between the pDOS of the bare facet and the outcome of that facet's interaction (i.e. either adsorption or dissociation of MeOH) with MeOH. These findings would pave the way towards the in-silico design of catalysts.
Keywords: DFT; Electronic properties; Methanol; Zn-based systems; ZnO

Emergent stability in complex network dynamics - Meena, Chandrakala; Hens, Chittaranjan; Acharyya, Suman; Haber, Simcha; Boccaletti, Stefano; Barzel, Baruch (Nature Physics, 2023)
The stable functionality of networked systems is a hallmark of their natural ability to coordinate between their multiple interacting components. Yet, real-world networks often appear random and highly irregular, raising the question of what are the naturally emerging organizing principles of complex system stability. The answer is encoded within the system's stability matrix-the Jacobian-but is hard to retrieve, due to the scale and diversity of the relevant systems, their broad parameter space and their nonlinear interaction dynamics. Here we introduce the dynamic Jacobian ensemble, which allows us to systematically investigate the fixed-point dynamics of a range of relevant network-based models. Within this ensemble, we find that complex systems exhibit discrete stability classes. These range from asymptotically unstable (where stability is unattainable) to sensitive (where stability abides within a bounded range of system parameters). Alongside these two classes, we uncover a third asymptotically stable class in which a sufficiently large and heterogeneous network acquires a guaranteed stability, independent of its microscopic parameters and robust against external perturbation. Hence, in this ensemble, two of the most ubiquitous characteristics of real-world networks-scale and heterogeneity-emerge as natural organizing principles to ensure fixed-point stability in the face of changing environmental conditions. Despite looking highly irregular, most real-world networks exhibit natural stability to external perturbations. A study of the properties of the stability matrix of networks now sheds light on the principles underlying this emerging stability.

Enantioselective intramolecular decarboxylative C-H bond func-tionalization of quinazolinones with amino acids by visible light photoredox catalysis - Sonavane, Sameer R.; Mhaske, Santosh B. (Chemistry-An Asian Journal, 2023)
The direct visible light-mediated intramolecular decarboxylative C-H functionalization of Csp(2)-H bond adjacent to the nitrogen of a heteroarene has been achieved by iridium-catalyzed photodecarboxylative radical cyclization. This method offers rapid entry to the synthesis of quinazolinone scaffolds from easily accessible starting materials. The newly developed protocol is mild, operationally simple, oxidant free and general. The utility of this unique Csp(3)-Csp(2) bond forming reaction has been demonstrated in the syntheses of Circumdatin, Sclerotigenine and Benzomalvin A class of quinazolinone natural products and their congeners. The present work represents an interesting example of use of memory of chirality in decarboxylative C-C bond forming enantioselective photoredox reaction.
Keywords: C-H functionalization; memory of chirality; Minisci reaction; photodecarboxylative cyclization; photoredox catalysis; quinazolinone alkaloid; Radical

Etherification of biomass-derived glycerol to oxygenated fuel additives using dodecatungstophosphoric-silica-supported catalyst: characterization and kinetic studies - Magar, Subhash B.; Kapoor, Ashish; Jana, Sumit Kumar; Pal, Dan Bahadur; Rode, Chandrashekhar V. (Biomass Conversion and Biorefinery, 2023)
Commercial biodiesel production is becoming popular due to its sustainability and reduced greenhouse gas emissions in comparison to fossil fuels. Biodiesel production involves the co-generation of crude glycerol that is not directly viable. Valorization of glycerol is essential from techno-economic perspective to achieve goals of circular economy. In this study, the glycerol etherification was carried out using tert-butyl alcohol in presence of dodecatungstophosphoric/silica (DTP/SiO2) catalyst for production of tert-butyl glycerol ethers that can be used as fuel additives. A series of DTP/SiO2 catalysts were prepared with various compositions by impregnating heteropoly acids (HPA, H3PW12O40). The product analysis was performed to monitor mono-, di-, and tri-tert-butyl glycerol ethers. The kinetic studies were conducted based on Langmuir-Hinshelwood model. The rate constants were determined from experimental data by regression analysis. The catalysts were characterized by X-ray diffraction, SEM/EDX, and thermogravimetric analysis. Varying DTP loadings resulted in different catalytic activities. Activation energy (38.23 kJ/mol), activation enthalpy (25.94 kJ/mol), activation entropy (-163.8 J/mol/K), and Gibbs free energy of activation (88.67 kJ/mol) were attained for DTP/SiO2 (20%) catalyst that exhibited the best selectivity for di-tert-butyl glycerol ethers.
Keywords: Catalytic; etherification; fuel additives; Hinselwood; Impregnation; kinetics; Langmuir

Evolutionary conservation of protein dynamics: insights from all-atom molecular dynamics simulations of `peptidase' domain of Spt16 - Gaur, Neeraj K.; Ghosh, Biplab; Goyal, Venuka Durani; Kulkarni, Kiran; Makde, Ravindra D. (Journal of Biomolecular Structure and Dynamics, 2023)
Protein function is encoded in its sequence, manifested in its three-dimensional structure, and facilitated by its dynamics. Studies have suggested that protein structures with higher sequence similarity could have more similar patterns of dynamics. However, such studies of protein dynamics within and across protein families typically rely on coarse-grained models, or approximate metrics like crystallographic B-factors. This study uses mu s scale molecular dynamics (MD) simulations to explore the conservation of dynamics among homologs of similar to 50 kDa N-terminal module of Spt16 (Spt16N). Spt16N from Saccharomyces cerevisiae (Sc-Spt16N) and three of its homologs with 30-40% sequence identities were available in the PDB. To make our data-set more comprehensive, the crystal structure of an additional homolog (62% sequence identity with Sc-Spt16N) was solved at 1.7 angstrom resolution. Cumulative MD simulations of 6 mu s were carried out on these Spt16N structures and on two additional protein structures with varying degrees of similarity to it. The simulations revealed that correlation in patterns of backbone fluctuations vary linearly with sequence identity. This trend could not be inferred using crystallographic B-factors. Further, normal mode analysis suggested a similar pattern of inter-domain (inter-lobe) motions not only among Spt16N homologs, but also in the M24 peptidase structure. On the other hand, MD simulation results highlighted conserved motions that were found unique for Spt16N protein, this along with electrostatics trends shed light on functional aspects of Spt16N. Communicated by Ramaswamy H. Sarma.
Keywords: Backbone fluctuations; FACT complex; histone binding; interdomain motion; M24 peptidase

Exceptional cyclability of thermally stable PVdF-co-HFP/SiO2 nanocomposite polymer electrolytes for sodium ion batteries - Das, Akhila; Melepurakkal, Amrutha; Sreeram, Pranav; Gireesh, K. T.; Balakrishnan, Neethu T. M.; Fatima, M. J. Jabeen; Pullanchiyodan, Abhilash; Ahn, Jou-Hyeon; V. Shelke, Manjusha; Raghavan, Prasanth (Journal of Energy Storage, 2023)
Thermally stable composite polymer electrolyte (CPE) devising PVdF-co-HFP polymer with in-situ generated silica (SiO2) as filler is synthesised via non-solvent- induced phase inversion technique. The filler loading of in-situ synthesised silica in PVdF-co-HFP is varied from 0 to 9 wt% and its morphological, thermal and electrochemical characterization is carried out. Among the different composite electrolytes, the PVdF-co-HFP containing 6 wt% SiO2 shows the uniform microporous structure with a highest porosity (84 %), surface area (784.14 m(2) g(-1)), electrolyte uptake (262 %) and electrolyte retention value (0.48). The incorporation of in-situ SiO2 on CPE shows not only the enhancement in thermal stability but also reduced thermal shrinkage with an increase in the filler content. The electrochemical studies of PVdF-co-HFP containing 6 wt% SiO2 shows a higher ionic conductivity (0.71 mS cm(-1)) and potential stability >4.5 V verses Na/Na+. The Na-ion half-cells assembled with PVdF-co-HFP/SiO2 composite electrolyte show a specific capacity of similar to 120 mAh g(-1) at 0.3C rate in room temperature and a stable cycle performance with a Coulombic efficiency of around 100 % for 200 cycles.
Keywords: Composite electrolytes; Coulombic efficiency; polymer electrolytes; Sodium ion batteries; specific capacity; thermal stability

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

Fast normalization and despeckled method for skin optical coherence tomography image via deep learning - Rahaman, Jarjish; Lukas, Brandon; May, Julia; Puyana, Carolina; Tsoukas, Maria; Avanaki, Kamran (Photonics in Dermatology and Plastic Surgery 2023, 2023)
Optical coherence tomography (OCT) is well-known for its high-resolution, non-invasive imaging modality with many medical uses, including skin imaging. Nevertheless, speckle noise limits the analytical capabilities of this imaging tool, causing deterioration in contrast and less exact detection of tissue microstructural heterogeneity. To address this issue, we proposed OCT despeckling approach by combing it with normalization to reduce the speckle noise more effectively. The proposed method contains multiple steps including phase correlation for alignment of misaligned frames, frame averaging which minimizes speckle noise, region-wise pixels normalization that helps to normalize intensity pixels, a modified BM3D filtering to suppress the white and speckle, and contrast enhancement to improve the contrast appropriately. To establish the approach, we applied 130 distinct B-scan skin OCT images and validate and evaluate the performance using qualitatively and quantitatively. Although the output obtained by the algorithm is promising, the method is time-consuming because of a series of steps. To reduce the time complexity, we also develop a supervised deep learning model by mapping between noisy-despeckled image pairs. The effectiveness and applicability of our DL approach were assessed using 130 skin OCT B-scans from various body areas taken from 45 healthy people between the ages of 20 and 60. With the support of the experimental results, we demonstrate that our DL model is capable to normalize and despeckling OCT images simultaneously.
Keywords: CNN; deep learning; denoising; Optical coherence tomography; speckle

FeCl2-catalyzed rearrangement of aryl peroxyoxindole into 1,3-benzooxazin-4-One - Mohanta, Nirmala; Samal, PragnyaParamita; Krishnamurty, Sailaja; Gnanaprakasam, Boopathy (Advanced Synthesis & Catalysis, 2023)
We report an FeCl2-catalyzed radical rearrangement of aryl peroxyoxindoles into 1,3-benzooxazin-2-ones to obtain a variety of aryl substituted 1,3-benzooxazin-4-ones in moderate to good yields. Mechanistically, this skeletal rearrangement of peroxyoxindoles proceeded via radical pathway and was well supported with a series of experimental findings and DFT studies.
Keywords: 1; 3-Benzooxazin-4-one; FeCl2; Peroxyoxindole; rearrangement; Ring expansion

Food-grade xylitol production from corncob biomass with acute oral toxicity studies - Dasgupta, Diptarka; Ahuja, Vishal; Singh, Raghuvir; More, Snehal; Mudliar, Sandeep; Kumar, Madan (World Journal of Microbiology & Biotechnology, 2023)
Xylitol, a sugar substitute, is widely used in various food formulations and finds a steady global market. In this study, xylitol crystals were produced from corncob by fermentation (as an alternative to the chemical catalytic process) by a GRAS yeast Pichia caribbica MTCC 5703 and characterized in detail for their purity and presence of any possible contaminant that may adversely affect mammalian cell growth and proliferation. The acute and chronic oral toxicity trials demonstrated no gross pathological changes with average weekly weight gain in female Wistar rats at high xylitol loading (LD50 > 10,000 mg/kg body weight). The clinical chemistry analysis supported the evidence of no dose-dependent effect by analyzing blood biochemical parameters. The finding suggests the possible application of the crystals (> 98% purity) as a food-grade ingredient for commercial manufacture pending human trials.
Keywords: Acute oral toxicity; Corncob; Fermentation; Shelf life analysis; xylitol

G4-binding drugs, chlorpromazine and prochlorperazine, repurposed against COVID-19 infection in hamsters - Roy, Shuvra Shekhar; Sharma, Shalu; Rizvi, Zaigham Abbas; Sinha, Dipanjali; Gupta, Divya; Rophina, Mercy; Sehgal, Paras; Sadhu, Srikanth; Tripathy, Manas Ranjan; Samal, Sweety; Maiti, Souvik; Scaria, Vinod; et al. (Frontiers in Molecular Biosciences, 2023)
The COVID-19 pandemic caused by SARS-CoV-2 has caused millions of infections and deaths worldwide. Limited treatment options and the threat from emerging variants underline the need for novel and widely accessible therapeutics. G-quadruplexes (G4s) are nucleic acid secondary structures known to affect many cellular processes including viral replication and transcription. We identified heretofore not reported G4s with remarkably low mutation frequency across >5 million SARS-CoV-2 genomes. The G4 structure was targeted using FDA-approved drugs that can bind G4s - Chlorpromazine (CPZ) and Prochlorperazine (PCZ). We found significant inhibition in lung pathology and lung viral load of SARS-CoV-2 challenged hamsters when treated with CPZ or PCZ that was comparable to the widely used antiviral drug Remdesivir. In support, in vitro G4 binding, inhibition of reverse transcription from RNA isolated from COVID-infected humans, and attenuated viral replication and infectivity in Vero cell cultures were clear in case of both CPZ and PCZ. Apart from the wide accessibility of CPZ/PCZ, targeting relatively invariant nucleic acid structures poses an attractive strategy against viruses like SARS-CoV-2, which spread fast and accumulate mutations quickly.
Keywords: Conserved motif; FDA-approved drugs; G-quadruplex binding drugs; hamster model of COVID-19; RNA G-quadruplex

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.

Genomic surveillance reveals early detection and transition of delta to omicron lineages of SARS-CoV-2 variants in wastewater treatment plants of Pune, India - Rajput, Vinay; Pramanik, Rinka; Malik, Vinita; Yadav, Rakeshkumar; Samson, Rachel; Kadam, Pradnya; Bhalerao, Unnati; Tupekar, Manisha; Deshpande, Dipti; Shah, Priyanki; Shashidhara, L. S.; Boargaonkar, Radhika; et al. (Environmental Science and Pollution Research, 2023)
The COVID-19 pandemic has emphasized the urgency for rapid public health surveillance methods to detect and monitor the transmission of infectious diseases. The wastewater-based epidemiology (WBE) has emerged as a promising tool for proactive analysis and quantification of infectious pathogens within a population before clinical cases emerge. In the present study, we aimed to assess the trend and dynamics of SARS-CoV-2 variants using a longitudinal approach. Our objective included early detection and monitoring of these variants to enhance our understanding of their prevalence and potential impact. To achieve our goals, we conducted real-time quantitative polymerase chain reaction (RT-qPCR) and Illumina sequencing on 442 wastewater (WW) samples collected from 10 sewage treatment plants (STPs) in Pune city, India, spanning from November 2021 to April 2022. Our comprehensive analysis identified 426 distinct lineages representing 17 highly transmissible variants of SARS-CoV-2. Notably, fragments of Omicron variant were detected in WW samples prior to its first clinical detection in Botswana. Furthermore, we observed highly contagious sub-lineages of the Omicron variant, including BA.1 (similar to 28%), BA.1.X (1.0-72%), BA.2 (1.0-18%), BA.2.X (1.0-97.4%) BA.2.12 (0.8-0.25%), BA.2.38 (0.8-1.0%), BA.2.75 (0.01-0.02%), BA.3 (0.09-6.3%), BA.4 (0.24-0.29%), and XBB (0.01-21.83%), with varying prevalence rates. Overall, the present study demonstrated the practicality of WBE in the early detection of SARS-CoV-2 variants, which could help track future outbreaks of SARS-CoV-2. Such approaches could be implicated in monitoring infectious agents before they appear in clinical cases.
Keywords: Bioinformatics pipeline; COVID-19; Early warning; India; Next-generation sequencing; Omicron; Public health; SARS-CoV-2; wastewater; Wastewater-based epidemiology

Green adeptness in synthesis of non-toxic copper and cobalt oxide nanocomposites with multifaceted bioactivities - Mane, Pramod C.; Kadam, Deepali D.; Khadse, Ashok N.; Chaudhari, Aditya R.; Ughade, Supriya P.; Agawane, Sachin B.; Chaudhari, Ravindra D. (Cancer Nanotechnology, 2023)
Background: In the present era, we are facing different health problems mainly concerning with drug resistance in microorganisms as well as in cancer cells. In addition, we are also facing the problems of controlling oxidative stress and insect originated diseases like dengue, malaria, chikungunya, etc. originated from mosquitoes. In this investigation, we unfurled the potential of Achatina fulica mucus in green synthesis of mucus mediated copper oxide bio-nanocomposites (SM-CuONC) and cobalt oxide bio-nanocomposites (SM-Co3O4NC). Herein we carried out the physico-chemical characterization like UV-Vis spectra, X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM), Transmission electron microscopy (TEM), Energy Dispersive X-ray Analysis (EDAX) and X-ray photoelectron spectroscopy (XPS) of as synthesized bio-nanocomposites. Both the bio-nanocomposites were tested for their potential as antimicrobial activity using well diffusion assay, anticancer activity by MTT assay, antioxidant activity by phosphomolybdenum assay and mosquito larvicidal activity.Results: The results of this study revealed that, SM-CuONC and SM-Co3O4NC were synthesized successfully using A. fulica mucus. The FESEM and TEM data reveal the formation of nanoparticles with quasi-spherical morphology and average particle size of similar to 18 nm for both nanocomposites. The EDAX peak confirms the presence of elemental copper and cobalt in the analyzed samples. The X-ray diffraction analysis confirmed the crystalline nature of the CuO and Co3O4. The result of anti microbial study exhibited that, SM-CuONC showed maximum antimicrobial activity against Escherichia coli NCIM 2065 and Aspergillus fumigatus NCIM 902 which were noted as 2.36 +/- 0.31 and 2.36 +/- 0.59 cm resp. at 60 mu g/well concentration. The result of anticancer activity for SM-CuONC was exhibited as, 68.66 +/- 3.72, 62.66 +/- 3.61 and 71.00 +/- 2.36 percent kill, while SM-Co3O4NC exhibited 61.00 +/- 3.57, 72.66 +/- 4.50 and 71.66 +/- 4.22 percent kill against Human colon cancer (HCT-15), Cervical cancer (HeLa), and Breast cancer (MDA-MB-231) cell lines, respectively, at 20 mu g/well concentration. Both the nanocomposites also exhibited better antioxidant activity. Total antioxidant activity for SM-CuONC at 50 mu g/ml concentration was found to be highest as 55.33 +/- 3.72 while that of SM-Co(3)O(4)Ns was 52.00 +/- 3.22 mM of ascorbic acid/mu g respectively. Both bio-nanocomposites also exhibited 100% mosquito larvicidal activity at concentration ranging from 40 to 50 mg/l. During cytotoxicity study it is noted that at 5 mu g/well concentration, SM-CuO and SM-Co3O4NCs suspension showed more than 97% viability of normal (L929) cell lines. We also studied phytotoxicity of both bio-nanocomposites on Triticum aestivum. In this study, 100% seed germination was observed when seeds are treated with SM-CuONC and SM-Co3O4NC at 500 mg/l and 250 mg/l concentration respectively.Conclusions: This study concludes that in future as synthesized SM-CuONC and SM-Co3O4NC can be used in pharmaceutical, health care system for betterment and welfare of human life as both bio-nanocomposites exhibits better antimicrobial, anticancer, antioxidant and mosquito larvicidal potential.
Keywords: Achatina fulica mucus; Bio-nanocomposites; Biological activities; Characterization; Toxicity

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.

Hierarchical covalent organic framework-foam for multi-enzyme tandem catalysis - Paul, Satyadip; Gupta, Mani; Dey, Kaushik; Mahato, Ashok Kumar; Bag, Saikat; Torris, Arun; Gowd, E. Bhoje; Sajid, Hasnain; Addicoat, Matthew A.; Datta, Supratim; Banerjee, Rahul (Chemical Science, 2023)
Covalent organic frameworks (COFs) are ideal host matrices for biomolecule immobilization and biocatalysis due to their high porosity, various functionalities, and structural robustness. However, the porosity of COFs is limited to the micropore dimension, which restricts the immobilization of enzymes with large volumes and obstructs substrate flow during enzyme catalysis. A hierarchical 3D nanostructure possessing micro-, meso-, and macroporosity could be a beneficial host matrix for such enzyme catalysis. In this study, we employed an in situ CO2 gas effervescence technique to induce disordered macropores in the ordered 2D COF nanostructure, synthesizing hierarchical TpAzo COF-foam. The resulting TpAzo foam matrix facilitates the immobilization of multiple enzymes with higher immobilization efficiency (approximately 1.5 to 4-fold) than the COF. The immobilized cellulolytic enzymes, namely beta-glucosidase (BGL), cellobiohydrolase (CBH), and endoglucanase (EG), remain active inside the TpAzo foam. The immobilized BGL exhibited activity in organic solvents and stability at room temperature (25 degrees C). The enzyme-immobilized TpAzo foam exhibited significant activity towards the hydrolysis of p-nitrophenyl-beta-d-glucopyranoside (BGL@TpAzo-foam: K-m and V-max = 23.5 +/- 3.5 mM and 497.7 +/- 28.0 mu M min(-1)) and carboxymethylcellulose (CBH@TpAzo-foam: K-m and V-max = 18.3 +/- 4.0 mg mL(-1) and 85.2 +/- 9.6 mu M min(-1) and EG@TpAzo-foam: K-m and V-max = 13.2 +/- 2.0 mg mL(-1) and 102.2 +/- 7.1 mu M min(-1)). Subsequently, the multi-enzyme immobilized TpAzo foams were utilized to perform a one-pot tandem conversion from carboxymethylcellulose (CMC) to glucose with high recyclability (10 cycles). This work opens up the possibility of synthesizing enzymes immobilized in TpAzo foam for tandem catalysis.

High open-circuit voltage in lead sulfide quantum dot solar cells via solution-phase ligand exchange with low electron affinity cadmium halides - Dambhare, Neha V.; Biswas, Arindam; Sharma, Anjali; Shinde, Dipak Dattatray; Mahajan, Chandan; Mitra, Anurag; Rath, Arup K. (JOURNAL OF MATERIALS CHEMISTRY A, 2023)
The deployment of colloidal quantum dots (QDs) in building high-performance solar cells and other optoelectronic applications relies on the passivation of unsaturated surface atoms through ligand engineering to attain a trap-free energy bandgap and strong QD coupling while maintaining the quantum confinement effect. Despite major advancements in surface passivation strategies, the open circuit voltage (V-oc) of lead sulfide (PbS) QD solar cells is limited by undesirable sub-bandgap states and high-bandtail states. The most advanced solution-phase ligand exchange strategy for PbS QDs depends on lead halide ligands, which improved the photocurrent and fill factor in QD solar cells significantly, but only an incremental change in V-oc is observed. Here we showcase a solution-phase hybrid ligand passivation strategy for PbS QDs using shallow electron affinity cadmium halide and thiol ligands. The cadmium halide ligand treatment results in the sub-monolayer substitution of surface Pb atoms by Cd atoms. The photophysical properties of QDs improve significantly to show intense band edge emission, diminished trap emission and reduced Urbach tail states. The photovoltaic devices built using cadmium halide-treated QDs show low reverse saturation current, which helps to attain a record 0.7 V V-oc (for a 1.28 eV bandgap) and 12.3% PCE.

High rate, high temperature, dendrite free plating/stripping of Li in 3-dimensional honeycomb boron carbon nitride to realize an ultrastable lithium metal anode - Patrike, Apurva; Karbhal, Indrapal; Wasnik, Kundan; Torris, Arun; Maibam, Ashakiran; Krishnamurty, Sailaja; Shelke, V, Manjusha (Journal of Energy Storage, 2023)
Lithium (Li) metal could be the anode of choice for energy dense Li-batteries owing to its high theoretical specific capacity. However, low coulombic efficiency and poor safety on account of the occurrence of the Li-dendrites during charging-discharging pose a bottleneck for practical applications. In this work, we report a high-rate plating and stripping of Li through host engineering to realize ultrastable Li metal anode (LMA). Benchmark plating/stripping efficiency could be achieved via uniquely structured, highly ordered honeycomb boron carbon nitride (HBCN) as a functional scaffold. Boron and nitrogen doping, large surface area and ordered mesoporous structure induce homogeneous solid electrolyte interface (SEI) layer formation and provide numerous nucleation sites with subsequent dendrite-free growth with 99.98 % coulombic efficiency at 8 mA cm(-2) high current and 10 mAh cm(-2) capacity over 3000 cycles. Via post-cycling advanced characterizations techniques of Ex-situ XPS, 3D X-ray micro-tomography analyses and FESEM, we demonstrate the formation of a stable SEI layer and morphological changes that occurred during Li plating cycles in the HBCN structure. Computational studies validate the high lithium plating-stripping efficacy of HBCN to its highly ordered porous nature, exothermic Li-binding and upshift in the Fermi levels. When tested at elevated temperature (50 degrees C), a stable Li plating-stripping in HBCN is realised at 4 mA cm(-2) current and 10 mAh cm(-2) capacity values with similar to 100 % C.E. Furthermore, we report the results of testing a Li metal cell comprised of Li deposited HBCN anode and LiFePO4 (LFP) cathode.
Keywords: Boron carbon nitride; Dendrite-free Li metal anode; Functional scaffold; High temperature plating/stripping of Li; Molecular planarity parameter; X-ray micro-tomography

Histidinal-based potent antimalarial agents - Meena, Chhuttan L.; Hingamire, Tejashri; Gupta, Tanya; Deshmukh, Bhagyashree; Karmodiya, Krishanpal; Joshi, Rakesh; Shanmugam, Dhanasekaran; Sanjayan, Gangadhar J. (ChemMedChem, 2023)
Herein we report the synthesis and evaluation of peptide-histidinal conjugated drug scaffolds, which have the potential to target the hemoglobin-degrading proteases falcipain-2/3 from the human malaria parasite. Scaffolds with various substitutions were tested for antimalarial activity, and compounds 8 g, 8 h, and 15 exhibited EC50 values of similar to 0.018 mu M, similar to 0.069 mu M, and similar to 0.02 mu M, respectively. Structure-based docking studies on falcipain-2/3 proteases (PDB:2GHU and PDB:3BWK) revealed that compounds 8 g, 8 h, and 15 interact strongly with binding sites of falcipain-2/3 in a substrate-like manner. In silico ADME studies revealed that the molecules of interest showed no or minimal violations of drug-likeness parameters. Further, phenotypic assays revealed that compound 8 g and its biotinylated version inhibit hemoglobin degradation in the parasite food vacuole. The identification of falcipain-2/3 targeting potent inhibitors of the malaria parasite can serve as a starting point for the development of lead compounds as future antimalarial drug candidates.
Keywords: artemisinin; chloroquine; digestive vacuole; docking; falcipains; falciparum; P

Hydrogen from catalytic non-thermal plasma-assisted steam methane reforming reaction - Bajpai, Abhinav; Mehta, Shweta; Joshi, Kavita; Kumar, Sushant (International Journal of Hydrogen Energy, 2023)
Steam methane reforming reaction was carried out in a dielectric barrier plasma reactor. A systematic study is conducted to understand the influence of input power, flow rate, and water for the conversion, yield, and selectivity of the reaction over strategically designed catalysts. In particular, the production rate and selectivity of the products (H2, CO and C2 hydrocarbons) are monitored. CeO2 was used as packing material, mixed with oxides of manganese or copper and their combination. The optimum Cu/CeO2 catalyst illustrated the production rate of 248.7 mmolg-1h-1 and 11.25 mmolg-1h-1 for H2, and CO, respectively at specific energy input of 19.8 JL-1. DFT calculations exhibit apparent change in electronic structure of the CeO2 after inclusion of oxides of manganese and copper that enhance interaction with methane. Based on these findings, a plausible mechanism is elucidatedSteam methane reforming reaction was carried out in a dielectric barrier plasma reactor. A systematic study is conducted to understand the influence of input power, flow rate, and water for the conversion, yield, and selectivity of the reaction over strategically designed catalysts. In particular, the production rate and selectivity of the products (H2, CO and C2 hydrocarbons) are monitored. CeO2 was used as packing material, mixed with oxides of manganese or copper and their combination. The optimum Cu/CeO2 catalyst illustrated the production rate of 248.7 mmolg-1h-1 and 11.25 mmolg-1h-1 for H2, and CO, respectively at specific energy input of 19.8 JL-1. DFT calculations exhibit apparent change in electronic structure of the CeO2 after inclusion of oxides of manganese and copper that enhance interaction with methane. Based on these findings, a plausible mechanism is elucidated which can help to design catalyst for other applications in non-thermal plasma atmosphere. & COPY; 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Keywords: DFT; Dielectric barrier discharge; Non-thermal plasma; selectivity; Specific energy input; Steam methane reforming

Identification of G-quadruplex structures in MALAT1 lncRNA that interact with nucleolin and nucleophosmin - Ghosh, Arpita; Pandey, Satya Prakash; Joshi, Dheeraj Chandra; Rana, Priya; Ansari, Asgar Hussain; Sundar, Jennifer Seematti; Singh, Praveen; Khan, Yasmeen; Ekka, Mary Krishna; Chakraborty, Debojyoti; Maiti, Souvik (Nucleic Acids Research, 2023)
Nuclear-retained long non-coding RNAs (lncRNAs) including MALAT1 have emerged as critical regulators of many molecular processes including transcription, alternative splicing and chromatin organization. Here, we report the presence of three conserved and thermodynamically stable RNA G-quadruplexes (rG4s) located in the 3 & PRIME; region of MALAT1. Using rG4 domain-specific RNA pull-down followed by mass spectrometry and RNA immunoprecipitation, we demonstrated that the MALAT1 rG4 structures are specifically bound by two nucleolar proteins, Nucleolin (NCL) and Nucleophosmin (NPM). Using imaging, we found that the MALAT1 rG4s facilitate the localization of both NCL and NPM to nuclear speckles, and specific G-to-A mutations that disrupt the rG4 structures compromised the localization of both NCL and NPM in speckles. In vitro biophysical studies established that a truncated version of NCL (& UDelta;NCL) binds tightly to all three rG4s. Overall, our study revealed new rG4s within MALAT1, established that they are specifically recognized by NCL and NPM, and showed that disrupting the rG4s abolished localization of these proteins to nuclear speckles

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