One-pot synthesized efficient molybdenum-niobium-oxide nanocatalyst for selective C-O and C-N coupling reactions at mild conditions - Kalbande, Pavan Narayan; Singh, Nittan; Swapna, Bhattu; Umbarkar, Shubhangi; Sudarsanam, Putla (Catalysis Communications, 2023)
An efficient molybdenum-niobium-oxide nanomaterial was synthesized by a one-pot hydrothermal method for selective C-O (glycerol ketalization) and C-N coupling (benzylamine oxidation) reactions. The catalytically favourable properties, such as defective metal sites, truncated surfaces, and uniform metal dispersion in the MoO3-Nb2O5 nanorods, calcined at 500 degrees C (MoNb OPS-5), were confirmed by Raman, HR-TEM, and STEM-EDX, respectively. Because of improved Lewis/Bronsted acidic strength, the MoNb OPS-5 catalyst showed higher activity in glycerol ketalization and benzylamine oxidation at mild conditions, giving superior selectivity to solketal (97%) and dibenzylimine (99%), respectively. The MoNb OPS-5 catalyst showed high structural stability and considerable good reusability efficacy.
Keywords: C-O and C-N coupling; Glycerol and benzylamine; Mo-Nb-O nanocatalyst; nanocatalysts; One-pot hydrothermal synthesis

Opaque cell-specific proteome of Candida albicans ATCC 10231 - Abdulghani, Mazen; Telang, Saraswati; Desai, Manisha; Kadam, Shivdas; Kazi, Rubina; Shelar, Amruta; Patil, Rajendra; Maurya, Radheshyam; Zore, Gajanan (Medical Mycology, 2023)
Candida albicans, a polymorphic opportunistic pathogen of humans, can exist in different morphological forms like yeast, hyphae, pseudohyphae, chlamydospores, and white and opaque cells. Proteomic analysis of opaque form of C. albicans ATCC 10231 is carried out in the present study using microflow liquid chromatography-tandem mass spectrometry and validated using expression analysis of selected genes using reverse transcription quantitative real-time PCR and mitochondrial membrane potential assay. This is the first report identifying opaque cell-specific proteins of C. albicans. A total of 188 proteins were significantly modulated under opaque form compared to white cells, of which 110 were upregulated, and 78 were downregulated. It was observed that oxidative phosphorylation (OxPhos) and oxidative stress are enhanced in C. albicans cells growing under opaque form as proteins involved in OxPhos (Atp1, Atp3, Atp16, Atp7, Cox6, Nuc2, Qcr7, and Sdh12) and oxidative stress response (Gcs1, Gtt11, Gpx2, Sod1, Ccp1, and Lys7) were significantly upregulated. The maximum upregulation of 23.16- and 13.93-fold is observed in the cases of Ccp1 and Nuc2, respectively. The downregulation of proteins, namely Als1, Csh1, Sap9, and Rho1, determining cell surface chemistry indicates modulation in cell wall integrity and reduced adhesion of opaque cells compared to white cells. This study is significant as it is the first draft of the proteomic profile of opaque cells that suggests enhanced OxPhos, oxidative stress, and modulation in cell surface chemistry indicating reduced adhesion and cell wall integrity, which could be associated with reduced virulence in opaque form. However, a deeper investigation is needed to explore it further. Lay Summary Opaque form is one of the least studied morphological forms of Candida albicans. To the best of our knowledge, this is the first report providing opaque cell-specific proteome. It suggests enhanced oxidative phosphorylation, oxidative stress, and modulation in cell surface chemistry, which could be associated with reduced virulence in opaque form.
Keywords: albicans; C; LC-MS; MS; opaque; Oxidative stress; OxPhos; protein

Organic field effect transistors comprising copolymers synthesized without structure-directing moieties with enhanced carrier mobility - Swain, Gitanjali; Javaregowda, Bharathkumar H.; Dambhare, Neha V.; Krishnamoorthy, Kothandam (ACS Applied Electronic Materials, 2023)
Conjugated materials are synthesized by C-C bond formation reactions. Trimethyltin and boronic acid are two widely used structure-directing moieties. While using the ethynyl moiety as a part of the monomer, additional structure-directing moieties are not needed. However, ethynylene will be part of the conjugated material. Often, the polymers with an ethynylene moiety negatively impact the polymers' properties. However, the ethynylene moiety could minimize the dihedral angle if the monomer has steric functionalities. For example, BODIPY is an attractive monomer due to its high molar extinction coefficient, partial quinoidal character, and high quantum yield. However, materials based on BODIPY exhibited poor charge carrier mobility due to steric hindrance generated by four methyl groups. Herein, we copolymerize BODIPY with ethynylene comprising i-indigo and thieno-i-indigo. The copolymer with thieno-i-indigo showed increased molecular weight and significantly reduced band gap compared to the copolymer with i-indigo. The copolymer with i-indigo showed immeasurably low hole transport mobility. On the other hand, the copolymer with thieno-i-indigo exhibited 0.003 cm2V(-1) s(-1). These measurements were made using field effect transistors. We also measured the charge carrier mobility using the space charge-limited current method. Both copolymers exhibited a mobility of 10(-3) cm(2) V-1 s(-1).
Keywords: acetylene linkage; BODIPY; field effect transistor; iso-indigo; Sonogashira coupling; thienoisoindigo

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

Origin of optoelectronic contradictions in 3,4-cycloalkyl[c]-chalcogenophenes: a computational study - Masilamani, Ganesh; Krishna, Gamidi Rama; Debnath, Sashi; Bedi, Anjan (Polymers, 2023)
The planar morphology of the backbone significantly contributes to the subtle optoelectronic features of pi-conjugated polymers. On the other hand, the atomistic tuning of an otherwise identical pi-backbone could also impact optoelectronic properties systematically. In this manuscript, we compare a series of 3,4-cycloalkylchalcogenophenes by tuning them atomistically using group-16 elements. Additionally, the effect of systematically extending these building blocks in the form of oligomers and polymers is studied. The size of the 3,4-substitution affected the morphology of the oligomers. In addition, the heteroatoms contributed to a further alteration in their geometry and resultant optoelectronic properties. The chalcogenophenes, containing smaller 3,4-cycloalkanes, resulted in lower bandgap oligomers or polymers compared to those with larger 3,4-cycloalkanes. Natural bonding orbital (NBO) calculations were performed to understand the disparity alongside the contour maps of frontier molecular orbitals (FMO).
Keywords: chalcogenophene; DFT calculation; Morphology; optoelectronic properties; steric effect

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

Pd(II)-catalyzed tandem cycloannulative-alkenylation of o-alkynyl-phenols/anilines with (E)-β-Iodovinyl sulfones: a direct strategy to construct 3-(Vinyl sulfonyl)benzoheterole derivatives - Reddy, Raju Jannapu; Sharadha, Nunavath; Krishna, Gamidi Rama (Journal of Organic Chemistry, 2023)
Benzoheterolesand vinyl sulfones are the most promisingpharmaceuticalrelevance motifs, yet the hybrid analogues of these scaffolds stillneed to be explored. We report herein a general and highly efficientPd(OAc)(2)-catalyzed intramolecular cyclization and vinylationof o-alkynylphenols/o-alkynylanilineswith (E)-beta-iodovinyl sulfones under mild reactionconditions. A direct C(sp(2))-C(sp(2)) cross-couplingis enabled for the diversity-oriented synthesis of vinyl sulfone-tetheredbenzofurans and indoles in good to high yields with excellent stereoselectivity.Notably, this tandem process was consistent at the gram scale, andin situ, generation of 2-(phenylethynyl)phenol has also been utilizedin a scalable synthesis. Late-stage synthetic transformations werealso further explored, including isomerization and desulfonylative-sulfenylation.Moreover, several control experiments were accomplished, and we proposeda plausible mechanism based on existing experimental results.

Phased short-interfering RNA siRD29(-) regulates GIBBERELLIN 3-OXIDASE 3 during stolon-to-tuber transitions in potato - Malankar, Nilam; Kondhare, Kirtikumar; Saha, Kishan; Mantri, Mohit; Banerjee, Anjan (Plant Physiology, 2023)
Phased short-interfering RNAs (phasiRNAs) fine tune various stages of growth, development, and stress responses in plants. Potato (Solanum tuberosum) tuberization is a complex process, wherein a belowground modified stem (stolon) passes through developmental stages like swollen stolon and minituber before it matures to a potato. Previously, we identified several phasiRNA-producing loci (PHAS) from stolon-to-tuber transition stages. However, whether phasiRNAs mediate tuber development remains unknown. Here, we show that a gene encoding NB-ARC DOMAIN-CONTAINING DISEASE RESISTANCE PROTEIN (StRGA4; a PHAS locus) is targeted by Stu-microRNA482c to generate phasiRNAs. Interestingly, we observed that one of the phasiRNAs, referred as short-interfering RNA D29(-), i.e. siRD29(-), targets the gibberellin (GA) biosynthesis gene GIBBERELLIN 3-OXIDASE 3 (StGA3ox3). Since regulation of bioactive GA levels in stolons controls tuber development, we hypothesized that a gene regulatory module, Stu-miR482c-StRGA4-siRD29(-)-StGA3ox3, could govern tuber development. Through transient expression assays and small RNA sequencing, generation of siRD29(-) and its phase was confirmed in planta. Notably, the expression of StGA3ox3 was higher in swollen stolon compared to stolon, whereas siRD29(-) showed a negative association with StGA3ox3 expression. Antisense (AS) lines of StGA3ox3 produced more tubers compared to wild type. As expected, StRGA4 overexpression (OE) lines had high levels of siRD29(-) and mimicked the phenotypes of StGA3ox3-AS lines, indicating the functionality of this module in potato. In vitro tuberization assays (with or without a GA inhibitor) using StGA3ox3 antisense lines and overexpression lines of StGA3ox3 or StRGA4 revealed that StGA3ox3 controls the tuber stalk development. Taken together, our findings suggest that a phasiRNA, siRD29(-), mediates the regulation of StGA3ox3 during stolon-to-tuber transitions in potato. A phasiRNA module, Stu-miR482c-StRGA4-siRD29(-), regulates the expression of a gibberellin biosynthesis gene StGA3ox3 during stolon-to-tuber transitions in potato.

Phenol hydrogenation to cyclohexanol catalysed by palladium supported on CuO/CeO2 - Kasabe, Mirabai M.; Kotkar, Vaibhav R.; Dongare, Mohan K.; Umbarkar, Shubhangi B. (Chemistry-an asian jounrnal, 2023)
Hydrogenation of phenol to cyclohexanone/cyclohexanol is an important reaction in production of nylon-6, nylon-66 and in petroleum industry. Liquid phase phenol hydrogenation over Pd-CuO/CeO2 was carried out under mild conditions. Palladium impregnated over CuO/CeO2 synthesized by co-precipitation method showed excellent catalytic activity for phenol hydrogenation (99% conversion with 80% cyclohexanol yield) at 90 degrees C and 10 bar H-2 pressure in water. Commercial 10%Pd/C showed only 8% phenol conversion under identical conditions. The detailed characterization revealed significant improvement in surface area of ceria after addition of CuO and decrease in crystallite size with creation of defects in CeO2 lattice. XPS analysis showed Pd loading on CuO/CeO2 to cause hydrogen spillover on the surface leading to increase in the oxygen vacancies. The interaction of phenol with catalyst surface studied by detailed FTIR analysis, revealed activation of phenol on oxygen vacancy of ceria as phenoxide ion with perpendicular orientation of aromatic ring on catalyst surface.
Keywords: Cyclohexanol; Hydrogen spillover; oxygen vacancies; Pd-CuO/CeO2; phenol hydrogenation

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

Photogating induced high sensitivity and speed from heterostructure of few-layer MoS2 and reduced graphene oxide-based photodetector - Das, Chayan; Kumar, Ashok; Kumar, Suresh; Dambhare, Neha V.; Kumar, Mahesh; Rath, Arup K.; Sahu, Satyajit (Physical Chemistry Chemical Physics, 2023)
Over the past few years, two-dimensional transition metal dichalcogenides (2D-TMDC) have attracted huge attention due to their high mobility, high absorbance, and high performance in generating excitons (electron and hole pairs). Especially, 2D molybdenum disulfide (MoS2) has been extensively used in optoelectronic and photovoltaic applications. Due to the low photo-to-dark current ratio (I-photo/dark) and low speed, pristine MoS2-based devices are unsuitable for these applications. So, they need some improvements, i.e., by adding layers or decorating with materials of complementary majority charges. In this work, we decorated pristine MoS2 with reduced graphene oxide (rGO) and got improved dark current, I-photo/dark, and response time. When we compared the performance of pristine MoS2 based device and rGO decorated MoS2 based device, the rGO/MoS2-based device showed an improved performance of responsivity of 3.36 A W-1, along with an I-photo/dark of about 154. The heterojunction device exhibited a detectivity of 4.75 x 10(12) Jones, along with a very low response time of 0.184 ms. The stability is also outstanding having the same device performance even after six months.

Photoinduced CO2 and N2 reductions on plasmonically enabled gallium oxide - Ojha, Niwesh; Thakkar, Kavita; Bajpai, Abhinav; Joshi, Kavita; Kumar, Sushant (Journal of Colloid and Interface Science, 2023)
Ag-containing ZnO/ b-Ga2O3 semiconductor, which exhibit reduced bandgap, increased light absorption, and hydrophilicity, have been found to be useful for photocatalytic CO2 reduction and N2 fixation by water. The charge-separation is facilitated by the new interfaces and inherent vacancies. The Ag@GaZn demonstrated the highest photocurrent response, about 20-and 2.27-folds that of the Ga and GaZn sam-ples, respectively. CO, CH4, and H2 formed as products for photo-reduction of CO2. Ag@GaZn catalyst exhibited the highest AQY of 0.121 % at 400 nm (31.2 W/m2). Also, Ag@GaZn generated 740 lmolg-1 of NH4+ ions, which was about 18-folds higher than Ga sample. In situ DRIFTS for isotopic-labelled 13CO2 and 15N2 reaffirmed the photo-activity of as-synthesized catalysts. Density functional theory pro-vided insight into the relative affinity of different planes of heterostructures towards H2O, CO2 and N2 molecules. The structure-photoactivity rationale behind the intriguing Ag@GaZn sample offers a funda-mental insight into the role of plasmonic Ag and design principle of heterostructure with improved pho-toactivity and stability.(c) 2022 Elsevier Inc. All rights reserved.
Keywords: CO2 reduction; DRIFTS density functional theory; hydrophilicity; Photocurrent response

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

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

Polyethylene-grafted sheet-like silsesquioxane nanocomposites with unprecedented adhesion to polar substrates - Sharma, Vivek; Paulbudhe, Uday; Bachhar, Nirmalya; Chikkali, Samir H.; Kumaraswamy, Guruswamy (ACS Applied Polymer Materials, 2023)
Polyethylene is a highly apolar polymer with very pooradhesionto most substrates, necessitating the use of tie layers. Therefore,the synthesis of functional polyethylene is a long-standing challengein catalytic ethylene polymerization. Here, we report the preparationof a nanocomposite comprising polyethylene covalently grafted ontosheet-like silsesquioxanes, with unprecedented adhesion to metal andglass. A norbornene-grafted, layered Mg-silsesquioxane is treatedwith Grubbs second-generation catalyst (G-II), and the identity ofcovalently tethered G-II is unambiguously ascertained. Covalentlytethered G-II catalyzes the ring opening metathesis polymerizationof cyclooctene to poly(cyclooctene). The resulting poly(cyclooctene)is catalytically hydrogenated to yield polyethylene. This polyethylenenanocomposite exhibited a bonding strength of the order of 100 MPaon stainless steel and aluminum, 10-fold higher than reported forengineered polyethylene copolymers. The nanocomposite exhibits anincrease in the polar component of surface energy, yet remains compatibleand cocrystallizes with a polyethylene matrix.
Keywords: adhesion; clay; Nanocomposite; Polyethylene; silsesquioxane

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

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

Potential of Y. lipolytica epoxide hydrolase for efficient production of enantiopure (R)-1,2-octanediol - Godase, Vijaya P. P.; Kumar, V. Ravi; Kumar, Ameeta Ravi (AMB Express, 2023)
The recombinant Yleh from a tropical marine yeast Yarrowia lipolytica NCIM 3589 exhibited a high epoxide hydrolase activity of 9.34 +/- 1.80 mu mol min(-1) mg(-1) protein towards 1,2-epoxyoctane (EO), at pH 8.0 and 30 degrees C. The reaction product was identified as 1,2-Octanediol (OD) by GC-MS using EO and H2O18 as substrate, affirming the functionality of Yleh as an epoxide hydrolase. For EO, the K-m, V-max, and k(cat)/K-m values were 0.43 +/- 0.017 mM, 0.042 +/- 0.003 mM min(-1), and 467.17 +/- 39.43 mM(-1) min(-1), respectively. To optimize the reaction conditions for conversion of racemic EO by Yleh catalyst to enantiopure (R)-1,2-octanediol, initially, Response Surface Methodology was employed. Under optimized reaction conditions of 15 mM EO, 150 mu g purified Yleh at 30 degrees C a maximal diol production of 7.11 mM was attained in a short span of 65 min with a yield of 47.4%. Green technology using deep eutectic solvents for the hydrophobic substrate (EO) were tested as co-solvents in Yleh catalyzed EO hydrolysis. Choline chloride-Glycerol, produced 9.08 mM OD with an increased OD yield of 60.5%. Thus, results showed that deep eutectic solvents could be a promising solvent for Yleh-catalyzed reactions making Yleh a potential biocatalyst for the biosynthesis of enantiopure synthons. [GRAPHICS] .
Keywords: Deep Eutectic solvents; Optimization; Recombinant epoxide hydrolase; Response surface methodology; Yarrowia lipolytica

PPO-ZIF MMMs possessing metal-polymer interactions for propane/ propylene separation - Kunjattu, H. Shebeeb; Kharul, Ulhas K. (Journal of Membrane Science, 2023)
An assertive formation of ZIF-based mixed matrix membranes (MMMs) with polyphenylene oxide (PPO), a high permeability polymer as a host, is presented. The interfacial interactions between the filler particles and polymer matrix are established by DSC and XPS analyses. The ZIF loading could be achieved up to 40% without hampering the stability of the resulting MMMs. These membranes were evaluated for pure gas permeability, specifically aiming at C3H6/C3H8 separation, a highly desired application in industry. The ZIF-PPO hybrids display promising pure gas as well as mixed gas permeation performance. The 40% ZIF-8 and ZIF-67 loaded membrane display promising C3H6/C3H8 selectivity of 27.5 and 25, with a permeability of 12 and 13 barrer, respectively. The enhanced selectivity is attributed to the absence of defects eliminated due to metal-polymer interactions. The permeation study of a 30% ZIF-8 loaded membrane while varying transmembrane pressure and long-time exposure (150 h) of propylene at 60 psi indicated the excellent stability of the membrane. The sorption analysis further confirmed the molecular sieving characteristics of the ZIF@PPO MMMs. The mixed gas permeation performance showed promising results of high permeability as well as maintaining selectivity over a wide range of compositions.
Keywords: Interfacial interactions; Mixed matrix membrane; Olefin-paraffin separation; poly(phenyleneoxide); Zeolitic imidazole framework

Pt-anchored-zirconium phosphate nanoplates as high-durable carbon-free oxygen reduction reaction electrocatalyst for PEM fuel cell applications - Kumar, Sachin; Yoyakki, Athira; Pandikassala, Ajmal; Soni, Roby; Kurungot, Sreekumar (Advanced Sustainable Systems, 2023)
Commercially available platinum-supported carbon (Pt/C) catalysts are the most widely used oxygen reduction reaction (ORR) electrocatalysts in polymer electrolyte membrane fuel cells (PEMFCs). However, inadequate active triple-phase boundary formation and carbon oxidation in Pt/C during PEMFC operation shorten its lifetime and efficiency. In this direction, a new class of carbon-free electrocatalysts for ORR is prepared by dispersing Pt nanoparticles on ZrP (Zirconium phosphates) nanoplates. In one case (ZrP@Pt), the Pt nanoparticles are found to be closely distributed and completely covering the ZrP nanoplates, whereas in the second case (Pt/ZrP), the Pt nanoparticles selectively restrict dispersion along the edges of the support. ZrP as the support displays an intrinsic proton conductivity of approximate to 0.5 x 10(-4) S cm(-1) at 70 degrees C, with an activation energy (E-a) of 0.19 eV. Pt/ZrP shows better durability after 3000 start-stop cycles. The mass activity of Pt/ZrP is increased by 4.6 times compared to Pt/C, which exhibits a loss in mass activity by 1.37 times. The single-cell level validation of ZrP@Pt, Pt/ZrP, and Pt/C as the electrocatalysts in PEMFC at an operating potential of 0.60 V shows the achievable current densities of 0.600, 0.890, and 0.890 A cm(-2).
Keywords: carbon-free electrocatalysts; fuel cells; oxygen reduction reaction; zirconium phosphate

Quantum dot (Aun/Agn, n=3-8) capped single lipids: interactions and physicochemical properties - Maneri, Asma H. H.; Varode, Shruti Suhas; Maibam, Ashakiran; Ranjan, Priyatosh; Krishnamurty, Sailaja; Joshi, Krati (Physical Chemistry Chemical Physics, 2023)
Realizing the potential of nano-hybrid biomaterials in various applications (nanoprobes to drug delivery), special attention has been devoted towards their synthesis and development. Nonetheless, several questions pertaining to the interface chemistry between the constituent entities (biomolecules and organic/inorganic part) of these hybrids, still remain unresolved. Keeping these unsolved issues in mind, the present theoretical investigation focuses on determining the electronic/physicochemical properties and interactions within gold and silver quantum dot-capped single lipid molecules. Quantum dots of varying sizes and shapes have been chosen and then coupled with lipid molecules (1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC), 1,2-dimyristoyl-sn-glycero-3-phosphoethanolamine (DMPE), 1,2-dimyristoyl-sn-glycero-3-phosphoglycerol, sodium salt (DMPG)), at the choline/glycerol, carboxylate and phosphate site. It has been identified that Au Qds interact strongly as compared to Ag clusters. In addition to the type, the shape and size of the Qd also influences their attachment with lipids. Among various sites, the phosphate site provides a considerably stronger platform for the coupling of Qds. On the other hand, attachment at the choline site leads to significantly lower interaction energies. The trend noted in interaction energies coincides with the structure-electronic property analysis (interatomic bond distances, charge transfer, PO2- stretching frequencies), which further helps in deducing the nature of interactions. The molecular dynamics simulations performed on selected Qd-lipid complexes established that the Qd interacting with lipids at the phosphate site remains fairly stable at room temperature without undergoing fragmentation into individual components. On the other hand, at the choline site, the Qd-to-lipid coupling is unstable and therefore they experience disintegration at 300 K temperature. Additionally, a unique glycerol-to-phosphate site crossover is evidenced, which reaffirms that the phosphate site is selectively preferred by Qds for binding with lipid molecules.

Radical cascade cyclization of unactivated alkene-tethered indoles with aryldiazonium salt and sodium metabisulfite to access Azo- and Sulfonylated-2,3-Dihyro-1H-pyrrolo[1,2-a]indoles - Kumar, Pawan; Rai, Archana; Kumar, Manish; Krishna, Gamidi Rama; Das, Utpal (Journal of Organic Chemistry, 2023)
A method for the construction ofheterocyclic scaffold2,3-dihyro-1H-pyrrolo[1,2-a]indolesvia arylsulfonylradical-triggered cascade cyclization of unactivated alkene-tetheredindoles in the absence of any external photocatalyst has been developed.This protocol features easily accessible starting materials such assodium metabisulfite and aryldiazonium tetrafluoroborates at roomtemperature and offers good functional group compatibility, enablingthe introduction of various functionalized sulfonyl and azo groupsinto pyrrolo[1,2-a]indoles.

Rapid bioinspired N-acyliminium ion strategy for the ABC core of the stemona alkaloids - Chavan, Subhash P.; Kalbhor, Dinesh B.; Gonnade, Rajesh G. (Asian Journal of Organic Chemistry, 2023)
A concise and highly diastereoselective bioinspired key cationic cyclization strategy for the asymmetric synthesis of the tricyclic core of the (-)-stemoamide, together with 8,9-bis-epi-stemoamide has been described. The key N-acyliminium ion precursors were accessed from L-tartaric acid and L-malic acid respectively. The use of ethyl acetoacetate derived bifunctional allylidenetriphenylphosphorane reagent in the early stage of the synthetic strategy is advantageous for the rapid construction of highly functionalized key pyrrolo[1,2-& alpha;]azepine frameworks.
Keywords: alkaloids; Biomimetic synthesis; Claisen rearrangement; cyclization; Regioselectivity

Reaction pathways and kinetics of N-acetyl-d-glucosamine hydrolysis in sub- and supercritical water - Kulkarni, Sphurti P. P.; Joshi, Sunil S. S.; Kulkarni, Amol A. A. (New Journal of Chemistry, 2023)
Subcritical and supercritical water hydrolysis of N-acetyl-d-glucosamine (NAG) to value-added chemicals has been studied in detail. Experiments were carried out using a continuous flow reactor by varying temperature (250-400 degrees C), pressure (5-25 MPa) and residence time (2-60 s). A wide product distribution was obtained during the reactions, including solid, liquid and gaseous compounds, sensitive to the state of water: sub- or supercritical. Subcritical conditions promoted the formation of solid compounds, whereas gasification was favored in supercritical water. The prominent products present in the liquid fraction were glycolic acid, acetic acid, formic acid, 5-HMF and acetamide. The formation of a few distinct nitrogen-containing heterocyclic compounds was observed only in supercritical water. Following instantaneous deacetylation of NAG, several oxidation, reduction and secondary reactions occur during hydrolysis of NAG in subcritical and supercritical water. A kinetic model for the prediction of yields of acetic acid, glycolic acid and formic acid is developed. The network of reactions showed specifc deviations from conventional understanding. The current findings show that it is possible to develop a suitable process to make a set of value-added chemicals from chitinous biomass.

Recyclable Pd nanoparticles immobilized on amine functionalized LDH for the Suzuki-Miyaura cross-coupling reaction - Patil, Seema P. P.; Jadhav, Sanjay N. N.; Inamdar, Firoz A. A.; Ameen, Mohd Aatif; Rode, Chandrashekhar V. V.; Rajmane, Archana S. S.; Kumbhar, Arjun S. S. (Chemical Papers, 2023)
In the present work, we invented a Pd nanoparticle immobilized on an amine-functionalized LDH catalyst (PdNP@NH2LDH-Al-MCM-41) for cross-coupling reactions. The palladium was grafted onto the support by treating the Pd(OAc)(2) with NH2-LDH-Al-MCM-41 in acetone at room temperature. The prepared catalyst was characterized by FT-IR, SEM, TGA, TEM, and XPS techniques. The TEM characterization of the catalyst showed the uniform distribution of PdNPs with sizes ranging from 3 to 6 nm located inside the mesoporous. The Suzuki-Miyaura cross-coupling reaction was used to demonstrate the catalytic efficiency of the prepared PdNPs@NH2-LDH-Al-MCM-41 catalyst. The prepared and analyzed catalyst showed good to excellent activity in the Suzuki-Miyaura cross-coupling reaction of various aryl bromides with different aryl boronic acids in ethanol at 80 degrees C. The catalyst showed TON up to similar to 47 and TOF similar to 47 h(-1). The catalytic results exhibited that the catalyst is completely recoverable with simple filtration. The catalytic efficiency shows a slight decrease in activity for the Suzuki-Miyaura cross-coupling reactions even after five repeated recycles. TEM images of the freshly prepared and reused catalysts (after five catalytic cycles) showed palladium nanoparticles remain unchanged at the end of the reactions. [GRAPHICS] .
Keywords: LDH; PdNPs; Recyclability; Suzuki-Miyaura coupling

Regioselective synthesis of benzannulated [5,6]-oxaspirolactones via Cu(II)-catalyzed cycloisomerization of 2-(5-Hydroxyalkynyl)benzoates - Thorat, Sagar S.; Shimpi, Sagar P.; Sambherao, Pooja I.; Krishna, Gamidi Rama; Kontham, Ravindar (Journal of Organic Chemistry, 2023)
Spiroketals and oxaspirolactones are widely found in biologically active natural products, serving as important structural motifs. In this study, we present a Cu-(II)-catalyzed cascade cycloisomerization of 2-(5-hydroxyalkynyl)-benzoates, enabling the regioselective synthesis of benzannulated [5,6]-oxaspirolactones containing an isochromen-1-one moiety. This strategy offers a rapid and efficient approach to access a diverse array of benzannulated [5,6]-oxaspirolactones. The methodology presented here showcases a broad substrate scope, delivering good yields and scalability up to gram scale. The structures of the oxaspirolactones were unequivocally confirmed through single-crystal X-ray analysis and by analogy using H-1 and C-13-H-1 NMR data.
Keywords: Construction; Isocumarins; Strategies

Regulation of trehalose metabolism in insects: from genes to the metabolite window - Tellis, Meenakshi B.; Kotkar, Hemlata M.; Joshi, Rakesh S. (Glycobiology, 2023)
Trehalose is a major circulatory sugar in the haemolymph of insects. It provides instant energy and protection against stress. Trehalose metabolism is associated with insect growth and development. The architecture and spatio-temporal expression dynamics of trehalose metabolism and transport genes are key for regulation. These genes are controlled by various transcription factors, largely linked to nutrition, insect development, and metamorphosis. Also, trehalose levels are affected by substrate affinities and modifications of enzymes involved in the pathway. A feedback mechanism involving the precursors and products can regulate trehalose metabolism. Further, the neuroendocrine system controls trehalose levels under normal and stressed conditions by producing different hormones. Hypotrehalosemic hormones work under surplus energy conditions to activate haemolymph trehalose uptake and degradation. In contrast, hypertrehalosemic hormones stimulate trehalose production in the fat body and its transport to the haemolymph. However, trehalose metabolism regulation in insects needs to be studied in detail. This review discusses aspects of trehalose synthesis, transport, and degradation dynamics in developmental transition and stress response. Unraveling the epigenetic factors, transcriptional control and chemical or genetic modulators can provide further insights into the intricate regulation of trehalose in a development- and tissue-specific manner. This molecular information about effectors and regulators of trehalose metabolism can be applied in developing diverse biotechnological applications.
Keywords: Hormone; Insect development; Metabolic regulation; Stress; trehalose

Repurposing small molecules of Tephrosia purpurea against SARS-CoV-2 main protease - Sahoo, Rosaleen; Sahu, Parameswar; Swargam, Sandeep; Kumari, Indu; Behera, Banshidhar (Journal of Biomolecular Structure and Dynamics, 2023)
Coronavirus infection is a communicable disease caused by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) which emerged as a global pandemic with deteriorating effect on the world's population. Main protease (M-pro) of SARS-CoV-2 plays a significant role in the viral replication, transcription and disease propagation as well as a potential candidate for drug discovery and development for COVID-19 infection. The current study employed state of art structure-based drug discovery to decipher the role of phytochemicals of Tephrosia purpurea against M-pro. Tephrosia purpurea is being used as a traditional medicinal plant for the treatment of cough, breathlessness and fever as per the Indian Materia Medica. Screening of the phytochemicals of Tephrosia purpurea against M-pro was performed using molecular docking approach to identify the top 5 hits (+)-tephrorin B, deguelin, vitamin p, lanceolarin and 3beta-hydroxy-20(29)-lupene with binding energy of -8.4, -8.1, -8.0, -7.8, and -7.8 kcal/mol, respectively. Furthermore, identified top 5 hits were subjected to drug-likeness and toxicity prediction as well as MM-GBSA calculation. Out of the five molecules four molecules were predicted not to comprise any mutagenic and carcinogenic effects. Top two molecules based on the drug-likeness properties for oral bio-availability were further analysed by molecular dynamics simulation at 100 ns timescale. It was observed from the dynamic behaviour of the two complexes that the addition of these molecules changed the conformation and stability of the apo protein; thus may act as inhibitors for M-pro. Communicated by Ramaswamy H. Sarma
Keywords: molecular dynamics; SARS-CoV-2; Tephrosia purpurea

Response of cardiac pulse parameters in humans at various inclinations via 360° rotating platform for simulated microgravity perspective - Jagtap, Sagar; Kumar, Ajay; Mahale, Bhoopesh; Dixit, Jyotsana; Kalange, Ashok E.; Kanawade, Rajesh; Gangal, Shashikala; Vidyasagar, Pandit (NPJ Microgravity, 2023)
On the Earth, the human body is designed and adapted to function under uniform gravitational acceleration. However, exposure to microgravity or weightlessness as experienced by astronauts in space causes significant alterations in the functioning of the human cardiovascular system. Due to limitations in using real microgravity platforms, researchers opted for various ground-based microgravity analogs including head-down tilt (HDT) at fixed inclination. However, in the present study, an investigation of response of various cardiac parameters and their circulatory adaptation in 18 healthy male subjects was undertaken by using an indigenously developed 360 & DEG; rotating platform. Cardiac pulse was recorded from 0 & DEG; to 360 & DEG; in steps of 30 & DEG; inclination using piezoelectric pulse sensor (MLT1010) and associated cardiac parameters were analyzed. The results showed significant changes in the pulse shape while an interesting oscillating pattern was observed in associated cardiac parameters when rotated from 0 & DEG; to 360 & DEG;. The response of cardiac parameters became normal after returning to supine posture indicating the ability of the cardiovascular system to reversibly adapt to the postural changes. The observed changes in cardiac parameters at an inclination of 270 & DEG;, in particular, were found to be comparable with spaceflight studies. Based on the obtained results and the proposed extended version of fluid redistribution mechanism, we herewith hypothesize that the rotation of a subject to head down tilt inclination (270 & DEG;) along with other inclinations could represent a better microgravity analog for understanding the cumulative cardiac response of astronauts in space, particularly for short duration space missions.

Rh-catalyzed asymmetric hydroformylation of olefins using phosphorus ligands - Kumar, Rohit; Sen, Anirban; Chikkali, Samir H. (Journal of chemical sciences, 2023)
Easily accessible BINOL-based monodentate phosphite ligand L1 and hybrid ligand L2 have been synthesized in good yield by following a one-pot, two-step protocol. A single 31P resonance at 146.6 ppm confirmed the formation of L1. Subsequent 1-2D NMR and mass spectrometric analysis authenticated the existence of L1. These ligands afforded excellent activity and regio-selectivity in the Rh-catalyzed AHF of styrenic substrates. L1 showed excellent regioselectivity but did not discriminate between the two enantiomers, while L2 displayed an enantiomeric excess (ee) of up to 20%. In our attempts to understand the reasons for low ee, the coordination behavior of L2 was investigated. The coordination study revealed that L2 coordinates with the Rh as a monodentate ligand, although there are two P-sites. It was found that only the phosphine arm was coordinated to the Rh and the phosphite arm stayed away from the Rh core at the ambient temperature, leading to moderate ee.Graphical abstractOne-step synthesis of a phosphite (L1) and a phosphine-phosphite (L2) ligand and their implication in the asymmetric hydroformylation of olefins with excellent regioselectivity (>95%) and moderate enantioselectivity (up to 20%) is reported.
Keywords: catalysis; coordination; Hydroformylation; Phosphine-phosphite ligand; Phosphite ligand

Rh-catalyzed C-H functionalization of the (Pyrazol-5-yl)pyridine core of GBT-440 - Kalshetti, Rupali G.; Halnor, Swapnil V.; Ramana, Chepuri V. (Synthesis-Stuttgart, 2023)
The Rh-catalyzed cross dehydrogenative coupling (CDC)/alkylation of the pyrazolylpyridine unit of GBT-440 proceeded smoothly under ambient conditions and selectively on the pyrazole unit while directed by the pyridine. The scope of these reactions was established by employing simple as well as conjugated olefins for CDC and various diazo esters and the TIPS-EBX reagent for alkylation. At the outset, a focused small molecule library around the bis-heterocyclic core of GBT440 was developed via C-H functionalization.
Keywords: C-H activation; cross dehydrogenative coupling; diazo ester; GBT-440; Rh catalysis; TIPS-EBX

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

Salicylaldehydate coordinated two-dimensional-conjugated metal-organic frameworks - Mohammed, Abdul Khayum; Pena-Sanchez, Pilar; Pandikassala, Ajmal; Gaber, Safa; AlKhoori, Ayesha A.; Skorjanc, Tina; Polychronopoulou, Kyriaki; Kurungot, Sreekumar; Gandara, Felipe; Shetty, Dinesh (Chemical Communications, 2023)
A novel class of copper-based 2D-c-MOF was synthesized from 1,3,5-triformylphloroglucinol using green mechano-chemistry. Herein, metal coordination with the salicylaldehyde functional moiety was explored for the first time in MOFs. Moreover, an intrinsic semiconductive copper-based SA-MOF thin film was fabricated using an in situ salt-free method at room temperature.

Seasonal dynamics and tree foliar habit drive the rhizobacterial diversity in congeneric Ficus species from Northern Western Ghats, India - Salunkhe, Vaishnavi H.; Kunte, Pooja S.; Paul, Dhiraj; Kasodekar, Amol K.; Kadoo, Narendra Y. (Rhizosphere, 2023)
Tree species, annual climatic cycle, and geochemical properties influence the tree rhizospheric microbiome. However, its understanding in the moist deciduous forest of Northern Western Ghats (NWG), India, is limited. Moreover, the effects of foliar habits of trees and seasonal variations on rhizobacterial communities across congeneric tree species are unexplored. Hence, we employed high throughput 16 S rRNA gene sequencing to examine the effects of foliar habits of congeneric tree species and seasonal influences on the rhizobacterial community. For this study, rhizospheric soil from Ficus arnottiana (deciduous) and Ficus talboti (evergreen) trees from NWG, India, was collected during three seasons (summer, monsoon, and winter) and subjected to high throughput sequencing. A total of 3031 amplicon sequence variants (ASV) were observed, of which 1257 and 1181 ASV were unique to F. arnottiana and F. talboti, respectively, and 593 ASV were common to both species. The phyla Actinobacteria, Proteobacteria, Acidobacteria, and Chloroflexi were ubiquitous and contributed >90% to the rhizobacterial community. Some bacterial phyla were exclusively associated with either of the tree species and seasons. Different bacterial phyla performed similar functions in different seasons, indicating their functional redundancy and emphasizing their resilience and adaptability across seasons. It was observed that seasonal dynamics mainly drove the rhizobacterial diversity; however, it was also influenced by the foliar habits of the trees and geochemical properties. The study enhances the understanding of congeneric tree microbiomes and offers valuable insights into their potential applications through microbiome engineering.
Keywords: Amplicon variants; Bacterial diversity; Ficus arnottiana; Ficus talboti; Rhizosphere

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

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

Self-powered wearable breath sensor cum nanogenerator using AuNR-rGO-PVDF nanocomposite - Bang, Amruta D.; Ghalawat, Monika; Poddar, Pankaj; Kulkarni, Sulabha K.; Adhyapak, Parag V. (IEEE Sensors Journal, 2023)
Breathing is the most important function of living being. It is well known that breath contains 90% humidity along with various gases and volatile organic compounds (VOCs). These gases are released during various metabolic activities in the body. These gases present in the breath can act as biomarkers to showcase healthiness or abnormalities in the body. Therefore, breath sensors are the need of time to detect diseases at early stages and in noninvasive way. Herein, we report, simple breath sensor using Au nanorods (AuNRs) and its nanocomposite with reduced graphene oxide (rGO) and polyvinylidene fluoride (PVDF). The nanocomposites system is designed in such a way that each component has its advantages for breath sensing. Here, AuNR being a good humidity sensitive material detects the breath efficiently. The ss phased PVDF being a very good ferroelectric material, contributes for voltage generation during sensing and enables the device to be self powered. The highly conducting rGO increases the sensitivity and voltage generation by facilitating the electron transport in the nanocomposite system. The nanocomposite was optimized with respect to PVDF, rGO and Au concentration. The as-synthesized materials were characterized by physiochemical characterization techniques such as field emission scanning electron microscopy (FESEM), X-ray diffraction analysis (XRD), UV-Visible spectroscopy, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The ss phase formation of the PVDF was confirmed from the XRD peak at 20.41 degrees. SEM results revealed that AuNR have length 15-20 nm and aspect ratio similar to 3-4. Breath sensing tests were carried out for as synthesized nanocomposite material. The nanocomposite exhibited high sensitivity towards breath and generated the voltage of similar to 0.7 V within 0.8 s.
Keywords: Au nanorods (AuNRs); breath analyzer; breath sensor; nanogenerator

Settling and spreading behaviour of particle clusters in quiescent liquids in confined vessels - Pal, Sayan; Kulkarni, Amol A. (Particuology, 2023)
Here we report experiments on particle cluster settling at high Reynolds number in quiescent liquid contained in a vessel. The particles were observed to spread at the vessel bottom surface in a nearcircular annular shape after settling irrespective of the shape of the vessel cross-section and particle shape, size, and types. Effect of different parameters such as mass, type and aspect ratio of the particles, height, and viscosity of liquid was investigated on spreading behaviour. Formation of the hemispherical bottom cap of the cluster that bounces upon hitting the vessel bottom surface was found to be responsible for the final circular annular shape of the settled structure. Particle leakage from the cluster was seen in the form of a tail. In the liquid having viscosity beyond 100 cP, cluster breakage was observed that resulted in hindered settling and asymmetric shapes of finally settled particles. The observations are useful to understand the overall area over which settling and spreading of such clusters can be observed. (c) 2023 Published by Elsevier B.V. on behalf of Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of Sciences.
Keywords: Particle cluster; Settling; spreading; Temporal evolution

Shape-controlled MoO3/MnO x nanocatalyst for the selective synthesis of 2-phenylquinoxaline drug motifs - Singh, Nittan; Putla, Suresh Babu; Pratap Singh, Chandrodai; Kalbande, Pavan Narayan; Choudhary, Priyanka; Krishnamurty, Sailaja; Krishnan, Venkata; Bhatte, Kushal; Sudarsanam, Putla (ACS Applied Nano Materials, 2023)
We have developed a highly effective shape-controlled MoO3/MnOx nanocatalyst for the selective synthesis of 2-phenylquinoxaline drug motifs at room temperature without any external oxidant. Electron microscopy images reveal that the MnOx material contains rod-shaped particles (length: 500-1000 nm and width: 150-200 nm) and the MoO3 species are uniformly dispersed in the MoO3/MnOx material. The MoO3/MnOx nanocatalyst calcined at 500 degrees C (MoO3/MnOx-5) contains abundant strong acid sites and an optimum ratio of Mn4+/Mn3+, which are responsible for the C-N cross-coupling reaction between 2-phenylethylamine and o-phenylenediamine, giving higher yields (>96%) of 2-phenylquinoxaline at mild conditions. The broad scope of this catalytic strategy at room temperature and without an external oxidant was confirmed by achieving >90% yields of functional 2-phenylquinoxalines from C-N cross-coupling of various o-phenylenediamines and 2-phenylethylamines. The outstanding reusability efficiency of the MoO3/MnOx-5 nanocatalyst up to five cycles without the need for a regeneration step as well as the effective scalability highlighted the practicability of the MoO3/MnOx-based catalytic protocol for carbon-heteroatom coupling reactions at room temperature and without an external oxidant. Using computational studies, the possible reasons for the selective synthesis of 2-phenylquinoxaline over the MoO3/MnOx-5 nanocatalyst were elucidated.
Keywords: cascade C-N cross-coupling; DFT studies; room temperature andopen air; shape-controlled MoO3/MnOx nanocatalyst; structure-activity correlation

Six-membered NHC stabilized monomeric zinc complexes - Gour, Kritika; Kundu, Gargi; Dash, Soumya Ranjan; Vanka, Kumar; Tothadi, Srinu; Sen, Sakya S. (European Journal of Inorganic Chemistry, 2023)
This paper describes the rare use of a 6-membered saturated N-heterocyclic carbene (NHC) known as 1,3-di(2,6-diisopropylphenyl) tetrahydropyrimidine-2-ylidene (abbreviated as 6-SI-Dipp) as a ligand in zinc chemistry. We report on the investigation of the reactions between 6-SI-Dipp and ZnX2, which resulted in a range of new monomeric 6-SIDipp center dot ZnX2 complexes (X=Et (1), Cl (2), Br (3), and I (4)). We also prepared a new NHC zinc complex where the two substituents of the zinc atom are different, 6-SIDipp center dot Zn(Et)Br (7) through the reaction of the proligand [6-SIDippH]Br with ZnEt2. We have observed that the reactions of complex 1 with sulfur and HBpin led to the removal of the ZnEt2 moiety, resulting in the formation of a C=S double bond and a B H activation product, respectively. Lastly, the reaction of 1 with five-membered NHCs led to the exchange of carbene and the formation of either 5-IDipp center dot ZnEt2 (8) or 5-SIDipp center dot ZnEt2 (9).
Keywords: Lewis adduct; NHC; X-ray diffraction; zinc

Solvation structure and dynamics of a small ion in an organic electrolyte - Kore, Shivshankar; Sahoo, Rudhi Ranjan; Santra, Binit; Sarkar, Archishman; Chowdhury, Tubai; Deshmukh, Samadhan H.; Hazarika, Sulagna; Chatterjee, Srijan; Bagchi, Sayan (Journal of Photochemistry and Photobiology A-Chemistry, 2023)
Organic carbonates are commonly used as electrolytes in commercial lithium-ion batteries. A detailed interpretation of the solvation structure and dynamics of the electrolyte around ions is necessary to understand the charge/discharge process in batteries. This work combines infrared absorption spectroscopy with quantum chemical calculations and molecular dynamics simulations to decipher the solvation structure of propylene carbonate, a cyclic carbonate, around the dissolved thiocyanate ion. Two dimensional infrared spectroscopy and polarization-selective pump probe spectroscopies have been utilized to extract the timescales of solvent fluctuation and the solute reorientational dynamics. The similarity in the slow timescales for the solute and the solvent dynamics signifies that similar processes control both dynamics.

Spatio-temporal variation of the microbiome and resistome repertoire along an anthropogenically dynamic segment of the Ganges River, India - Samson, Rachel; Rajput, Vinay; Yadav, Rakeshkumar; Shah, Manan; Dastager, Syed; Khairnar, Krishna; Dharne, Mahesh (Science of the Total Environment, 2023)
Aquatic ecosystems are regarded as a hub of antibiotic and metal resistance genes. River Ganges is a unique riverine system in India with socio-cultural and economic significance. However, it remains underexplored for its microbiome and associated resistomes along its anthropogenically impacted course. The present study utilized a nanopore sequenc-ing approach to depict the microbial community structure in the sediments of the river Ganges harboring antibiotic and metal resistance genes (A/MRGs) in lower stretches known for anthropogenic impact. Comprehensive microbiome analyses revealed resistance genes against 23 different types of metals and 28 classes of antibiotics. The most dominant ARG category was multidrug resistance, while the most prevalent MRGs conferred resistance against copper and zinc. Seasonal differences dismally affected the microbiota of the Ganges. However, resistance genes for fosmidomycin and tetracycline varied with season ANOVA, p < 0.05. Interestingly, 333 and 334 ARG subtypes were observed at all the locations in pre-monsoon and post-monsoon, respectively. The taxa associated with the dominant ARGs and MRGs were Pseudomonas and Burkholderia, which are important nosocomial pathogens. A substantial phage diversity for pathogenic and putrefying bacteria at all locations attracts attention for its use to tackle the dissemination of antibiotic and metal-resistant bacteria. This study suggests the accumulation of antibiotics and metals as the driving force for the emergence of resistance genes and the affiliated bacteria trafficking them. The present metagenomic as-sessment highlights the need for comprehensive, long-term biological and physicochemical monitoring and mitigation strategies toward the contaminants associated with ARGs and MRGs in this nationally important river.
Keywords: Antibiotics (ARGs); Bacteriophages; Heavy metals (MRGs); Metagenomics; Microbiome; River Ganges

Speed breeding opportunities and challenges for crop improvement - Sharma, Shivani; Kumar, Amit; Dhakte, Priyanka; Raturi, Gaurav; Vishwakarma, Gautam; Barbadikar, Kalyani M.; Das, B. K.; Shivaraj, S. M.; Sonah, Humira; Deshmukh, Rupesh (Journal of Plant Growth Regulation, 2023)
Crop improvement in light of the rapidly changing climate and the increasing human population continues to be one of the primary concerns for researchers across the globe. The rate at which current crop improvement programs are progressing is essentially inadequate to meet the food demand. There is an urgent need for redesigning the crops for climate resilience and sustainable yield and nutrition. The rate of crop improvement is largely impeded owing to the long generation time taken by crop plants during the breeding process. As a solution in this direction, speed breeding is now being practiced at a large scale to reduce generation time to accommodate multiple generations of crops per year. To enhance the efficiency of breeding, researchers are now adopting an integrated approach where speed breeding is used along with modern plant breeding and genetic engineering technologies. In the present review, we have summarized the technological aspects, opportunities, and limitations associated with speed breeding. The application of speed breeding such as mapping population development, haplotype-based breeding, transgenic breeding, and genome-edited line advancement has also been discussed. Speed breeding is a promising technology that expedites the goals of food and industrial crop improvement by reducing the breeding cycles for establishing nutritional security and sustainable agriculture.
Keywords: Genome editing; Genomic selection; Haplotype breeding; Speed breeding; Transgenic breeding

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

Sulfonated zinc phthalocyanine coating as an efficient and ecofriendly corrosion inhibitor for copper surfaces: an in silico led design and its experimental validation - Dekshinamoorthy, Amuthan; Samal, Pragnya Paramita; Krishnamurty, Sailaja; Khatri, Praveen K.; Jain, Suman Lata; Ray, Anjan; Vijayaraghavan, Saranyan (Langmuir, 2023)
The current study highlights the successful integration of an in silico design with experimental validation to create a highly effective corrosion inhibitor for copper (Cu) surfaces. The synthesized sulfonated zinc phthalocyanine (Zn-Pc) is electrochemically characterized and demonstrates an impressive 97% inhibition efficiency, comparable to the widely used industrial corrosion inhibitor, BTA, for Cu surfaces. The corrosion inhibition is comprehensively analyzed through potentiodynamic polarization and impedance spectroscopy techniques, supported by their respective equivalent circuits. Furthermore, the sample undergoes thorough characterization using scanning electron microscopy, energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, contact angle measurements, and atomic force microscopy. Density functional theory calculations reveal that sulfonated Zn-Pc exhibits the highest interaction energy, underscoring its exceptional inhibition properties. These results open possibilities for utilizing computational methods to design and optimize corrosion inhibitors for protection of Cu surfaces.

Synthesis, biological evaluation and docking studies of silicon incorporated diarylpyrroles as MmpL3 inhibitors: an effective strategy towards development of potent anti-tubercular agents - Vasudevan, N.; Motiwala, Zenia; Ramesh, Remya; Wagh, Sachin B.; Shingare, Rahul D.; Katte, Revansiddha; Anand, Amitesh; Choudhary, Sushil; Kumar, Ajay; Gokhale, Rajesh S.; Kulkarni, Kiran A.; Reddy, D. Srinivasa (European Journal of Medicinal Chemistry, 2023)
Growing global demand for new molecules to treat tuberculosis has created an urgent need to develop novel strategies to combat the menace. BM212 related compounds were found to be potent anti-TB agents and they inhibit mycolic acid transporter, MmpL3, a known potent drug target from Mycobacterium tuberculosis. In order to enhance their inhibitory potency, several silicon analogues of diarylpyrroles related to BM212 were designed, synthesized, and evaluated for anti-tubercular activities. In Alamar blue assay, most of the silicon-incorporated compounds were found to be more potent than the parent compound (BM212), against Mycobacterium tuberculosis (MIC = 1.7 & mu;M, H37Rv). Docking results from the crystal structure of MmpL3 and silicon analogues as pharmacophore model also strongly correlate with the biological assays and suggest that the incorporation of silicon in the inhibitor scaffold could enhance their potency by stabilizing the hydrophobic residues at the binding pocket. The best docking hit, compound 12 showed an MIC of 0.1 & mu;M against H37Rv with an acceptable in vitro ADME profile and excellent selectivity index. Overall, the present study indicates that, the designed silicon analogues, especially compound 12 could be a good inhibitor for an intrinsically flexible drug-binding pocket of MmpL3 and has potential for further development as anti-tubercular agents.
Keywords: antibiotic; BM212; docking studies; MmpL3 inhibitor; Silicon analogue; tuberculosis

Synthesis of advanced asbestos-free material using rice husk ash and marble waste for thermal insulation applications - Verma, Sarika; Bajpai, Harsh; Suresh, S.; Mili, Medha; Gupta, Ritesh Kumar; Shetty, Rohit; Kamble, Sanjay; Khan, Mohd. Akram; Hashmi, S. A. R.; Srivastava, A. K. (Biomass Conversion and Biorefinery, 2023)
The importance and utilization of advanced thermal insulating materials increase due to their broad and irreplaceable energy conservation role. This paper describes the novel way of achieving insulating material. In two waste by-products, namely rice husk ash (RHA), agriculture waste, and marble waste powder (MWP), industrial waste has been utilized to make asbestos-free advanced material for thermal insulation. A novel method for making asbestos-free advanced material for thermal insulation using RHA and marble waste's inherent characteristics has developed mechano-chemical for appropriate physico-chemical consolidation, densification, and ceramic processing route. The Si and Ca sources undergo a series of chemical transformations accompanied by mass transfer and thermal reactions during the synthesis process. The formation of this silicate compound occurs due to the presence of higher contents of CaO in marble waste powder (MWP) and silica in rice husk ash (RHA), resulting in thermal insulating characteristics in the advanced thermal insulation material (ATIM). Raman spectra of ATIM after heating at 1100 degrees C were mainly amorphous, which had a broad peak at 1072 cm(-1). This shows thermal transformation occurs after the heating process, the admixture of tailored powder, and fly ash (FA). The density of the ATIM is found to be 1150 kg/m(3). The phase transformation (glass transition temperature) was found in all the samples between 600 and 800 degrees C. The mechanical properties, namely the compressive strength and impact strength evaluation test, showed that the material meets the standard specifications for ceramic tiles. The thermal conductivity (W/mK) was calculated from different temperature 30, 50, 100,150, and 200 degrees C and found to be 0.571, 0.541, 0.516, 0.498, and 0.477, respectively. According to the test results, it is concluded that ATIM from MWP, RHA, and FA were excellent insulating components. The novel feature of the reported process is the development of non-toxic and asbestos-free thermal insulating low-cost material wherein chemically designed and mineralogically formulating desired phases lead to the homogeneous and effective thermal insulating matrix. The process is feasible, simple, cheap, and highly energy-efficient, increases production efficiency, and is environmentally friendly. The widespread use of advanced material for a broad application spectrum ranges from aerospace, automobile, electronics, transportation, construction, to other industries.
Keywords: Asbestos; Fly ash; Marble waste; Material; Rice husk ash; Thermal insulation

Synthesis of N-functionalized 2,3-disubstituted benzofurans/naphthofurans from para-quinone methides and isocyanides via the [4+1] annulation pathway - Kale, Someshwar B.; Kumar, Manish; Shinde, Dinesh R.; Krishna, Gamidi Rama; Das, Utpal (Organic Chemistry Frontiers, 2023)
A scandium triflate catalyzed [4 + 1] cycloaddition reaction of 2-hydroxy-substituted para-quinone methides and isocyanides has been developed. This operationally simple, efficient and practical protocol provides straightforward access to a variety of N-functionalized 2,3-disubstituted benzofuran/naphthofuran derivatives with broad functional group compatibility and good scalability.

Tailoring COFs: transforming nonconducting 2D layered COF into a conducting quasi-3D architecture via interlayer knitting with polypyrrole - Jain, Chitvan; Kushwaha, Rinku; Rase, Deepak; Shekhar, Pragalbh; Shelke, Ankita; Sonwani, Disha; Ajithkumar, Thalasseril G.; Vinod, Chathakudath Prabhakaran; Vaidhyanathan, Ramanathan (Journal of the American Chemical Society, 2023)
Improving the electronic conductivity and the structural robustness of covalent organic frameworks (COFs) is paramount. Here, we covalently cross-link a 2D COF with polypyrrole (Ppy) chains to form a quasi-3D COF. The 3D COF shows well-defined reflections in the SAED patterns distinctly indexed to its modeled crystal structure. This knitting of 2D COF layers with conjugated polypyrrole units improves electronic conductivity from 10(-9) to 10(-2 )S m(-1). This conductivity boost is affirmed by the presence of density of states near the Fermi level in the 3D COF, and this elevates the COF's valence band maximum by 0.52 eV with respect to the parent 2D pyrrole-functionalized COF, which agrees well with the opto-electro band gaps. The extent of HOMO elevation suggests the predominant existence of a polaron state (radical cation), giving rise to a strong EPR signal, most likely sourced from the cross-linking polypyrrole chains. A supercapacitor devised with COF20-Ppy records a high areal capacitance of 377.6 mF cm(-2), higher than that of the COF loaded with noncovalently linked polypyrrole chains. Thus, the polypyrrole acts as a ``conjugation bridge'' across the layers, lowering the band gap and providing polarons and additional conduction pathways. This marks a far-reaching approach to converting many 2D COFs into highly ordered and conducting 3D ones.
Keywords: covalent organic frameworks; Electrical conductivity

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

Taming the parent oxoborane - Kundu, Gargi; Amrutha, P. R.; Raj, K. Vipin; Tothadi, Srinu; Vanka, Kumar; Sen, Sakya S. (Chemical Science, 2023)
Despite recent advancements in the chemistry of multiply bound boron compounds, the laboratory isolation of the parent oxoborane moiety, HBO has long remained an unsolved and well-recognized challenge. The reaction of 6-SIDipp(.)BH3 [6-SIDipp = 1,3-di(2,6-diisopropylphenyl)tetrahydropyrimidine2-ylidene] with GaCl3 afforded an unusual boron-gallium 3c-2e compound (1). The addition of water to 1 resulted in the release of H-2 and the formation of a rare acid stabilized neutral parent oxoborane, LB(H)]O (2). Crystallographic and density functional theory (DFT) analyses support the presence of a terminal B=O double bond. Subsequent addition of another equivalent of water molecule led to hydrolysis of the B-H bond to the B-OH bond, but the `B=O' moiety remained intact, resulting in the formation of the hydroxy oxoborane compound (3), which can be classified as a monomeric form of metaboric acid.

Targeted metabolite profiling and de novo transcriptome sequencing reveal the key terpene synthase genes in medicinally important plant, Couroupita guianensis Aubl - Thulasiram, Hirekodathakallu V.; Karegaonkar, Shrikant Jagannathrao; Sharma, Poojadevi; Kumar, Ashish; Ramkumar, Sudha; Pandreka, Avinash (Plant Genetic Resources-Characterization and Utilization, 2023)
The Lecythidaceae family tree, Couroupita guianensis Aubl, popularly known as Nagpushpa, is a widely cultivated ornamental tree with several uses in traditional medicine. The tree is revered as highly sacred in Indian traditional culture due to its uniquely shaped, fragrant flowers. Considering the significance, we were prompted to carry out the metabolite and transcriptome analysis of Nagapushpa. The flower, petals, stamen, stem and leaf of C. guianensis were metabolically profiled, and it was discovered that the flower tissue contained the highest terpenoid reservoir. A number of terpenoid pathway transcripts were also found in the flower tissue after transcriptome profiling. KEGG pathway mapping was carried out to correlate transcript sequences with the biosynthesis of different types of terpenes. We were able to clone three full-length terpene synthase gene candidates, i.e. monoterpene ocimene synthase, diterpene ent-kaurene synthase and sesquiterpene farnesene synthase. The transcript expression of selected terpene synthase genes was also verified in flower tissue. These cloned sequences were used for in silico structural investigations and protein function prediction at the level of 3D structure. The data presented in this study provide a comprehensive resource for the metabolic and transcriptomic profiles of C. guianensis. The study paves the way towards the elucidation of terpene biosynthetic pathway in C. guianensis and heterologous production of useful terpenoids in the future.
Keywords: Couroupita guianensis Aubl; flower; Metabolite profiling; terpene synthases; Transcriptomics

Template directed synthesis of boron carbon nitride nanotubes (BCN-NTs) and their evaluation for energy storage properties - Karbhal, Indrapal; Chaturvedi, Vikash; Yadav, Poonam; Patrike, Apurva; Shelke, Manjusha V. (Advanced Materials Interfaces, 2023)
A unique approach has been applied for the synthesis of 1D boron carbon nitride nanotubes (BCN-NTs) using MnO2 nanowires as templates. BCN-NTs have been evaluated in Na-ion batteries, Li-ion batteries, and supercapacitors as electrode material and exhibited excellent and stable electrochemical performance. BCN-NTs as an anode for Na-ion battery has been shown to be highly stable up to 3000 cycles with capacity retention of 95 mAh g(-1), at a high current density of 1 A g(-1). In the case of the Li-ion battery, these BCN-NTs show a specific capacity of 563 mAh g(-1) at a current density of 50 mA g(-1). Finally, when used as an electrode for a supercapacitor, BCN-NTs display a specific capacity of 221 F g(-1) at a current density of 3 A g(-1) and 168 F g(-1) even at a very high current density of 30 A g(-1) exemplifying the excellent rate performance. The multifunctionality and stable performance of BCN-NTs among various electrochemical energy storage systems highlight the robustness of the material and make it an excellent candidate for scalable production and commercialization.
Keywords: 1D-nanostructure; boron carbon nitride nanotubes (BCN-NTs); Co-doping; Li-ion battery; Na-ion battery; Supercapacitors

Tetraalkylammonium-based dicationic ionic liquids (ILs) for CO2 capture - Kulkarni, Prashant S.; Ranjane, Prathamesh; Mishra, Karun; Sundararajan, Swati; Kamble, Sanjay (New Journal of Chemistry, 2023)
This investigation includes the synthesis and characterization of a new series of ionic liquids (ILs) based on the tetraalkylammonium dication for the absorption of CO2, a step towards the development of more efficient and sustainable technologies. It was possible to synthesize amine-substituted PEG diacrylate by modifying poly(ethylene glycol) (PEG), which was then quaternized with 1-bromopentane to produce the IL PDBr. The other IL products, PDNTf2, PDBF4 and PDPF6, were synthesized via the metathesis of PDBr with the appropriate salt. The synthesized products were characterized using various techniques, such as FTIR, H-1 and C-13 NMR, elemental analysis, and density and viscosity meters, and evaluated as potential sorbents for CO2 capture. DSC and TGA were used to examine the thermal properties of the ILs. As observed from their thermal degradation behavior, the ILs exhibited two-stage disintegration with thermal stability up to 150 & DEG;C. The pressure drop method was used to study the sorption capacity of the ILs towards CO2. The sorption investigation showed that when the pressure is increased, the CO2 absorption increases. Equilibrium is reached in 40 minutes, demonstrating a rapid absorption rate. The IL with the [BF4](-) anion (PDBF4) demonstrated a maximum sorption capacity of 0.577 mole fraction of CO2, and can be regenerated and reused efficiently with less than 0.5% variation from its original absorption capacity. The CO2 absorption capacity for the ILs with other anions follows the trend: Br & AP; NTf2 < PF6 < BF4. This work shows that tetraalkylammonium-based dicationic ILs are adaptable, making them a suitable material for many applications, including sustainable CO2 capture technology.

TGF-beta 1 signalling in Alzheimer's pathology and cytoskeletal reorganization: a specialized Tau perspective - Kapoor, Mahima; Chinnathambi, Subashchandrabose (Journal of Neuroinflammation, 2023)
Microtubule-associated protein, Tau has been implicated in Alzheimer's disease for its detachment from microtubules and formation of insoluble intracellular aggregates within the neurons. Recent findings have suggested the expulsion of Tau seeds in the extracellular domain and their prion-like propagation between neurons. Transforming Growth Factor-beta 1 (TGF-beta 1) is a ubiquitously occurring cytokine reported to carry out immunomodulation and neuroprotection in the brain. TGF-beta-mediated regulation occurs at the level of neuronal survival and differentiation, glial activation (astrocyte and microglia), amyloid production-distribution-clearance and neurofibrillary tangle formation, all of which contributes to Alzheimer's pathophysiology. Its role in the reorganization of cytoskeletal architecture and remodelling of extracellular matrix to facilitate cellular migration has been well-documented. Microglia are the resident immune sentinels of the brain responsible for surveying the local microenvironment, migrating towards the beacon of pertinent damage and phagocytosing the cellular debris or patho-protein deposits at the site of insult. Channelizing microglia to target extracellular Tau could be a good strategy to combat the prion-like transmission and seeding problem in Alzheimer's disease. The current review focuses on reaffirming the role of TGF-beta 1 signalling in Alzheimer's pathology and cytoskeletal reorganization and considers utilizing the approach of TGF-beta-triggered microglia-mediated targeting of extracellular patho-protein, Tau, as a possible potential strategy to combat Alzheimer's disease.
Keywords: Alzheimer's disease; Cytoskeleton reorganization; Extracellular Tau; microglia; TGF-beta; TGF-beta 1

Theory-directed designing of an intrinsic-activity-modulated metal-doped copper oxide electrode for nitrate to ammonia synthesis - Tyagi, Nitin Kumar; Mahapatra, Bikash K.; Ghimire, Suvash; Manna, Narugopal; Kumar, Deepak; Kumar, Vijay; Mukhopadhyay, Kausik; Singh, Santosh K. (ACS Applied Energy Materials, 2023)
Synthesis of ammonia via electrochemical reduction ofnitrate isone of the most sustainable routes both for environmental protectionas well as energy saving initiatives. However, this process is limitedto the development of high-performance free-standing catalytic electrodeswith improved selectivity and Faradaic efficiency. Herein, we reporttheory-guided designing and fabrication of free-standing non-noblemetal (Mn, Fe, and Co)-doped copper oxide (CuO) electrodes by usinga simple and scalable electrode preparation method. The density functionaltheory (DFT)-based calculations show that the doped-Co sites in theCu surface facilitate the generation and supply of H+ tothe adsorbed NO3 (-) during the reductionprocess; as a result, the Co-CuO catalyst displays higher selectivitytoward nitrate reduction. The Co-doped Cu electrode (Co-CuO)delivers a higher NH3 yield (5492 mu g cm(-2)) at a reduction potential of -0.91 V vs RHE while maintaininga Faradaic efficiency of >95%. The alloying of Co to the coppermetalnot only facilitates the proton donation to the adsorbed reactant(NO3 (-)) but also tunes the Cu d-center,resulting in the active site modulation responsible for the activationof catalysts.
Keywords: Active sites; ammonia synthesis; electrocatalysis; Faradaic efficiency; High selectivity; metal-doped electrode

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

Thermally constructed stable Zn-doped NiCoOx-z alloy structures on stainless steel mesh for efficient hydrogen production via overall hydrazine splitting in alkaline electrolyte - Kashale, Anil Ashok; Rasal, Akash Sanjay; Hsu, Fei-Chien; Chen, ChangChun; Kulkarni, Sayali Nitin; Chang, Chun Hao; Chang, Jia-Yaw; Lai, Yuekun; Chen, I. -Wen Peter (Journal of Colloid and Interface Science, 2023)
Hydrogen has a high energy density of approximately 120 to 140 MJ kg(-1), which is very high compared to other natural energy sources. However, hydrogen generation through electrocatalytic water splitting is a high electricity consumption process due to the sluggish oxygen evolution reaction (OER). As a result, hydrogen generation through hydrazine-assisted water electrolysis has recently been intensively investigated. The hydrazine electrolysis process requires a low potential compared to the water electrolysis process. Despite this, the utilization of direct hydrazine fuel cells (DHFCs) as portable or vehicle power sources necessitates the development of inexpensive , effective anodic hydrazine oxidation catalysts. Here, we prepared oxygen-deficient zinc-doped nickel cobalt oxide (Zn-NiCoOx-z) alloy nanoarrays on stainless steel mesh (SSM) using a hydrothermal synthesis method followed by thermal treatment. Furthermore, the prepared thin films were used as electrocatalysts , the OER and hydrazine oxidation reaction (HzOR) activities were investigated in three-and two-electrode systems. In a three-electrode system, Zn-NiCoOx-z/SSM HzOR requires-0.116 V (vs RHE) potential to achieve a 50 mA cm(-2) current density, which is dramatically lower than the OER potential (1.493 V vs RHE). In a two-electrode system (Zn-NiCoOx-z/SSM(-)IIZn-NiCoOx-z/SSM(+)), the overall hydrazine splitting potential (OHzS) required to reach 50 mA cm(-2) is only 0.700 V, which is dramatically less than the required potential for overall water splitting (OWS). These excellent HzOR results are due to the binder-free oxygen-deficient Zn-NiCoOx-z/ SSM alloy nanoarray, which provides a large number of active sites and improves the wettability of cat-alysts after Zn doping. (C) 2023 Elsevier Inc. All rights reserved.
Keywords: Hydrazine Oxidation Reaction; hydrogen evolution reaction; Oxygen Evolution Reaction; Oxygen-Deficient Materials; Zinc Doping

Ti3C2Tx-Nb2Mo3O14 composite as novel anode to realize high power density combined with high stability in a hybrid lithium-ion capacitor - Pawar, Meenakshi D.; Thripuranthaka, Marulasiddappa; Patrike, Apurva; Deshmukh, Ashvini B.; Chaturvedi, Vikash; Krishnan, Arun; Shivade, Rajkiran; Shelke, Manjusha V. (Energy Technology, 2023)
Lithium-ion capacitors (LICs), with their higher energy density at high power capability, stand out as the future generation of energy-storage devices. Herein, the nanocomposite of Ti3C2Tx MXene with Nb2Mo3O14 is prepared by a one-step hydrothermal method and studied as an electrode material for LIC. The asfabricated composite MXene niobium molybdenum oxide (MXNMO) achieves a high reversible capacity of 205 mAh g(-1) at 100 mA g(-1) current density with outstanding cyclability. Further, asymmetric LIC full-cell device composed of MXNMO anode with supercapacitor grade activated carbon as a cathode delivers an energy density of 37.8 Wh kg(-1) (0.25 A g(-1)) and a higher power density of 4244 W kg(-1) (5 A g(-1)) along with the excellent durability showing 85% capacitance retention over 4000 cycles at 0.5 A g(-1).
Keywords: lithium-ion capacitors; MXene; niobium molybdenum oxides; pseudocapacitive anode materials

Titanium trisulfide nanosheets and nanoribbons for field emission- based nanodevices - Pawbake, Amit S.; Khare, Ruchita T.; Island, Joshua O.; Flores, Eduardo; Ares, Jose R.; Sanchez, Carlos; Ferrer, Isabel J.; Pawar, Mahendra; Frank, Otakar; More, Mahendra A.; van der Zant, Herre S. J.; Castellanos-Gomez, Andres; et al. (ACS Applied Nano Materials, 2023)
The field emission (FE) properties of TiS3 nanosheets and nanoribbons, synthesized by direct sulfuration of bulk titanium, are investigated. The nanosheets show an enhanced FE behavior with a low turn-on field of similar to 0.3 V/ mu m, required for drawing an emission current density of similar to 10 mu A/cm2. Interestingly, the TiS3 nanosheet emitter delivered a large emission current density of similar to 0.9 mA/ cm2 at a relatively low applied electric field of similar to 0.4 V/mu m. We have estimated the values of the field enhancement factor (beta), which are found to be similar to 5 x 104 for the TiS3 nanosheet emitter and similar to 4 x 103 for the nanoribbon emitter. We attribute the superior FE performance to the presence of atomically sharp edges and the reduced thickness of TiS3, as reflected in the high value of beta. In fact, the nanosheet sample presents a higher density of ultrathin layers (similar to 12 nm-thick), and thus, they have a larger edge to volume ratio than the nanoribbon samples (which are similar to 19 nm-thick). The superior FE behavior of TiS3 nanosheets over nanoribbons makes them a propitious field emitter and can be utilized for various FE-based applications, demanding large emission currents and lower operational voltages. Moreover, the FE current stability recorded on these samples confirms their promising performance. Thus, the present investigation brings out a great promise of TiS3 nanosheets and nanoribbons as field emitters for vacuum nanoelectronics devices.
Keywords: Current stability; field emission; nanoribbon; nanosheets; TiS3

Total synthesis and absolute configuration determination of the α-glycosidase inhibitor (3S,4R)-6-Acetyl-3-hydroxy-2,2-dimethylchroman-4-yl (Z)-2-Methylbut-2-enoate from Ageratina grandifolia - Dandawate, Monica; Choudhury, Rahul; Krishna, Gamidi Rama; Reddy, D. Srinivasa (Journal of Natural Products, 2023)
Herein, we report the first total synthesis of & alpha;-glycosidaseinhibitor (3R, 4S)-6-acetyl-3-hydroxy-2,2-dimethylchroman-4-yl(Z)-2-methylbut-2-enoate as well as its enantiomer.Our synthesis confirms the chromane structure separately proposedby Navarro-Vazquez and Mata, on the basis of DFT computations. Furthermore,our synthesis allowed us to determine the absolute configuration ofthe natural compound as (3S, 4R)and not (3R, 4S).

Transient response to perturbations in flow synthesis of citrate capped gold nanoparticles - Bari, Atul H.; Shukla, Neerja; Gavriilidis, Asterios; Kulkarni, Amol A. (Biochemical Engineering Journal, 2023)
This work reports the transient behavior of continuous flow synthesis of gold nanoparticles (Au NPs) when subjected to perturbations in operating conditions using controlled experiments. The intricacies are captured through a detailed mathematical model. Reversed Turkevich protocol was used for synthesis of Au NPs. The synthesis was first studied in batch mode to investigate the reaction kinetics and reproducibility of the process. The optimal set of operating conditions viz., residence time, flow rate, temperature was then used for flow synthesis in a 2 m, 1/16 & DPRIME;Polytetrafluoroethylene (PTFE) reactor with micromixer. Reactor clogging was avoided by using segmented flow. Inline UV measurement was used for real time monitoring of the process. Transient experiments were performed by abruptly changing the operating conditions. A mathematical model was found to be accurate in predicting the transient behavior of the exit precursor concentration and the particle size for unsteady state synthesis. Even a small change in process variables for short duration was found to disturb the quality of Au NPs for a significantly longer duration. Of the three operating parameters, the effect of temperature variation was seen to have a prolonged effect where the system remained in unsteady state for long time.
Keywords: continuous flow synthesis; gold nanoparticles; Particle size; segmented flow; Unsteady behavior

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

Ultra-fast electro-reduction and activation of graphene for high energy density wearable supercapacitor asymmetrically designed with MXene - Karim, Golam Masud; Dutta, Pronoy; Majumdar, Abhisek; Patra, Amalika; Deb, Sujit Kumar; Das, Snehasish; Dambhare, Neha V.; Rath, Arup K.; Maiti, Uday Narayan (Carbon, 2023)
Controlled perforation of graphene is vital to surpass the performance of supercapacitors that rely on their pristine form. However, their practical utilization has been halted by energy-inefficient and lengthy processing. Here, we are reporting a pulse Joule heating strategy for on-site reduction and activation to realize a multimodal porous framework made of perforated graphene using millisecond current pulses. The multimodal porosity and surface functionalities of graphene were regulated at an ultrafast rate by passing a transient current. Asdeveloped ready-to-use electrode composed of nano-to-macro multimodal porosity displays high areal capacitance of 380.2 mF cm-2 in symmetric two-electrode configuration, which is nearly 1.6 times higher than the nonelectro activated counterpart. Furthermore, a high-performance wearable asymmetric supercapacitor with an areal energy density of 107.8 mu Wh cm-2 was realized using this multimodal porous graphene in combination with suitable negative electrodes made of MXene. High energy density, together with stable and repeatable performance of the wearable device for 10000 cycles of charge-discharge and 5000 cycles of bending, signifies the importance of the as-developed device for practical wearable applications. Direct, simple processing of electrodes and orders of magnitude lower cost-and-processing-time can make the process appealing for practical wearable and other energy storage applications.
Keywords: asymmetric supercapacitor; Graphene activation; Joule heating; Solid-state supercapacitor; Wearable device

Ultrasound assisted synthesis of spirooxindolo-1,2,4-oxadiazoles via [3+2] cycloaddition reaction and their anti-cancer activity - Kanchrana, Madhu; Allaka, Bhargava Sai; Krishna, Gamidi Rama; Basavoju, Srinivas (ARKIVOC, 2023)

Understanding the nucleation and growth kinetics of the microwave-assisted synthesis of silver nanowires - Sonawane, Jayesh R.; Patil, Suneha; Kulkarni, Amol A. (Industrial & Engineering Chemistry Research, 2023)
Here, we present a detailed study of understanding the nucleation and growth kinetics of silver nanowire synthesis under microwave irradiation. The approach includes studying the effect of various parameters (viz., microwave power, reaction temperature, reaction time, substrate concentration, etc.) on the rate of nucleation and growth, as well as on the yield and morphology of silver nanowires. It is found that microwave power is the most important factor in leading to almost complete conversion of the substrate along with high aspect ratio nanowires in a short reaction time. Based on the observations, here, we have proposed a three-step growth kinetics mechanism for the synthesis of silver nanowires under the influence of microwaves. The approach comprises the autocatalytic growth of stable multiple twin particles after the nucleation process and their unidirectional growth to form nanowires. The FW autocatalytic model and the JMAK Avrami model were used to validate the proposed mechanism of AgNW formation based on our experimental results. The model predictions match very well with the conversion and yield of AgNWs. At the optimized conditions, wires with a 42 nm diameter and 94% yield were achieved within 4 min.

Understanding the stability of an unprecedented Si-Be bond within quantum confinement - Maneri, Asma Harun; Krishnamurty, Sailaja; Joshi, Krati (ACS Omega, 2023)
As of today, the Si-Be bond remains underexplored in the literature, and therefore its anomalous behavior continues to be an unsolved puzzle to date. Therefore, the present study aims at evaluating the integrity of an unprecedented Si-Be bond within quantum confinement. To accomplish this, first-principles-based calculation are performed on Be-doped silicon clusters with atomic sizes 6, 7, and 10. Silicon clusters are sequentially doped with one, two, and three Be atoms, and their thermal response is registered in the temperature range of 200-1500 K, which discloses several research findings. During the course of the simulations, the clusters face various thermal events such as solid cluster phase, rapid structural metamorphosis, and fragmentation. Si-Be nanoalloy clusters are noted to be thermally stable at lower temperatures (200-700 K); however, they begins to disintegrate earlier at a temperature as low as 800 K. This lower stability is attributed to the weak nature of Si and Be heteroatomic interactions, which is corroborated from the structural and electronic property analysis of the doped clusters. In addition to this, the performance of Be-doped clusters at finite temperatures is also compared with the thermal response of two other popular systems, viz., C-and B-doped silicon clusters.

Understanding the thermal stability of a 3d, 4d, and 5d element doped aluminium nanocluster through BOMD simulations - Samudre, Nikhil S.; Singh, Chandrodai Pratap; Krishnamurty, Sailaja (Molecular Simulation, 2023)
Endohedrally doped atomic clusters have generated considerable interest among computational chemists on account of their tunable chemical properties that mimic a super atom. Such endohedrally doped clusters have also been experimentally realised in the more recent past. The present work explores the practical existence of 3d, 4d and 5d doped aluminium clusters, more specifically doped Al13 cluster, by evaluating systematically their structural stability through the first principle molecular dynamical simulations. Born-Oppenheimer Molecular Dynamics (BOMD) simulations have been carried out on Al12X atomic clusters where X = Ti, V, Fe, Co, Ni, Cu, Zn, Y, Mo, Ru, Rh and W are in endohedral position. The thermal stability of such endohedrally doped clusters is quantified through parameters such as delta(rms), MSD and is an element of(pro). Electronic structure calculations reveal that endohedral doping of only Rh, Cu and Zn is preferred in the Al-13 cluster. Other dopants prefer to remain on the surface positions. However, finite temperature calculations reveal that the Al12Zn cluster undergoes surface modifications from 300K leading to a distorted icosahedral structure. Al12Cu cluster in quartet spin state is the only thermally stable cluster with Cu remaining in the endohedral position and structure retaining icosahedral confirmation till 700K.
Keywords: Al-13 atomic cluster; BOMD simulations; DFT; Endohedral doping; super atom

Unleashing methylammonium-guanidinium lead iodide hybrid perovskite spherulitic microstructures: a structural and morphological investigation - Mukul, Monika; Kaliaperumal, Selvaraj; Rani, Mamta; Tripathi, Surya Kant (MRS Communications, 2023)
Perovskites can offer an attractive replacement option for existing commercial solar technologies. Herein microstructure plays an important role in improving the efficiency and stability of solar cells. Previously unidentified spherulitic microstructures of self-assembled polycrystalline perovskites are explored in this report. For this an intermediate phase of a promising guanidinium (GUAI)-rich perovskite has been investigated for its structural and morphological properties. This study infuses new insight into the evolution of perovskite microstructure from heterogeneity to homogeneity, as a result unravels the structure of perovskite embryonic spherulites, lamellar arrangements, transcrystalline nature, novel spherulites bridging, hole nucleation, impingement, and defects.
Keywords: Microstructure; Morphology; Nucleation & growth; Perovskites; Phase transformation; X-ray diffraction (XRD)

Unlike RNA-TBA (rTBA), iso-rTBA, the 2 `-5 `-linked RNA-thrombin-binding aptamer, is a functional equivalent of TBA - Wagh, Atish A. A.; Kumar, Vaijayanti A. A.; Ravindranathan, Sapna; Fernandes, Moneesha (Chemical Communications, 2023)
An antiparallel, functional RNA G-quadruplex of the 2 `-5 `-linked thrombin-binding aptamer (iso-rTBA) is reported for the first time. It can inhibit clotting and is remarkably stable to nuclease-degradation, besides having high thermal stability. It is thus, a superior candidate to TBA, rTBA or isoTBA, for further development as an anticoagulant.

Unlocking the potential of proton conductivity in guanidinium-based ionic covalent organic nanosheets (iCONs) through pore interior functionalization - Kumar, Sushil; Hu, Jiahui; Pandikassala, Ajmal; Kurungot, Sreekumar; Addicoat, Matthew A.; Szekely, Gyorgy (Applied Materials Today, 2023)
Recently, scientists have been exploring the incorporation of proton carriers such as water and phosphoric acid (PA) into the pores and channels of porous materials to enhance proton conduction performance. Ionic covalent organic nanosheets (iCONs) have been identified as promising functional materials due to their inbuilt ionic interfaces, which can facilitate strong interaction with counter ions present inside the pore structure and thus shorten ion transport pathways. However, there is a lack of research related to proton conductivity in iCONs loaded with PA. To address this, we prepared three functionalized guanidinium-based iCONs using a solvothermal condensation reaction between guanidinium amine (TG) and functionalized terephthaldehyde (Da, Dha, and Dma). PA was also incorporated into the iCON structure via ex situ loading to observe its effects on proton conduction performance. The results showed that both the iCONs and PA-iCONs were highly stable in water, organic solvents, acidic and basic media. Amongst these PA-iCONs, one with hydroxyl-functionalization (PA-DhaTG) displayed high proton conductivity at 90 degrees C and 95% relative humidity due to a Grotthuss mechanism for protons. These functionalized guanidinium-based iCONs could prove useful for applications in energy conversion devices.
Keywords: chemical stability; Functionalized pore interior; Guanidinium group; ionic covalent organic nanosheets; proton conductivity

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

Unusual ligand assistance in molecular electrocatalysis via interfacial proton charge assembly - Mukhopadhyay, Sanchayita; Kottaichamy, Alagar Raja; Chame, Pallavi Vyankuram; Ghosh, Prasenjit; Vinod, Chathakudath Prabhakaran; Makri Nimbegondi Kotresh, Harish; Kanade, Sandeep C.; Thotiyl, Musthafa Ottakam (Journal of Physical Chemistry Letters, 2023)
We show that the ability of the ligand to reorganizethe electricdouble layer (EDL) often dominates the electrocatalysis contrary totheir inductive effect in the spectrochemical series, leading to counterintuitiveelectrocatalysis. With water oxidation and chlorine evolution as theprobe reactions, the same catalytic entity with carboxy functionalizedligand exhibited surprisingly higher electrochemical activity in comparisonto the aggressively electron-withdrawing nitro functionalized ligands,which is contrary to their actual location in the spectrochemicalseries. Spectroscopic and electrochemical analyses suggest the enrichmentof catalytically active species in the carboxy substituted ligandvia proton charge assembly in the EDL that in turn enhances the kineticsof the overall electrochemical process. This demonstration of lessobvious ligands becoming indispensable in electrocatalysis suggestsa blind designing of ligands solely based on their inductive effectshould be reconsidered as it will prevent the utilization of the maximumpotential of the molecule in electrocatalysis.

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

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

Wadsworth-emmons reaction by using the fluorapatite catalyst: kinetic studies - Vishwakarma, Rakhi; Vinod, Chathakudath P.; Rathod, Virendra; Kantam, Mannepalli Lakshmi (Industrial & Engineering Chemistry Research, 2023)
Wadsworth-Emmons reaction was successfully carriedout byusing the fluorapatite (FAP) catalyst. The reaction of 2-methoxybenzaldehydeand triethylphosphonoacetate using FAP afforded & alpha;,& beta;-unsaturatedester with 100% conversion and 80% selectivity. A kinetic model wasvalidated at different temperatures by Langmuir-Hinshelwood-Hougen-Watson(LHHW), and the absence of mass transfer resistance was verified bythe Weisz Prater criterion. The effect of different catalysts, temperature,catalyst loading, solvent, mole ratio, and speed of stirring was studied.The FAP catalyst was characterized by Fourier transform infrared spectroscopy,Brunauer-Emmett-Teller method, nitrogen adsorption-desorption,transmission electron microscopy, energy-dispersive X-ray spectroscopy,temperature programmed desorption (TPD-NH3), X-ray diffraction,and X-ray photoelectron spectroscopy. The FAP catalyst was found tobe stable up to three recycles with no loss in activity.

Wavelet coherence phase analysis decodes the universal switching mechanism of Ras GTPase superfamily - Motiwala, Zenia; Sandholu, Anand S.; Sengupta, Durba; Kulkarni, Kiran (iScience, 2023)
The Ras superfamily of GTPases regulate critical cellular processes by shuttling between GTP-bound ON and GDP-bound OFF states. This switching mechanism is attributed to the conformational changes in two loops, SWI and SWII, upon GTP binding and hydrolysis. Since these conformational changes vary across the Ras superfamily, there is no generic parameter to define their functional states. A unique wavelet coherence (WC) analysis-based approach developed here shows that the structural changes in switch regions could be mapped onto the wavelet coherence phase couplings (WPCs). Thus, WPCs could serve as unique parameters to define their functional states. Disentanglement of WPCs in oncogenic GTPases shows how breakdown of structural allostery leads to their aberrant function. These observations stand out even for simulated ensemble of switch region conformers. Overall, for the first time, we show that WPCs could unravel the latent structural deviations in Ras proteins to decode their universal switching mechanism.

Whole genome sequencing and comparative genomics of Indian isolates of wheat spot blotch pathogen bipolaris sorokiniana reveals expansion of pathogenicity gene clusters - Yadav, Sagar; Raazi, Zarrine; Shivaraj, Sheelavanta Matha; Somani, Deepika; Prashant, Ramya; Kulkarni, Abhijeet; Kumar, Rajeev; Biradar, Suma; Desai, Shreenivas; Kadoo, Narendra (Pathogens, 2023)
Spot blotch is a highly destructive disease in wheat caused by the fungal pathogen Bipolaris sorokiniana (teleomorph, Cochliobolus sativus). It is prevalent in warm and humid areas, including Africa, Asia, Latin America, and the USA. In the present study, twelve isolates of B. sorokiniana were collected from wheat fields in three different geographical locations in India. The pathogenicity of seven sporulating isolates was assessed on `DDK 1025', a spot blotch-susceptible wheat variety under greenhouse conditions. The isolate `D2' illustrated the highest virulence, followed by `SI' and `BS52'. These three isolates were sequenced using the Illumina HiSeq1000 platform. The estimated genome sizes of the isolates BS52, D2, and SI were 35.19 MB, 39.32 MB, and 32.76 MB, with GC contents of 48.48%, 50.43%, and 49.42%, respectively. The numbers of pathogenicity genes identified in BS52, D2, and SI isolates were 2015, 2476, and 2018, respectively. Notably, the isolate D2 exhibited a relatively larger genome with expanded arsenals of Biosynthetic Gene Clusters (BGCs), CAZymes, secretome, and pathogenicity genes, which could have contributed to its higher virulence among the tested isolates. This study provides the first comparative genome analysis of the Indian isolates of B. sorokiniana using whole genome sequencing.
Keywords: Bipolaris sorokiniana; CAZyme; comparative genomics; spot blotch; whole genome sequencing

2-Pyridone-directed CuII-catalyzed general method of C(sp2)-H activation for C-S, C-Se, and C-N cross-coupling: easy access to aryl thioethers, selenide ethers, and sulfonamides and DFT study - Pati, Tanmay K.; Molla, Sabir Ali; Ghosh, Narendra Nath; Kundu, Mrinalkanti; Ajarul, Sk; Maity, Pradip; Khamrai, Uttam; Maiti, Dilip K. (Journal of Organic Chemistry, 2024)
We have demonstrated N-substituted 2-pyridones as an N,O-directing group for selective C(sp(2))-H-activated thiolation, selenylation, and sulfonamidation of ortho C-H bonds of benzamides. This method utilizes a cost-effective Cu(II)-salt catalyst instead of precious metal catalysts, achieving high yields, including gram-scale synthesis and excellent functional group tolerance. We applied this protocol to access 30 different compounds with high yields, demonstrating thiolation of fluorine-substituted benzamides as well. Density functional theory (DFT) calculations support the mechanism, including acetate-supported concerted metalation deprotonation (CMD) steps and the unique role of dimethyl sulfoxide (DMSO) solvent. The facile synthesis of pharmaceutically important sulfonamides and other compounds highlights the method's potential in chemistry and medicinal chemistry.

4-aminoantipyrine linked bis-1,2,3-triazole based probes for Cu(II) sensing - Lal, Bajrang; Kumar, Sachin; Tittal, Ram Kumar; Singh, Gurleen; Singh, Jandeep; Ghule, Vikas D.; Mathpati, Ramling S.; Sabane, Jagjivan K. (Journal of Molecular Structure, 2024)
Herein, two molecular probes of 4-aminoantipyrine-linked bis-1,2,3-triazoles have been studied for metal ion sensing applications. The crystal structure of one of the probes named as 4,4 `-((4,4 `-(((1,5-dimethyl- 3- oxo- 2- phenyl- 2,3- dihydro- 1H- pyrazol- 4-yl) azanediyl) bis(methylene))bis(1H-1,2,3-triazole-4,1-diyl))bis(methylene))dibenzonit rile (3b) crystalizes in Monoclinic crystal system in P 1 21/n 1 space group. Both probes responded more strongly and selectively to Cu(II) than other tested metal ions (K+, Na+, Mg2+, Ba2+, Ca2+, Cr3+, Mn2+, Co2+, Zn2+, Cd2+, Ni2+, Hg2+, and Pb2+). Job's plot suggested a 1:1 stoichiometric ratio of ligand and metal ion. Both probes showed an association constant of 2.48 x 10(3) M-1 and 3.73 x 10(3) M-1 through Benesi-Hildebrand (B-H) plot. The geometries of both probes and their complexes were optimized by DFT using B3LYP/6-311 G(d,p) and B3LYP/LanL2DZ basis sets, and properties were supported by Mulliken atomic charge and Molecular electrostatic potential. Molecular docking on both probes and their complexes with Type-II topoisomerases(PDB ID: 4G0V) protein was conducted to foretastes anticancer activity.
Keywords: 2; 3-Triazole; 4-aminoantipyrine; and Molecular docking; Bis-1; Cu2+ Sensor; DFT; X-ray crystallography

ABPBI-based hollow fiber membranes for forward osmosis (FO) possessing low reverse salt flux - Thorat, Nitin M.; Lele, Ashish K.; Kharul, Ulhas K. (Desalination and Water Treatment, 2024)
The poly(2,5-Benzimidazole), known for its excellent thermochemical stability, was evaluated as a membrane material for forward osmosis. The dope in methane sulfonic acid was used to make hollow fiber membranes. The availability of bound MSA in HFMs was compared with its neutral form. Aqueous solutions of two common salts reported for FO (NaCl and MgCl2) were used as a draw solution at varying concentrations. The performance was determined in terms of water flux and reverse salt flux. The long-term performance of the membrane was assessed. The heat pretreatment of membranes was beneficial in offering low reverse salt flux, a crucial parameter in FO. The heat treatment at 350 degrees C exhibited excellent performance of low-RSF, irrespective of the draw solute used. The presence of MSA in the membrane matrix was found to be beneficial. Present HFMs exhibited reverse salt flux as low as 0.003 mol m-2 h-1 using 2 mol L-1 MgCl2 as a draw solution. The water flux of present membranes was lower than that of reported FO-membranes, which is attributable to the larger thickness of the present membranes. The findings will be used to make ABPBI-based membranes in thin form to elevate the fluxes and their practical applicability.
Keywords: ABPBI; Forward osmosis; Hollow fiber membrane; Low reverse salt flux

Access to NHC-Boryl mono- and bis-selenide and utility as mild selenium transfer reagent including to the C-F bond - Kundu, Gargi; Amrutha, P. R.; Tothadi, Srinu; Sen, Sakya S. (Chemistry- a european journal, 2024)
Reactions of 5-SIDipp & sdot; BH3 (5-SIDipp=1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene) (1) with diphenyldiselenide provide access to 5-SIDipp-boryl mono- (5-SIDipp & sdot; BH2SePh) (2) and bis-selenide (5-SIDipp & sdot; BH(SePh)2) (3). The facile cleavage of the B-Se bond makes 2 a neutral source of selenium nucleophiles in substitutions reactions with benzyl bromides, and provide access to the corresponding selenoethers. The direct transformations of one of the C(sp2)-F bonds of C5F5N and C6F5CF3 to C-Se bonds have also been achieved by the use of 2 without employing transition-metal catalysts. While it was previously established that C6F6 could undergo complete defluoroselenation under harsh conditions, we successfully achieved partial defluorination of C6F6 by employing 2 as a mild selenide transfer reagent. During the formation of C-Se bonds through the cleavage of C-F bonds, the potential by-product NHC & sdot; BH2F undergoes ring expansion of the NHC, leading to the formation of the six-membered diaazafluoroborinane (7). Access to NHC & sdot; boryl mono- and bis-selenides from NHC & sdot; BH3 has been achieved. The boryl mono selenide has been demonstrated to function as a selenium transfer reagent, enabling the synthesis of selenoethers from benzyl bromide. Additionally, it can also facilitate the conversion of the challenging aromatic C-F bond to a C-Se bond, resulting in concomitant ring expansion of NHC & sdot; haloborane.image
Keywords: boron; C-F Bond Activation; N-Heterocyclic carbene; Ring expansion; Selenium

Activation of carbon disulfide by a hypersilyl germylene - Ajithkumar, V. S.; Khilari, Nripen; Ghanwat, Pratiksha B.; Venugopal, Geethu; Koley, Debasis; Sen, Sakya S. (Dalton Transactions, 2024)
In this work, the insertion of CS2 into the Ge-Si bond of PhC(NtBu)2Ge-Si(SiMe3)3 (1) has been investigated, resulting in the formation of PhC(NtBu)2Ge-C( 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 S)-S-Si(SiMe3)3 (2). Interestingly, the addition of NHC to 2 allows the release of NHCCS2 with concomitant regeneration of 1. Addition of another equivalent of 1 or an analogous hypersilyl silylene, [PhC(NtBu)2Si-Si(SiMe3)3], to 2 led to the formation of compounds with a GeS (3) or a SiS (4) bond. In this work, the insertion of CS2 into the Ge-Si bond of PhC(NtBu)2Ge-Si(SiMe3)3 (1) has been investigated, resulting in the formation of PhC(NtBu)2Ge-C(S)-S-Si(SiMe3)3 (2).

Advanced 3D network of N-doped graphitic carbon with FeNi alloy embedding for high-performance rechargeable Zn-air batteries - Pandikassala, Ajmal; Kurian, Maria; Gangadharan, Pranav K.; Torris, Arun; Kurungot, Sreekumar (Advanced Sustainable Systems, 2024)
Despite the significant progress in Zn-air batteries (ZABs), their widespread use in the rechargeable sector is hindered due to the scarcity of efficient bifunctional oxygen catalysts that can catalyze both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). To address this, an ORR/OER bifunctional electrocatalyst is designed with ultrafine alloyed FeNi nanoparticles encapsulated in a 3D interconnected N- doped carbon network structure, featuring a carbon nitride backbone enclosed in graphitic carbon. The FeNi electrocatalyst (3DFeNiPDC) showed good bifunctional activity toward both ORR and OER in the basic medium with a low overpotential value of 30 mV for ORR and 6 mV for OER compared to its state-of-the-art counterparts Pt/C, and RuO2, respectively. Utilizing 3DFeNiPDC in a rechargeable Zn-air battery (RZAB) yields an open circuit voltage (OCV) of 1.35 V, a maximum power density of 232 mW cm-2, and an energy density of 707 W h kg-1. Additionally, a flexible RZAB employing 3DFeNiPDC demonstrates an OCV of 1.4 V with various bending angles. These finding suggest 3DFeNiPDC as a viable alternative to noble metal-based RZABs, offering superior bifunctional electrocatalytic activity and stability, particularly with its enhanced air-breathing properties facilitating improved operability under practical conditions. The bifunctional electrocatalytic activity of FeNi alloy nanoparticles embedded in a 3D- interconnected N-doped graphitic carbon (3DFeNiPDC) for both oxygen reduction and oxygen evolution is studied. The 3D architecture and core-shell characteristics of FeNi alloy nanoparticles provide better activity and stability for oxygen electrocatalysis. The electrocatalytic activity of 3DFeNiPDC has been exploited for liquid-state and solid-state flexible rechargeable zinc-air batteries. image
Keywords: Oxygen Evolution Reaction; oxygen reduction reaction; rechargeable flexible zinc-air battery

Alternative synthetic route for the pharmacophore of anticancer agent: triazolopyridazine derivative - Karche, Ranjit S.; Bankar, Shubham R.; Jadhav, Vrushali H. (Tetrahedron Letters, 2024)
ATAD2 has received attention as one of the potential oncogene with tumor-promoting aspects in many malignancies. ATAD2 is a highly conserved bromodomain family protein that exerts its biological functions by mainly AAA ATPase and bromodomain. Several small molecule inhibitors have been described in the literature. AZ13824374 (1) recently reported by Holt and co-workers showed promising in vitro (bio-chemical, cellular) and antiproliferative activity in range of breast cancer models. In this work, we described scalable synthetic route for triazolopyridazine derivative (2), a key intermediate of AZ13824374 (1) without using CO in the process. Triazolopyridazine helps to attain the bioactive conformation for AZ13824374 (1) through its crucial interaction with Tyr 1021 of ATAD2. Additionally, triazolopyridazine is extensively used as an intermediate for anticancer agents. This encouraged us to develop cost-effective and scalable process for it.
Keywords: Alternative process; Anticancer; Triazolopyridazine

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

Aminoacylase efficiently hydrolyses fatty acid amino acid conjugates of Helicoverpa armigera potentially to increase the pool of glutamine - Kallure, Gopal S.; Sahoo, Shubhranshu Shekhar; Kale, Rutuja S.; Barvkar, Vitthal T.; Kontham, Ravindar; Giri, Ashok P. (Insect Biochemistry and Molecular Biology, 2024)
One of the most prevalent bioactive molecules present in the oral secretion (OS) of lepidopteran insects is fatty acid amino acid conjugates (FACs). Insect dietary components have influence on the synthesis and retaining the pool of FACs in the OS. We noted differential and diet-specific accumulation of FACs in the OS of Helicoverpa armigera by using Liquid Chromatography-Quadrupole Time of Flight Mass Spectrometry. Interestingly, we identified FACs hydrolyzing enzyme aminoacylase (HaACY) in the OS of H. armigera through proteomic analysis. Next, we have cloned, expressed, and purified active recombinant HaACY in the bacterial system. Recombinant HaACY hydrolyzes all the six identified FACs in the OS of H. armigera larvae fed on host and non-host plants and releases respective fatty acid and glutamine. In these six FACs, fatty acid moieties vary while amino acid glutamine was common. Glutamine obtained upon hydrolysis of FACs by HaACY might serve as an amino acid pool for insect growth and development. To understand the substrate choices of HaACY, we chemically synthesized, purified, and characterized all the six FACs. Interestingly, rHaACY also shows hydrolysis of synthetic FACs into respective fatty acid and glutamine. Our results underline the importance of diet on accumulation of FACs and role of aminoacylase(s) in regulating the level of FACs and glutamine.
Keywords: Aminoacylase; Fatty acid amino acid conjugates; Glutamine; Helicoverpa armigera; Oral secretion

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

Application of eco-friendly cationic celluloses for effective sludge dewatering - Menon, Snehal; Suresha, P. R.; Khairnar, Ajay; Kalyanraman, V. (Water Air and Soil Pollution, 2024)
The study presents the application of cationic celluloses in sludge dewatering. The source of cellulose used in this study were microcrystalline cellulose and alkaline-treated rice straw. The cationic celluloses were synthesized in a two-step reaction involving oxidation of cellulose with sodium periodate and followed by Schiff base reaction with Girard reagent T to introduce quaternary ammonium cations. The functional groups and chemical structure were confirmed by FTIR and NMR spectroscopy. The molecular weight and cationicity index of cationic cellulose were determined. Owing to their low molecular weight, the cationic celluloses functioned as coagulants and brought about charge neutralization through electric patches. The cationic celluloses were effective in promoting rapid sludge settling and improving the sludge filterability. The cationic celluloses are eco-friendly and non-toxic alternatives to acrylamide-based flocculants.
Keywords: biodegradable; Cationic cellulose; coagulation; Sludge dewatering; Wastewater treatment

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

Bacteriophages: status quo and emerging trends toward one health approach - Samson, Rachel; Dharne, Mahesh; Khairnar, Krishna (Science of The Total Environment, 2024)
The alarming rise in antimicrobial resistance (AMR) among the drug-resistant pathogens has been attributed to the ESKAPEE group (Enterococcus faecium, Staphylococcus aureus, Klebsiella pneumoniae, Acinetobacter baumanii, Pseudomonas aeruginosa, Enterobacter sp., and Escherichia coli). Recently, these AMR microbes have become difficult to treat, as they have rendered the existing therapeutics ineffective. Thus, there is an urgent need for effective alternatives to lessen or eliminate the current infections and limit the spread of emerging diseases under the ``One Health'' framework. Bacteriophages (phages) are naturally occurring biological resources with extraordinary potential for biomedical, agriculture/food safety, environmental protection, and energy production. Specific unique properties of phages, such as their bactericidal activity, host specificity, potency, and biocompatibility, make them desirable candidates in therapeutics. The recent biotechnological advancement has broadened the repertoire of phage applications in nanoscience, material science, physical chemistry, and soft
Keywords: Antimicrobial resistance (AMR); Bacteriophages; One-health; Therapeutics commercialization

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

Biocatalysis enables the scalable conversion of biobased furans into various furfurylamines - Giri, Pritam; Lim, Seonga; Khobragade, Taresh P.; Pagar, Amol D.; Patil, Mahesh D.; Sarak, Sharad; Jeon, Hyunwoo; Joo, Sangwoo; Goh, Younghwan; Jung, Seohee; Jang, Yu-Jeong; Choi, Seung Beom; et al. (NATURE COMMUNICATIONS, 2024)
Keywords: Biomass; OMEGA-TRANSAMINASE; OXIDASE; Reductive amination; SPECIFICITY

Bi(OTf)3-promoted cascade annulation of hydroxy-pyranones and unsaturated γ-ketoesters for the construction of polycyclic bridged pyrano-furopyranones - Rathod, Akshay B.; Borade, Balasaheb R.; Sambherao, Pooja I.; Kontham, Ravindar (Organic and biomolecular chemistry, 2024)
An efficient protocol for constructing complex three dimensional polycyclic bridged chromano-furopyranones and pyrano-furopyranones (closely related to bioactive natural products) via bismuth(III)-catalyzed cascade annulation of hydroxy-pyranones and unsaturated gamma-ketoesters is presented. This process involves intermolecular Michael addition, intramolecular hemiketalization, lactonization, formation of one C-C bond and two C-O bonds, rings, and contiguous stereocenters.
Keywords: 1 3-Dicarbonyl Compounds; alkynols; Coumarins; Fungus

Block copolymer self-assembly: exploitation of hydrogen bonding for nanoparticle morphology control via incorporation of triazine based comonomers by RAFT polymerization - Haque, Farah; Thompson, Steven W.; Ishizuka, Fumi; Kuchel, Rhiannon P.; Singh, Dharmendra; Sanjayan, Gangadhar J.; Zetterlund, Per B. (Small, 2024)
Synthesis of polymeric nanoparticles of controlled non-spherical morphology is of profound interest for a wide variety of potential applications. Self-assembly of amphiphilic diblock copolymers is an attractive bottom-up approach to prepare such nanoparticles. In the present work, RAFT polymerization is employed to synthesize a variety of poly(N,N-dimethylacrylamide)-b-poly[butyl acrylate-stat-GCB] copolymers, where GCB represents vinyl monomer containing triazine based Janus guanine-cytosine nucleobase motifs featuring multiple hydrogen bonding arrays. Hydrogen bonding between the hydrophobic blocks exert significant influence on the morphology of the resulting nanoparticles self-assembled in water. The Janus feature of the GCB moieties makes it possible to use a single polymer type in self-assembly, unlike previous work exploiting, e.g., thymine-containing polymer and adenine-containing polymer. Moreover, the strength of the hydrogen bonding interactions enables use of a low molar fraction of GCB units, thereby rendering it possible to use the present approach for copolymers based on common vinyl monomers for the development of advanced nanomaterials.

Boron- and oxygen-doped π-extended helical nanographene with circularly polarised thermally activated delayed fluorescence - Venugopal, Geethu; Kumar, Viksit; Jadhav, Ashok Badrinarayan; Dongre, Sangram D.; Khan, Abujunaid; Gonnade, Rajesh; Kumar, Jatish; Santhosh Babu, Sukumaran (Chemistry-A European Journal, 2024)
Helical nanographenes have garnered substantial attention owing to their finely adjustable optical and semiconducting properties. The strategic integration of both helicity and heteroatoms into the nanographene structure, facilitated by a boron-oxygen-based multiple resonance (MR) thermally activated delayed fluorescence (TADF), elevates its photophysical and chiroptical features. This signifies the introduction of an elegant category of helical nanographene that combines optical (TADF) and chiroptical (CPL) features. In this direction, we report the synthesis, optical, and chiroptical properties of boron, oxygen-doped pi-extended helical nanographene. The pi-extension induces distortion in the DOBNA-incorporated nanographene, endowing a pair of helicenes, (P)-B2NG, and (M)-B2NG exhibiting circularly polarized luminescence with glum of -2.3x10-3 and +2.5x10-3, respectively. B2NG exhibited MR-TADF with a lifetime below 5 mu s, and a reasonably high fluorescence quantum yield (50 %). Our molecular design enriches the optical and chiroptical properties of nanographenes and opens up new opportunities in multidisciplinary fields. B, O-doped pi-extended helical nanographene has been explored for its optical and chiroptical properties. The presence of helical and nanographene segments stabilize the helicity and imparts tunable optical properties. Helical nanographene display circularly polarized thermally activated delayed fluorescence. image
Keywords: circularly polarized luminescence; DOBNA; dual emission; nanographene; TADF

Breaking the inactivity of MXenes to drive Ampere-level selective oxygen evolution reaction in seawater - Gbadamasi, Sharafadeen; Loomba, Suraj; Haris, Muhammad; Khan, Muhammad Waqas; Maibam, Ashakiran; Mousavi, Seyed Mahdi; Mahmud, Sofiu; Thomsen, Lars; Tadich, Anton; BabaRao, Ravichandar; Xian, Jian; Mahmood, Nasir (MATERIALS SCIENCE & ENGINEERING R-REPORTS, 2024)
Keywords: 2D heterostructures; Metal-organic framework; Oxygen Evolution Reaction

Breaking the Pt electron symmetry and OH spillover towards ptir active center for performance modulation in direct ammonia fuel cell - Barik, Sidharth; Kharabe, Geeta Pandurang; Samal, Pragnya Paramita; Urkude, Rajashri R.; Kumar, Sachin; Yoyakki, Athira; Vinod, C. P.; Krishnamurty, Sailaja; Kurungot, Sreekumar (Small, 2024)
The growing interest in low-temperature direct ammonia fuel cells (DAFCs) arises from the utilization of a carbon-neutral ammonia source; however, DAFCs encounter significant electrode overpotentials due to the substantial energy barrier of the *NH2 to *NH dehydrogenation, compounded by the facile deactivation by *N on the Pt surface. In this work, a unique catalyst, Pt4Ir@AlOOH/NGr i.e., Pt4Ir/ANGr, is introduced composed of PtIr alloy nanoparticles controllably decorated on the pseudo-boehmite phase of AlOOH-supported nitrogen-doped reduced graphene (AlOOH/NGr) composite, synthesized via the polyol reduction method. The detailed studies on the structural and electronic properties of the catalyst by XAS and VB-XPS reveal the possible electronic modulations. The optimized Pt4Ir/ANGr composition exhibits a significantly improved onset potential and mass activity for AOR. The DFT study confirms the OHad species spillover by AlOOH and Pt4Ir (100) facilitates the conversion of the *NH2 to *NH with minimal energy barriers. Finally, testing of DAFC at the system level using a membrane electrode assembly (MEA) with Pt4Ir/ANGr as the anode catalyst, demonstrating the suitability of the catalyst for its practical applications. This study thus uncovers the potential of the Pt4Ir catalyst in synergy with ANGr, largely addressing the challenges in hydrogen transportation, storage, and safety within DAFCs. In this article, a versatile catalyst, Pt4Ir/ANGr, is introduced composed of PtIr alloy nanoparticles decorated on AlOOH/NGr composite. The AlOOH provides an -OH-rich surface conducive to the facile adsorption and decoration of the PtIr alloy nanoparticles and OHad species spillover from AlOOH to the Pt4Ir active center during AOR, further validating the higher experimental activity obtained in Pt4Ir/ANGr. image
Keywords: ammonia oxidation reaction (AOR); d-band center; density functional theory (DFT) study; direct ammonia fuel cells; hydroxyl spillover effect; XAS analysis

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

Cathode|electrolyte interface engineering by a hydrogel polymer electrolyte for a 3D porous high-voltage cathode material in a quasi-solid-state zinc metal battery by in situ polymerization - Puthiyaveetil, Priyanka Pandinhare; Torris, Arun; Dilwale, Swati; Kanheerampockil, Fayis; Kurungot, Sreekumar (SMALL, 2024)
This work highlights the development of a superior cathode|electrolyte interface for the quasi solid-state rechargeable zinc metal battery (QSS-RZMB) by a novel hydrogel polymer electrolyte using an ultraviolet (UV) light-assisted in situ polymerization strategy. By integrating the cathode with a thin layer of the hydrogel polymer electrolyte, this technique produces an integrated interface that ensures quick Zn2+ ion conduction. The coexistence of nanowires for direct electron routes and the enhanced electrolyte ion infiltration and diffusion by the 3D porous flower structure with a wide open surface of the Zn-MnO electrode complements the interface formation during the in situ polymerization process. The QSS-RZMB configured with an integrated cathode (i-Zn-MnO) and the hydrogel polymer electrolyte (PHPZ-30) as the separator yields a comparable specific energy density of 214.14 Wh kg(-1) with that of its liquid counterpart (240.38 Wh kg(-1), 0.5 M Zn(CF3SO3)(2) aqueous electrolyte). Other noteworthy features of the presented QSS-RZMB system include its superior cycle life of over 1000 charge-discharge cycles and 85% capacity retention with 99% coulombic efficiency at the current density of 1.0 A g(-1), compared to only 60% capacity retention over 500 charge-discharge cycles displayed by the liquid-state system under the same operating conditions.
Keywords: cathode-electrolyte interface tuning; dendrite inhibition; epitaxial zinc deposition; hydrogel polymer electrolyte; In situ polymerization; Quasi solidstate rechargeable zinc metal battery

Cell based assay using virus-like particles to screen AM type mimics for SARS-CoV-2 neutralisation - Gaur, Neeraj Kailash; Urankar, Shreegauri; Sengupta, Durba; Chepuri, V. Ramana; Makde, Ravindra D.; Kulkarni, Kiran (BIOCHEMICAL AND BIOPHYSICAL RESEARCH COMMUNICATIONS, 2024)
Keywords: MINIPROTEINS

Chemodialysis of organic acids using ABPBI-based hollow fiber membranes - Gawas, Saroj; Alladi, Lavanya; Kharul, Ulhas K. (Journal of Membrane Science, 2024)
Organic acids are a class of essential commodity chemicals used in various industries. Their production methods are shifting from conventional chemicals to fermentation, driven by green process strategies, environmental regulations, cost feasibility, etc. Separating formed acid from the fermentation broth is a primary technological barrier. Conventional methods are complex and impose environmental issues. A promising approach, `Chemodialysis,' capable of transforming the techno-economical feasibility of acid recovery scenario by reducing the number of steps, needs further investigation. This work evaluates scalable hollow fiber membranes based on poly(2,5-benzimidazole) (ABPBI) for chemically assisted dialysis, viz., Chemodialysis. Sorption analyses of commercially significant organic acids (acetic, lactic, and glycolic acid) and nonacidic solutes (NaCl and glucose) were performed using conventional flat sheet samples to assess their role in governing permeation characteristics. The transport properties of acids in the presence of NaCl and glucose as co-solutes were analyzed using hollow fiber membranes. The high selectivity of acid over nonacidic solutes ranges from 400-22,400, coupled with high acid permeability, enhances the applicability of Chemodialysis for the separation of acids using hollow fiber membranes. The fluxes of acids (acetic, glycolic, and lactic) through dense, similar to 100 mu m thick, scalable hollow fiber membranes ranging from 10.9 to 13.12 g/m(2)h are highly appreciable.
Keywords: 5-benzimidazole); Acid separation; Chemodialysis; Hollow fiber membranes; Organic acids; Poly(2

Circulatory levels of lysophosphatidylcholine species in obese adolescents: Findings from cross-sectional and prospective lipidomics analyses - Sharma, Sapna; Subrahmanyam, Yalamanchili Venkata; Ranjani, Harish; Sidra, Sidra; Parmar, Dharmeshkumar; Vadivel, Sangeetha; Kannan, Shanthini; Grallert, Harald; Usharani, Dandamudi; Anjana, Ranjit Mohan; Balasubramanyam, Muthuswamy; Mohan, Viswanathan; et al. (NUTRITION METABOLISM AND CARDIOVASCULAR DISEASES, 2024)
Keywords: Adolescent obesity; Asian Indians; biomarker; Lipidomics; Lysophosphatidyl- choline

Co-incorporated N-doped micro-meso porous carbon as an electrocatalyst for oxygen reduction reaction and Zn-air battery - Priya, Vaishna K.; Kharabe, Geeta Pandurang; Barik, Sidharth; Mohamed, A. Peer; Kurungot, Sreekumar; Hareesh, Unnikrishnan Nair Saraswathy (Energy and Fuels, 2024)
Metal-organic frameworks are considered ideal precursors for the preparation of transition-metal, heteroatom-doped carbon catalysts that are perceived to be efficient electrocatalysts for energy storage devices. Herein, we demonstrate the synthesis of ZIF-67-derived Co-incorporated N-doped porous carbon catalysts supported on high surface area microporous carbon prepared from a lotus seed shell. The combination of the two carbon catalysts in different weight ratios resulted in Co-incorporated N-doped carbon sheets with tuned surface area and porosity, enabling enhanced oxygen reduction reaction (ORR) activity in an alkaline medium. The optimized carbon catalyst ZL 600 (3:1) exhibited a half-wave potential of 0.79 V vs RHE and a limiting current density of -4.38 mA cm(-2) in 0.1 M KOH solution with higher stability and methanol tolerance. The optimized sample ZL 600 (3:1) demonstrated as a cathode in a zinc-air battery exhibited an open circuit voltage of 1.29 V with a flat discharge profile at a current rate of 10 mA cm(-2). The homemade system produced a specific capacity of 610 mAh g(-1) and a peak power density of 111 mW cm(-2), comparable to the cathode made with Pt/C. The high micro-mesoporosity, pyridinic and pyrrolic nitrogen contents, as well as enriched Co-active centers protected by carbon sheets favorably contributed to the efficient ORR mechanism.

Comparative proteomics of sugarcane smut fungus- Sporisorium scitamineum unravels dynamic proteomic alterations during the dimorphic transition - Kumaravel, Nalayeni; Ebinezer, Leonard Barnabas; Ashwin, N. M. R.; Franchin, Cinzia; Battisti, Ilaria; Carletti, Paolo; Sundar, Amalraj Ramesh; Masi, Antonio; Malathi, Palaniyandi; Viswanathan, Rasappa; Arrigoni, Giorgio (Journal of Proteomics, 2024)
Life cycle of the dimorphic sugarcane smut fungi, Sporisorium scitamineum , involves recognition and mating of compatible saprophytic yeast -like haploid sporidia (MAT -1 and MAT -2) that upon fusion, develop into infective dikaryotic mycelia. Although the dimorphic transition is intrinsically linked with the pathogenicity and virulence of S. scitamineum , it has never been studied using a proteomic approach. In the present study, an iTRAQ-based comparative proteomic analysis of three distinct stages was carried out. The stages were: the dimorphic transition period - haploid sporidial stage (MAT -1 and MAT -2); the transition phase (24 h post co -culturing (hpc)) and the dikaryotic mycelial stage (48 hpc). Functional categorization of differentially abundant proteins showed that the most altered biological processes were energy production, primary metabolism, especially, carbohydrate, amino acid, fatty acid, followed by translation, post -translation and protein turnover. Several differentially abundant proteins (DAPs), especially in the dikaryotic mycelial stage were predicted as effectors. Taken together, key molecular mechanisms underpinning the dimorphic transition in S. scitamineum at the proteome level were highlighted. The catalogue of stage -specific and dimorphic transition -associated -proteins and potential effectors identified herein represents a list of potential candidates for defective mutant screening to elucidate their functional role in the dimorphic transition and pathogenicity in S. scitamineum . Biological significance: Being the first comparative proteomics analysis of S. scitamineum , this study comprehensively examined three pivotal life cycle stages of the pathogen: the non-pathogenic haploid phase, the transition phase, and the pathogenic dikaryotic mycelial stage. While previous studies have reported the sugarcane and S. scitamineum interactions, this study endeavored to specifically identify the proteins responsible for pathogenicity. By analyzing the proteomic alterations between the haploid and dikaryotic mycelial phases, the study revealed significant changes in metabolic pathway -associated proteins linked to energy production, notably oxidative phosphorylation, and the citrate cycle. Furthermore, this study successfully identified key metabolic pathways that undergo reprogramming during the transition from the non-pathogenic to the pathogenic stage. The study also deciphered the underlying mechanisms driving the morphological and physiological alterations crucial for the S. scitamineum virulence. By studying its life cycle stages, identifying the key metabolic pathways and stage -specific proteins, it provides unprecedented insights into the pathogenicity and potential avenues for intervention. As proteomics continues to advance, such studies pave the way for a deeper understanding of plantpathogen interactions and the development of innovative strategies to mitigate the impact of devastating pathogens like S. scitamineum.
Keywords: dimorphism; fungi; iTRAQ; Smut; Sugarcane; Virulence

Computational identification of most potent atom pair catalysts for electrocatalytic nitrogen reduction reaction over hydrogen evolution reaction - Verma, Tushar Singh; Dar, Afshana Hassan; Dar, Manzoor Ahmad; Selvaraj, Kaliaperumal; Krishnamurty, Sailaja (Inter., 2024)
Robust electrocatalytic atom pair compositions (APCs) where Nitrogen Reduction Reaction (NRR) is more enhanced over competing Hydrogen Evolution Reaction (HER) is searched for using computational studies based on Density Functional Theory based methods. Atomic pairs are anchored on mechanically and thermally stable graphene surfaces. A wide range of transition metal based atom pair compositions from 3d, 4d, and 5d groups are systematically investigated for reduction of dinitrogen molecule with lower reduction barrier as compared to HER. APR compositions of Ni-Rh with an overall limiting potential of -0.22 V, Fe-W with an overall limiting potential of -0.26 V and Co-Pt with an overall limiting potential of -0.28 V are identified as the most potent atomic pairs for enhanced nitrogen reduction reaction over the HER. Finally, the performance of most potent composition, viz., Ni-Rh is validated to be consistent with respect to their thermodynamic stability and performance within the solvent effects.
Keywords: Atom pair catalysts; Density Functional Theory (DFT); Electrochemical nitrogen reduction reaction (eNRR); hydrogen evolution reaction (HER); IR stretching frequencies; N-N bond length

Concise and collective total syntheses of 2,4-disubstituted furan-derived natural products from hydroxyoxetanyl ketones - Sahoo, Shubhranshu Shekhar; Kataria, Priyanka; Kontham, Ravindar (Organic and biomolecular chemistry, 2024)
The furan moiety, prevalent in bioactive natural products and essential drugs, presents intriguing structural features that have spurred our exploration into streamlined chemical synthesis routes for related natural products. In this study, we demonstrate the concise total synthesis of eight 2,4-disubstituted furan-derived natural products (including methylfuroic acid, rabdoketones A and B, paleofurans A and B, tournefolin C, and shikonofurans A and B). Our methodology revolves around the utilization of hydroxyoxetanyl ketones as pivotal intermediates. The approach encompasses transformations such as selective organo-catalyzed cross-ketol addition, synthesis of hydroxymethyl-tethered furans through Bi(OTf)3 catalyzed dehydrative cycloisomerization of alpha-hydroxyoxetanyl ketones, and a hydrogen atom transfer (HAT)-mediated oxidation of primary alcohols into the corresponding acids. This comprehensive synthetic strategy highlights the versatility of hydroxyoxetanyl ketones as invaluable building blocks in the synthesis of furan-containing natural products. A unified total synthesis of eight 2,4-disubstituted furan-derived natural products has been achieved through Bi(iii)-catalyzed cascade cycloisomerization of alpha-hydroxyoxetanyl ketones and hydrogen atom transfer-mediated oxidation of primary alcohols as pivotal transformations.

Conductive metal-organic frameworks for zinc-air battery application: design principles, recent trends and prospects - Devi, Bandhana; Kurungot, Sreekumar (Journal of Materials Chemistry A, 2024)
Electrochemical energy conversion and storage systems have an indispensable place in the modern world to fulfill the increasing energy demands. Among the different storage devices, rechargeable zinc-air batteries (ZABs) have become one of the most promising energy technologies owing to the abundance and inexpensiveness of Zn, simple operation, environmental friendliness, and reasonable energy density. However, the sluggishness of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) occurring in ZABs is a serious obstacle in their progress and commercialization. This creates a need for the development of efficient bifunctional electrocatalysts for ORR and OER. Conductive metal-organic frameworks (cMOFs) imbibing the general properties of MOFs, like high surface area, tunable porosity, redox-active centers, and additional intrinsic conductivity, can be a very lucrative option for developing bifunctional ORR and OER electrocatalysts for ZAB applications. In this review, we discuss the conductivity and design strategies of conductive MOFs, the basic configuration of ZABs, and the use of cMOFs for ZAB applications. The future directions for the improvement of cMOFs for ZABs have been provided, which hopefully will incite interest among researchers for further exploring cMOFs for ZABs. Electrochemical energy conversion and storage systems have an indispensable place in the modern world to fulfill the increasing energy demands.
Keywords: Biofunctional Oxygen Electrocatalyst; Electrical conductivity; Energy storage; Fuel-Cells; li-ion batteries

Continuous flow ozonolysis of cardanol for greener synthesis of bio-based monomers - Kulkarni, Sphurti P.; Kulkarni, Amol A. (Journal of Flow Chemistry, 2024)
Synthesis of bio-based monomers via continuous flow ozonolysis of cardanol using a simple tubular reactor is demonstrated. The direct ozonolysis of cardanol produces unique monomer 8-(3-hydroxyphenyl) octanal (HPOA) and heptanal along with several other oxidation products. Maximum 47% yield of HPOA with 54.3% conversion of cardanol was obtained at 0 degrees C in 9 s. The complete conversion of cardanol was obtained at the ozone to cardanol molar flow ratios greater than 2 at all temperatures varied in the range of -10 degrees C to 20 degrees C. Owing to large gas-liquid ratios, the mass transfer limitation for transfer of ozone from gas to liquid was negligible; however, the extent of axial dispersion in the liquid phase was significant at lower liquid flow rates. The non-ideal behavior was incorporated in the axial dispersion model to predict the conversion of cardanol. Examination of kinetic rates by both ideal plug-flow model and plug-flow with axial dispersion model revealed that the reaction is fast and is least influenced by the axial-dispersion in the reactor at prevailing operating conditions. The findings of the current study show that continuous flow technique enables a simple and safer synthesis of high-value bio-based monomers via ozonolysis of cardanol compared to traditional batch methods.
Keywords: Axial-dispersion model; Cardanol; continuous flow; Helical coil; Ozonolysis

Continuous flow synthesis of mesoporous silica particles with tunable size and structure - Jundale, Rajashri B.; Prasad, Bhagavatula L. V.; Devi, R. Nandini; Kulkarni, Amol A. (Industrial and Engineering Chemistry Research, 2024)
We have developed a continuous process to prepare mesoporous silica particles of different sizes and narrow size distribution in a tubular reactor. The method is based on the use of well-known Stober synthesis in the presence of cationic surfactant in methanol-water solvent system and trimethylbenzene as pore swelling agent to form porous silica particles. We observed that reaction parameters had enormous effects on particle size, distribution, and numerous morphological aspects. We demonstrated that these properties may be modified by adjusting the reaction temperature, base concentration, and surfactant concentration. MSPs of spherical morphology with variable size from 400 to 1000 nm produced with the surface area >600 m(2)/g and pore diameter of 2-4 nm. Large scale production is demonstrated by increasing reactor volume using 1/4 in. PTFE tubing from 20 to 163 mL, with this production of MSPs increased from 0.35 to 3 g/h. The method has been extended for high yield production at the kilogram scale using this approach, which will pave the way toward the industrialization of mesoporous silica based materials.

Copper/Iron cocatalyzed depolymerization of postconsumer polycarbonate: a one-pot strategy to synthesize aryl ethers - Moyilla, Nageswararao; Padhi, Ganeshdev; Kalsi, Deepti; Barsu, Nagaraju (ACS SUSTAINABLE CHEMISTRY & ENGINEERING, 2024)
Keywords: aryl ethers; copper/iron cocatalysis; depolymerization; polycarbonates; Value-added products

CuNPs@Al2O3-cellulose composite for the ligand-free Suzuki cross-coupling reactions in batch and continuous flow process - Patil, Seema; Rajmane, Archana; Jadhav, Sanjay; Rode, Chandrashekhar; Kumbhar, Arjun (Journal of Organometallic Chemistry, 2024)
In the present work, we synthesized recyclable CuNPs@Al2O3-CELL composite from an inexpensive and commercially available synthetic reagent by a simple method. The catalyst was characterized by various techniques such as TGA (Thermogravimetric analysis), SEM (Scanning electron microscope), TEM (Transmission electron microscopy), XPS (X-ray photoelectron spectroscopy), EDS (Energy dispersive spectroscopy), and AAS (Atomic Absorption Spectroscopy). The composite was applied for the Suzuki coupling reactions in the batch and flow process. The aryl halides were easily coupled with arylboronic acids in 95 % ethanol at 78 C. We systematically investigated the role of reaction temperature, solvent, and catalyst loading, on the transient and steady-state behavior of the flow reactor through an automated flow chemistry platform. The CuNPs@Al2O3CELL catalytic particles demonstrate minimal deactivation and leaching over a continuous Suzuki coupling reaction at a 20 min nominal residence time at 100 C. Moreover, the catalyst can be recovered by simple filtration and reused at least five times with a moderate decrease in product yield. The excellent activity and stability of the catalyst have been attributed to the strong chelation of the Cu species with hydroxyl functional groups of the Al2O3-CELL composite. The catalytic system was highly efficient in Suzuki coupling of various aryl bromides with different aryl boronic acids, yielding good to excellent product yields (80-96 %) with a TON of 15.914-19.066 and TOF of 2.649-9.533 h(-1).
Keywords: Continuous flow process; CuNPs@Al2O3-CELL; ligand-free; recyclable; Suzuki coupling

De novo structure prediction of meteorin and meteorin-like protein for identification of domains, functional receptor binding regions, and their high-risk missense variants - Shankar, S. Shiva; Banarjee, Reema; Jathar, Swaraj M.; Rajesh, S.; Ramasamy, Sureshkumar; Kulkarni, Mahesh J. (Journal of Biomolecular Structure & Dynamics, 2024)
Meteorin (Metrn) and Meteorin-like (Metrnl) are homologous secreted proteins involved in neural development and metabolic regulation. In this study, we have performed de novo structure prediction and analysis of both Metrn and Metrnl using Alphafold2 (AF2) and RoseTTAfold (RF). Based on the domain and structural homology analysis of the predicted structures, we have identified that these proteins are composed of two functional domains, a CUB domain and an NTR domain, connected by a hinge/loop region. We have identified the receptor binding regions of Metrn and Metrnl using the machine-learning tools ScanNet and Masif. These were further validated by docking Metrnl with its reported KIT receptor, thus establishing the role of each domain in the receptor interaction. Also, we have studied the effect of non-synonymous SNPs on the structure and function of these proteins using an array of bioinformatics tools and selected 16 missense variants in Metrn and 10 in Metrnl that can affect the protein stability. This is the first study to comprehensively characterize the functional domains of Metrn and Metrnl at their structural level and identify the functional domains, and protein binding regions. This study also highlights the interaction mechanism of the KIT receptor and Metrnl. The predicted deleterious SNPs will allow further understanding of the role of these variants in modulating the plasma levels of these proteins in disease conditions such as diabetes.
Keywords: domains; Meteorin; meteorin-like; missense variants; protein-protein interactions; structure prediction

Depolymerization of waste polyethylene to linear alkenes via sequential dehydrogenation and metathesis - Khopade, Kishor V.; Rajput, Nikhita S.; Rangappa, Raghavendrakumar; Barsu, Nagaraju; Chikkali, Samir H. (Green Chemistry, 2024)
Polyethylene (PE) is the most abundantly sourced plastic and significant efforts are needed for its end-of-life management. The deconstruction of PE is an uphill task and requires the breaking of highly stable C-C bonds. Here we demonstrate that PE can be deconstructed to value-added dodecene, along with other long-chain alkenes. The PCP-iridium complex catalyzes the dehydrogenation of commercial and post-consumer polyethylene waste to produce dehydrogenated polyethylene (DHP) with 0.5-1.0% unsaturation. The DHP was subjected to an ethylene cross-metathesis reaction in the presence of suitable catalysts. Through meticulous optimization of reaction parameters, 63% selectivity toward dodecene, with 26% overall yield, was achieved. The practical significance of our method has been demonstrated by subjecting post-consumer plastic waste to dehydrogenation followed by ethylene metathesis to produce dodecene as a major product, together with long-chain alkenes. The PE deconstruction has been confirmed by recording molar mass before and after depolymerization using high-temperature gel permeation chromatography. The existence of dodecene has been unambiguously ascertained using GC, GC-MS, NMR, and IR spectroscopy. Thus, these results demonstrate the conversion of waste PE to value-added dodecene and long-chain alkenes under mild reaction conditions.

Design of human ACE2 mimic miniprotein binders that interact with RBD of SARS-CoV-2 variants of concerns - Gaur, Neeraj K.; Khakerwala, Zeenat; Makde, Ravindra D. (Journal of Biomolecular Structure & Dynamics, 2024)
The world of medicine demands from the research community solutions to the emerging problem of SARS-CoV-2 variants and other such potential global pandemics. With advantages of specificity over small molecule drugs and designability over antibodies, miniprotein therapeutics offers a unique solution to the threats of rapidly emerging SARS-CoV-2 variants. Unfortunately, most of the promising miniprotein binders are de novo designed and it is not viable to generate molecules for each new variant. Therefore in this study, we demonstrate a method for design of miniprotein mimics from the interaction interphase of human angiotensin converting enzyme 2 (ACE2). ACE2 is the natural interacting partner for the SARS-CoV-2 spike receptor binding domain (RBD) and acts as a recognition molecule for viral entry into the host cells. Starting with ACE2 N-terminal triple helix interaction interphase, we generated more than 70 miniprotein sequences. Employing Rosetta folding and docking scores we selected 10 promising miniprotein candidates amongst which 3 were found to be soluble in lab studies. Further, using molecular mechanics (MM) calculations on molecular dynamics (MD) trajectories we test interaction of miniproteins with RBD from various variants of concern (VOC). Presently, we report two key findings; miniproteins in this study are generated using less than 10 lab testing experiments, yet when tested through in-vitro experiments, they show submicro to nanomolar affinities towards SARS-CoV-2 RBD. Also in simulation studies, when compared with previously developed therapeutics, our miniproteins display remarkable ability to mimic ACE2 interphase; making them an ideal solution to the ever evolving problem of VOCs.
Keywords: ACE2 mimics; miniprotein; protein design; SARS-CoV-2; therapeutics; Variant of concern

Design, synthesis, anti-mycobacterial activity, molecular docking and ADME analysis of spiroquinoxaline-1,2,4-oxadiazoles via [3+2] cycloaddition reaction under ultrasound irradiation - Kanchrana, Madhu; Gamidi, Rama Krishna; Kumari, Jyothi; Sriram, Dharmarajan; Basavoju, Srinivas (MOLECULAR DIVERSITY, 2024)
Keywords: 2; 4-oxadiazoles; cytotoxicity activity; molecular; Mycobacterium tuberculosis; Spiroquinoxaline-1

Development of an in silico platform (TRIPinRNA) for the identification of novel RNA intramolecular triple helices and their validation using biophysical techniques - Rakheja, Isha; Bharti, Vishal; Sahana, S.; Das, Prosad Kumar; Ranjan, Gyan; Kumar, Ajit; Jain, Niyati; Maiti, Souvik (Biochemistry, 2024)
There are surprisingly few RNA intramolecular triple helices known in the human transcriptome. The structure has been most well-studied as a stability-element at the 3 ` end of lncRNAs such as MALAT1 and NEAT1, but the intrigue remains whether it is indeed as rare as it is understood to be or just waiting for a closer look from a new vantage point. TRIPinRNA, our Python-based in silico platform, allows for a comprehensive sequence-pattern search for potential triplex formation in the human transcriptome-noncoding as well as coding. Using this tool, we report the putative occurrence of homopyrimidine type (canonical) triple helices as well as heteropurine-pyrimidine strand type (noncanonical) triple helices in the human transcriptome and validate the formation of both types of triplexes using biophysical approaches. We find that the occurrence of triplex structures has a strong correlation with local GC content, which might be influencing their formation. By employing a search that encompasses both canonical and noncanonical triplex structures across the human transcriptome, this study enriches the understanding of RNA biology. Lastly, TRIPinRNA can be utilized in finding triplex structures for any organism with an annotated transcriptome.

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

Direct oxidation of alcohols to carboxylic acids using simple and economical Pd@Glu-HTC catalyst: practical and scalable approach towards biomass based value added chemicals - Kirdant, Swapnali P.; Bankar, Shubham R.; Jadhav, Vrushali H. (Biomass & Bioenergy, 2024)
Sustainable catalytic transformation of bio-based alcohols to high value-added fine chemicals is an important topic of research. This work described preparation of simple and economical Pd@Glu-HTC catalyst from biomass derived low cost D-glucose. Hydrothermal carbonization of glucose was carried out in first step to synthesize GluHTC support in a simpler, greener, economical and efficient manner followed by incorporation of palladium metal on surface of the catalyst in second step. The catalyst was characterized using techniques such as Fourier Transform Infrared Spectroscopy (FT-IR), Solid-state Cross-Polarization Magic Angle Spinning Carbon-13 (13C CPMAS), Energy-dispersive X-ray spectroscopy (EDAX), Powder X-ray diffraction (P-XRD), X-ray photoelectron spectroscopy (XPS), Thermogravimetric/Differential Thermal Analyzer (TG-DTA), Field emission scanning electron microscopy (FE-SEM) and High-resolution transmission electron microscopy (HR-TEM). The catalyst was evaluated for direct oxidation of alcohols to yield carboxylic acids and exhibited very good catalytic activity for wider substrate scope. Oxidation of alcohols was carried out using milder base, molecular oxygen and water as a solvent to achieve 92-99 % excellent yields. The practical utility of current strategy was also studied for gram scale synthesis of bio-based value added industrially important chemicals such as furoic acid (flavouring agent and preservative in industry), 2, 5-furan-dicarboxylic acid (monomer to 100 % fossil-free, recyclable polymer polyethylene furanoate (PEF), tetrahydro-2-furoic acid (production of many drugs) and vanillin (important product of flavor and fragrance industry). Pd@Glu-HTC catalyst was found to be reusable for four recycles and the catalytic performance was retained without any loss in its activity after four cycles.
Keywords: Bio-based chemicals; Carbonaceous catalyst; Carboxylic acid; Oxidation

Discovery of free glycated amines and glycated urea in diabetic plasma: potential implications in diabetes - Shaikh, Rashdajabeen Q.; Das, Sancharini; Chaurasiya, Arvindkumar; Ashtamy, Murali G.; Sheikh, Amreen B.; Fernandes, Moneesha; Tiwari, Shalbha; Unnikrishnan, Ambika G.; Kulkarni, Mahesh J. (ACS Omega, 2024)
The role of protein glycation in the pathogenesis of diabetes has been well established. Akin to proteins, free amino acids and other small-molecule amines are also susceptible to glycation in hyperglycemic conditions and may have a role in the pathogenesis of the disease. However, information about glycation of free amino acids and other small-molecule amines is relatively obscure. In the quest to discover small-molecule glycated amines in the plasma, we have synthesized glycated amino acids, glycated creatine, and glycated urea, and by using a high-resolution accurate mass spectrometer, a mass spectral library was developed comprising the precursor and predominant fragment masses of glycated amines. Using this information, we report the discovery of the glycation of free lysine, arginine, and leucine/isoleucine from the plasma of diabetic patients. This has great physiological significance as glycation of these amino acids may create their deficiency and affect vital physiological processes such as protein synthesis, cell signaling, and insulin secretion. Also, these glycated amino acids could serve as potential markers of diabetes and its complications. While other amines, such as creatinine and urea, accumulate in the plasma and act as biomarkers of diabetic nephropathy. For the first time, we report the detection of glycated urea in diabetic plasma, which is confirmed by matching the precursor and fragment masses with the in vitro synthesized glycated urea by using C-12(6) and C-13(6)-glucose. Further, we quantified glycated urea detected in two forms, monoglycated urea (MGU) and diglycated urea (DGU), by a targeted mass spectrometric approach in the plasma of healthy, diabetic, and diabetic nephropathy subjects. Both MGU and DGU showed a positive correlation with clinical parameters, such as blood glucose and HbA1c. Given that urea gets converted to glycated urea in hyperglycemic conditions, it is crucial to quantify MGU and DGU along with the urea for the diagnosis of diabetic nephropathy and study their physiological role in diabetes.

Dishevelled2 activates WGEF via its interaction with a unique internal peptide motif of the GEF - Omble, Aishwarya; Mahajan, Shrutika; Bhoite, Ashwini; Kulkarni, Kiran (COMMUNICATIONS BIOLOGY, 2024)
The Wnt-planar cell polarity (Wnt-PCP) pathway is crucial in establishing cell polarity during development and tissue homoeostasis. This pathway is found to be dysregulated in many pathological conditions, including cancer and autoimmune disorders. The central event in Wnt-PCP pathway is the activation of Weak-similarity guanine nucleotide exchange factor (WGEF) by the adapter protein Dishevelled (Dvl). The PDZ domain of Dishevelled2 (Dvl2PDZ) binds and activates WGEF by releasing it from its autoinhibitory state. However, the actual Dvl2PDZ binding site of WGEF and the consequent activation mechanism of the GEF have remained elusive. Using biochemical and molecular dynamics studies, we show that a unique ``internal-PDZ binding motif'' (IPM) of WGEF mediates the WGEF-Dvl2PDZ interaction to activate the GEF. The residues at P 2 , P 0 , P -2 and P -3 positions of IPM play an important role in stabilizing the WGEFpep-Dvl2PDZ interaction. Furthermore, MD simulations of modelled Dvl2PDZ-WGEFIPM peptide complexes suggest that WGEF-Dvl2PDZ interaction may differ from the reported Dvl2PDZ-IPM interactions. Additionally, the apo structure of human Dvl2PDZ shows conformational dynamics different from its IPM peptide bound state, suggesting an induced fit mechanism for the Dvl2PDZ-peptide interaction. The current study provides a model for Dvl2 induced activation of WGEF. This study identifies a unique ``internal-PDZ binding motif'' (IPM) of WGEF that mediates its interaction with Dvl2PDZ, leading to the release of GEF from its autoinhibitory state. It further unravels the underlying mutual Dvl2-IPM recognition aspects.

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

DNA-mediated formation of phase-separated coacervates of the nucleic acid-binding domain of TAR DNA-binding protein (TDP-43) prevents its amyloid-like misfolding - Patni, Divya; Patil, Anjali D.; Kirmire, Mona S.; Jha, Anjali; Jha, Santosh Kumar (ACS Chemical Neuroscience, 2024)
Sequestration of protein molecules and nucleic acids to stress granules is one of the most promising strategies that cells employ to protect themselves from stress. In vitro, studies suggest that the nucleic acid-binding domain of TDP-43 (TDP-43tRRM) undergoes amyloid-like aggregation to beta-sheet-rich structures in low pH stress. In contrast, we observed that the TDP-43tRRM undergoes complex coacervation in the presence of ssDNA to a dense and light phase, preventing its amyloid-like aggregation. The soluble light phase consists of monomeric native-like TDP-43tRRM. The microscopic data suggest that the dense phase consists of spherical coacervates with limited internal dynamics. We performed multiparametric analysis by employing various biophysical techniques and found that complex coacervation depends on the concentration and ratio of the participating biomolecules and is driven by multivalent interactions. The modulation of these forces due to environmental conditions or disease mutations regulates the extent of coacervation, and the weakening of interactions between TDP-43tRRM and ssDNA leads to amyloid-like aggregation of TDP-43tRRM. Our results highlight a competition among the native state, amyloid-like aggregates, and complex coacervates tuned by various environmental factors. Together, our results illuminate an alternate function of TDP-43tRRM in response to pH stress in the presence of the ssDNA.
Keywords: amyloid-likeaggregation; complex coacervation; DNA-protein interactions; Dynamics; pH stress; TDP-43

Dual modification of tau by pseudophosphorylation and glycation does not enhance amorphous aggregation - Chinnathambi, Subashchandrabose; Sonawane, Shweta Kishor; Chandrashekar, Madhura; Chidambaram, Hariharakrishnan; Thulasiram, Shrivatsa; Kulkarni, Mahesh J. (Cellular Physiology and Biochemistry, 2024)
<h1 class="article-paragraph" style="box-sizing: border-box; margin-top: 30px; margin-bottom: 10px; line-height: 20px; color: rgb(33, 37, 41); font-size: 14px; text-align: justify; font-style: italic; display: inline; font-family: system-ui, -apple-system, "Segoe UI", Roboto, "Helvetica Neue", "Noto Sans", "Liberation Sans", Arial, sans-serif, "Apple Color Emoji", "Segoe UI Emoji", "Segoe UI Symbol", "Noto Color Emoji";"> Background/Aims: <span style="color: rgb(33, 37, 41); font-family: system-ui, -apple-system, "Segoe UI", Roboto, "Helvetica Neue", "Noto Sans", "Liberation Sans", Arial, sans-serif, "Apple Color Emoji", "Segoe UI Emoji", "Segoe UI Symbol", "Noto Color Emoji"; font-size: 14px; text-align: justify;"> The neurofibrillary tangles consisting of Tau protein are an important pathology in Alzheimer’s disease. The paired helical filaments of Tau form most of the NFTs. These PHFs of Tau are found to carry numerous post-translational modifications, which stabilize them and aid in aggregation. The mechanistic function of Tau is to bind and stabilize the axonal microtubules. Hyperphosphorylation of Tau causes it to compromise its physiological function and accumulate in the neurons in the form of aggregates. Such residue-specific phosphorylation has been studied by employing Tau pseudophosphorylation mutants. But in addition to phosphorylation, several other modifications also aid in stabilizing the Tau PHF. Glycation is one such non-enzymatic PTM caused by sugars and their reactive intermediates. In this study, we employed the pseudophosphorylated Tau double mutants (262/404D, 262/396D, and 231/262) for studying their modification by methyl glyoxal, a reactive intermediate of glucose metabolism.  <h1 class="article-paragraph" style="box-sizing: border-box; margin-top: 30px; margin-bottom: 10px; line-height: 20px; color: rgb(33, 37, 41); font-size: 14px; text-align: justify; font-style: italic; display: inline; font-family: system-ui, -apple-system, "Segoe UI", Roboto, "Helvetica Neue", "Noto Sans", "Liberation Sans", Arial, sans-serif, "Apple Color Emoji", "Segoe UI Emoji", "Segoe UI Symbol", "Noto Color Emoji";"> Methods: <span style="color: rgb(33, 37, 41); font-family: system-ui, -apple-system, "Segoe UI", Roboto, "Helvetica Neue", "Noto Sans", "Liberation Sans", Arial, sans-serif, "Apple Color Emoji", "Segoe UI Emoji", "Segoe UI Symbol", "Noto Color Emoji"; font-size: 14px; text-align: justify;"> We studied various biophysical properties like aggregation propensity, Advanced glycation end-product formation, and global conformation of the Tau with dual modifications. Our study includes the use of <i style="box-sizing: border-box; color: rgb(33, 37, 41); font-family: system-ui, -apple-system, "Segoe UI", Roboto, "Helvetica Neue", "Noto Sans", "Liberation Sans", Arial, sans-serif, "Apple Color Emoji", "Segoe UI Emoji", "Segoe UI Symbol", "Noto Color Emoji"; font-size: 14px; text-align: justify;">in vitro <span style="color: rgb(33, 37, 41); font-family: system-ui, -apple-system, "Segoe UI", Roboto, "Helvetica Neue", "Noto Sans", "Liberation Sans", Arial, sans-serif, "Apple Color Emoji", "Segoe UI Emoji", "Segoe UI Symbol", "Noto Color Emoji"; font-size: 14px; text-align: justify;">techniques e.g., ThS fluorescence assay, electron microscopy, CD spectroscopy, SDS-PAGE.  <h1 class="article-paragraph" style="box-sizing: border-box; margin-top: 30px; margin-bottom: 10px; line-height: 20px; color: rgb(33, 37, 41); font-size: 14px; text-align: justify; font-style: italic; display: inline; font-family: system-ui, -apple-system, "Segoe UI", Roboto, "Helvetica Neue", "Noto Sans", "Liberation Sans", Arial, sans-serif, "Apple Color Emoji", "Segoe UI Emoji", "Segoe UI Symbol", "Noto Color Emoji";"> Results: <span style="color: rgb(33, 37, 41); font-family: system-ui, -apple-system, "Segoe UI", Roboto, "Helvetica Neue", "Noto Sans", "Liberation Sans", Arial, sans-serif, "Apple Color Emoji", "Segoe UI Emoji", "Segoe UI Symbol", "Noto Color Emoji"; font-size: 14px; text-align: justify;"> The overall result of the study suggest that the MG-induced Tau aggregation is influenced by the residue-specific Tau phosphorylation.  <h1 class="article-paragraph" style="box-sizing: border-box; margin-top: 30px; margin-bottom: 10px; line-height: 20px; color: rgb(33, 37, 41); font-size: 14px; text-align: justify; font-style: italic; display: inline; font-family: system-ui, -apple-system, "Segoe UI", Roboto, "Helvetica Neue", "Noto Sans", "Liberation Sans", Arial, sans-serif, "Apple Color Emoji", "Segoe UI Emoji", "Segoe UI Symbol", "Noto Color Emoji";"> Conclusion: <span style="color: rgb(33, 37, 41); font-family: system-ui, -apple-system, "Segoe UI", Roboto, "Helvetica Neue", "Noto Sans", "Liberation Sans", Arial, sans-serif, "Apple Color Emoji", "Segoe UI Emoji", "Segoe UI Symbol", "Noto Color Emoji"; font-size: 14px; text-align: justify;"> In conclusion, the combinatorial effect of discreet PTMs on Tau function could lead to a better understanding of Tauopathy.

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

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

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

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

Efficient one-pot process for synthesis of antiviral drug Ganciclovir - Sudrik, Vilas; Karpe, Dnyaneshwar; Jadhav, Vrushali; Lawande, Shamrao (Journal of Chemical Sciences, 2024)
A regioselective novel one-pot synthesis of heterocyclic purine derivative antiviral agent Ganciclovir in which initially guanine is treated with acetic anhydride in the presence of iodine (5%) to get diacetyl guanine intermediate, which undergoes in situ N-alkylation with AMDP in presence of catalytic acidic Amberlite IR-120 to get N-alkylated intermediate and finally deacetylation to get pure regioselective Ganciclovir, which is commercially viable and eco-friendly.Graphical abstractWe developed one-pot synthesis of antiviral drug Ganciclovir. Initially, Guanine is treated with acetic anhydride and iodine to yield diacetyl guanine 3. This intermediate then reacted with AMDP in the presence of acidic Amberlite IR-120 to obtain compound 5. Finally, deacetylation yields Ganciclovir 1, a commercially viable and eco-friendly process.
Keywords: Acidic Amberlite IR-120; acyclic nucleoside; anti-herpes; commercially viable; iodine; one-pot process; regiospecific

Efficient synthesis of a monomer for bioplastic-FDCA using glucose-HTC catalyst and pinnick oxidation from HMF & fructose - Kirdant, Swapnali P. P.; Bankar, Shubham R. R.; Jadhav, Vrushali H. H. (Catalysis Letters, 2024)
An efficient solvent mediated & use of metal-free catalyst strategy was developed for synthesis of FDCA over two steps. A simple & economical glucose-hydrothermally carbonized (Glu-HTC) catalyst was prepared and evaluated for synthesis of 2,5-Diformyl furan (DFF) from fructose & 5-hydroxymethylfurfural (HMF) in the 1(st) step. DFF was then converted to FDCA using Pinnick oxidation in the 2(nd) step. DFF was obtained in 82% & 86% yields from fructose & HMF respectively whereas FDCA was obtained in 94-95% yield from DFF. FDCA was thus formed in an overall yield of 78% and 81% from fructose & HMF respectively. This strategy eliminated use of expensive noble metals for FDCA synthesis and also intermediates such as HMFCA & FFCA were not observed after the reaction as DFF was completely oxidized to FDCA.
Keywords: 2; 5-Diformyl furan (DFF); 5-Furandicarboxylic acid; Biomass; D-fructose

Electrocatalytic glycerol conversion: a low-voltage pathway to efficient carbon-negative green hydrogen and value-added chemical production - Chauhan, Inderjeet; Bajpai, Himanshu; Ray, Bishakha; Kolekar, Sadhu K.; Datar, Suwarna; Patra, Kshirodra Kumar; Gopinath, Chinnakonda S. (ACS Applied Materials and Interfaces, 2024)
Electrochemical glycerol oxidation reaction (GLYOR) could be a promising way to use the abundantly available glycerol for production of value-added chemicals and fuels. Completely avoiding the oxygen evolution reaction (OER) with GLYOR is an evolving strategy to reduce the overall cell potential and generate value-added chemicals and fuels on both the anode and cathode. We demonstrate the morphology-controlled palladium nanocrystals, afforded by colloidal chemistry, and their established morphology-dependent GLYOR performance. Although it is known that controlling the morphology of an electrocatalyst can modulate the activity and selectivity of the products, still it is a relatively underexplored area for many reactions, including GLYOR. Among nanocube (Pd-NC), truncated octahedron (Pd-TO), spherical and polycrystalline (Pd-PC) morphologies, the Pd-NC electrocatalyst deposited on a Ni foam exhibits the highest glycerol conversion (85%) along with 42% glyceric acid selectivity at a low applied potential of 0.6 V (vs reversible hydrogen electrode (RHE)) in 0.1 M glycerol and 1 M KOH at ambient temperature. Owing to the much favorable thermodynamics of GLYOR on the Pd-NC surface, the assembled electrolyzer requires an electricity input of only similar to 3.7 kWh/m(3) of H-2 at a current density of 100 mA/cm(2), in contrast to the requirement of >= 5 kWh/m(3) of H-2 with an alkaline/PEM electrolyzer. Sustainability has been successfully demonstrated at 10 and 50 mA/cm(2) and up to 120 h with GLYOR in water and simulated seawater.
Keywords: electrocatalysis; Glycerol; green hydrogen; nanocube; Palladium; SDG

Electrochemical energy storage in an organic supercapacitor via a non-electrochemical proton charge assembly - Mukhopadhyay, Sanchayita; Kottaichamy, Alagar Raja; Devendrachari, Mruthyunjayachari Chattanahalli; Mendhe, Rahul Mahadeo; Kotresh, Harish Makri Nimbegondi; Vinod, Chathakudath Prabhakaran; Thotiyl, Musthafa Ottakam (Chemical Science, 2024)
Contrary to conventional beliefs, we show how a functional ligand that does not exhibit any redox activity elevates the charge storage capability of an electric double layer via a proton charge assembly. Compared to an unsubstituted ligand, a non-redox active carboxy ligand demonstrated nearly a 4-fold increase in charge storage, impressive capacitive retention even at a rate of 900C, and approximately a 2-fold decrease in leakage currents with an enhancement in energy density up to approximately 70% via a non-electrochemical route of proton charge assembly. Generalizability of these findings is presented with various non-redox active functional units that can undergo proton charge assembly in the ligand. This demonstration of non-redox active functional units enriching supercapacitive charge storage via proton charge assembly contributes to the rational design of ligands for energy storage applications.

Electrodeposited Co-Mn-Sn multicomponent alloy as an efficient electrocatalyst for hydrogen evolution reaction - Chandran, M. Athira; Karumuthil, Subash Cherumannil; Singh, Ashutosh K.; Prasad, Bhagavatula L. V. (International Journal of Hydrogen Energy, 2024)
Despite having exciting material characteristics, the potential of multi-component alloys (MCAs) as electrocatalysts has not been fully realized. In this work, efficient binary and ternary MCA electrocatalysts containing inexpensive metals like Co, Mn and Sn have been prepared via the electrodeposition process. When tested for hydrogen evolution reaction (HER) in an alkaline medium, ternary Co-Mn-Sn alloy displayed enhanced activity with the lowest overpotential of 136 mV, a Tafel slope of 111 mV dec 1 and a very low charge transfer resistance, making it superior to the binary alloys (Co-Mn and Co-Sn), or the single metal catalysts (Co, Mn and Sn). The ternary alloy also displayed high electro-chemical and structural stability, making it a viable electrocatalyst for the hydrogen economy.(c) 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Keywords: Clean energy; electrocatalysis; Electrodeposition; hydrogen evolution reaction; Multi-component alloy; Non-platinum group metals

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

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

Enhanced degradation of ciprofloxacin hydrochloride using hybrid advanced oxidation process of hydrodynamic cavitation and ozonation - Bodawar, Narendra; Shetty, Rohit; Kamble, Sanjay; Kulkarni, Prashant (Chemical Engineering & Technology, 2024)
The degradation of ciprofloxacin hydrochloride (CFX), an extensively utilized antibiotic for bacterial infections, has been studied through the application of advanced oxidation processes (AOPs) including hydrodynamic cavitation (HC), ozonation (O3), the Fenton reaction, chemical oxidation, and hybrid AOPs such as HC/O3 and Fenton/O3. Among these, the hybrid combination of HC/O3 demonstrated the highest CFX degradation of 99.82 % within 180 min having an initial concentration of 1000 ppm. The optimization of the HC/O3 process was conducted by varying parameters including initial concentration, pH, ozone (O3) gas flowrate, and temperature. Throughout the degradation process, CFX underwent intermediate formation, which gradually degraded over time. The hydrodynamic cavitation (HC) in combination with ozone, referred to as the HC/ozonation process, was used for the degradation of ciprofloxacin hydrochloride present in wastewater. This process underwent optimization with respect to various reaction parameters, including the initial concentration, ozone flow rate, pH level, temperature, the influence of ions, and the specific water matrix. At these optimized conditions a degradation efficiency of 99.82 % was achieved after 180 min. image
Keywords: active pharmaceutical ingredients; Advance Oxidation Processes; Ciprofloxacin hydrochloride; Hybrid AOPs; Hydrodynamic cavitation

Enhancing the crystallization kinetics and mechanical properties of poly(lactic acid) blends for 3D printing application - Kothavade, Premkumar; Yadav, Prashant; Gopal, Animesh; Pol, Harshawardhan; Kafi, Abdullah; Bateman, Stuart; Shanmuganathan, Kadhiravan (ACS Applied Polymer Materials, 2024)
3D printing of poly(lactic acid) (PLA) blends has been attempted to resolve issues such as inherent brittleness and slow crystallization rate of PLA. However, a persistent challenge remains in the form of phase separation or gradual migration of the blended soft polymer or plasticizers. To simultaneously enhance the miscibility of the blends and toughness of 3D-printed parts, a triblock copolymer PLA-PEG-PLA was synthesized and blended with PLA in varying proportions (5, 10, 15, and 20 wt %). Blending only 10-20 wt % low molecular weight PLA-PEG-PLA into PLA yielded a miscible blend that showed a 45-fold increase in elongation at break and a 23-fold enhancement in toughness over neat PLA. Scanning electron microscopy (SEM) images of fractured cross sections revealed a brittle to ductile transition in 3D-printed PLA/PLA-PEG-PLA samples. Isothermal crystallization studies and data analysis using the Avrami equation showed an enhancement in the crystal growth rate and overall rate of crystallization. The blends achieved half of their crystallinity in approximately 3 min, a significant improvement over the 9 min required by PLA alone. This underscores the efficiency of our approach. This was also evident in the spherulite growth of 3D-printed PLA and mPLA blends when examined using polarized optical microscopy (POM). To the best of our knowledge, this is the first report exploring the use of blends that include PLA and low molecular weight PLA-PEG-PLA triblock copolymers for 3D printing applications.
Keywords: Crystallization; FFF 3D printing; PLA-PEG-PLA triblock copolymer; poly(lacticacid); toughness

Environment friendly synthesis of reduced graphene oxide from spent lithium-ion battery graphite and its nanocomposite with MoO3 nanorods for photocatalytic hydrogen evolution - Kangutkar, Raju S.; Walko, Priyanka; Athira, K.; Manjanna, J.; Devi, R. Nandini (Energy & Fuels, 2024)
Photocatalytic water splitting from solar H2 generation systems is of great interest as a sustainable fuel and an environmentally benign approach. A photocatalyst should be cost-efficient and highly productive to obtain a green H2 fuel. Thus, photocatalytic water splitting is significant for real-world applications. In the present work, we have successfully synthesized MoO3@rGO nanocomposite material with heterojunction as a stable and high-performance photocatalyst for the H2 evolution reaction in deionized (DI) water and natural seawater. First, MoO3 was prepared through a low-temperature hydrothermal method and composites with graphene oxide (GO) and reduced graphene oxide (rGO) precursors, followed by ultrasonication. rGO was obtained from GO, which is obtained from the spent graphite (anode material) by the modified Hummer's method. The rGO powder was reduced by an ascorbic acid-reducing agent under microwave irradiation using GO. The nanocomposite materials were characterized using XRD, Raman spectra, XPS, photoluminescence, FE-SEM, HR-TEM, and BET. The photocatalytic water splitting ability of MoO3@rGO was measured under visible light (lambda >= 420 nm) irradiation with the TEOA sacrificial reagent. The H2 generation rate in DI water and natural seawater was found to be 2183.41 and 2294.26 mu mol g-1 h-1, with an apparent quantum efficiency (AQE) of 5.72 and 5.98%, respectively. Such a high rate of H2 generated is ascribed to the novel surface contact between MoO3 and the rGO sheet as evident from HR-TEM images, wherein the rGO sheet is seen wrapped around MoO3. Consequently, the synergistic effect between MoO3 and rGO sheets is expected without the use of any other cocatalysts. Thus, electron-hole recombination is significantly minimized during the water reduction reaction. We believe that the MoO3@rGO nanocomposite is a potential photocatalyst for energy production.

Experimental and kinetic modelling studies for the design of fixed bed methanol reactor over CuZA catalyst - Bagwan, Farahanaz M.; Dongapure, Pavan; Kulkarni, Amol A.; Vasireddy, Satyam Naidu (Chemical Engineering Research Design, 2024)
Direct conversion of CO 2 via hydrogenation to value-added chemicals is a vital approach for utilising CO 2 emitted into the atmosphere. In this paper, a critical analysis of reaction kinetic modelling studies is explored in a fixed bed reactor to improve methanol yield for different H 2 to CO 2 ratios by simulating a lab-scale reactor for adiabatic and isothermal conditions. The feed inlet temperature and pressure variations are applied to study the effect of both configurations on methanol production. The results show that the isothermal configuration yields 2.76% more methanol yield compared to the adiabatic reactor. The effect of H 2 to CO 2 molar ratios of 3, 6 and 9 on the performance of the catalyst and the influence of CO and CO 2 hydrogenation is investigated with model simulations. The overall methanol yield is increased from 19.03% to 36.41% with increase in H 2 to CO 2 molar ratio from 3 to 9. Experiments are performed using commercial copper-based catalyst for different temperatures of 210, 230 and 250 degrees C at a pressure of 40 bar for H 2 /CO 2 of 3 and GHSV of 720 h -1 as well as at optimal temperature of 250 degrees C and 50 bar with varying H 2 /CO 2 of 3, 6, 9 for 3 g and 6 g catalyst. The maximum methanol yield of 2.53% and space time yield of 13.59 mg/g cat .h is obtained at H 2 /CO 2 ratio of 9.
Keywords: CO2 conversion; CuZA catalyst; H2 toCO2 molar ratio; Kinetic modelling; Methanol

Explainable AI-assisted web application in cancer drug value prediction - Kothari, Sonali; Sharma, Shivanandana; Shejwal, Sanskruti; Kazi, Aqsa; D'Silva, Michela; Karthikeyan, M. (MethodsX, 2024)
<div class="u-margin-s-bottom" id="spara003" style="box-sizing: border-box; margin-top: 0px; margin-right: 0px; margin-left: 0px; padding: 0px; color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px; margin-bottom: 16px !important;"> In recent years, there has been an increase in the interest in adopting Explainable Artificial Intelligence (XAI) for healthcare. The proposed system includes <ul class="list" style="box-sizing: border-box; margin: 16px 0px; padding-right: 0px; padding-left: 0px; list-style: none; display: grid; grid-template-columns: fit-content(15%) fit-content(85%); gap: 0px 16px;"> • An XAI model for cancer drug value prediction. The model provides data that is easy to understand and explain, which is critical for medical decision-making. It also produces accurate projections. • A model outperformed existing models due to extensive training and evaluation on a large cancer medication chemical compounds dataset. • Insights into the causation and correlation between the dependent and independent actors in the chemical composition of the cancer cell. <div class="u-margin-s-bottom" id="spara007" style="box-sizing: border-box; margin-top: 0px; margin-right: 0px; margin-left: 0px; padding: 0px; color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px; margin-bottom: 16px !important;"> While the model is evaluated on Lung Cancer data, the architecture offered in the proposed solution is cancer agnostic. It may be scaled out to other cancer cell data if the properties are similar. The work presents a viable route for customizing treatments and improving patient outcomes in oncology by combining XAI with a large dataset. This research attempts to create a framework where a user can upload a test case and receive forecasts with explanations, all in a portable PDF report.

An explainable AI-assisted web application in cancer drug value prediction - Kothari, Sonali; Sharma, Shivanandana; Shejwal, Sanskruti; Kazi, Aqsa; D'Silva, Michela; Karthikeyan, M. (MethodsX, 2024)
<div class="u-margin-s-bottom" id="spara003" style="box-sizing: border-box; margin-top: 0px; margin-right: 0px; margin-left: 0px; padding: 0px; color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px; margin-bottom: 16px !important;"> In recent years, there has been an increase in the interest in adopting Explainable Artificial Intelligence (XAI) for healthcare. The proposed system includes <ul class="list" style="box-sizing: border-box; margin: 16px 0px; padding-right: 0px; padding-left: 0px; list-style: none; display: grid; grid-template-columns: fit-content(15%) fit-content(85%); gap: 0px 16px;"> • An XAI model for cancer drug value prediction. The model provides data that is easy to understand and explain, which is critical for medical decision-making. It also produces accurate projections. • A model outperformed existing models due to extensive training and evaluation on a large cancer medication chemical compounds dataset. • Insights into the causation and correlation between the dependent and independent actors in the chemical composition of the cancer cell. <div class="u-margin-s-bottom" id="spara007" style="box-sizing: border-box; margin-top: 0px; margin-right: 0px; margin-left: 0px; padding: 0px; color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px; margin-bottom: 16px !important;"> While the model is evaluated on Lung Cancer data, the architecture offered in the proposed solution is cancer agnostic. It may be scaled out to other cancer cell data if the properties are similar. The work presents a viable route for customizing treatments and improving patient outcomes in oncology by combining XAI with a large dataset. This research attempts to create a framework where a user can upload a test case and receive forecasts with explanations, all in a portable PDF report.

Exploring defect-engineered metal-organic frameworks with 1,2,4-triazolyl isophthalate and benzoate linkers - Chetry, Sibo; Lukman, Muhammad Fernadi; Bon, Volodymyr; Warias, Rico; Fuhrmann, Daniel; Moellmer, Jens; Belder, Detlev; Gopinath, Chinnakonda S.; Kaskel, Stefan; Poeppl, Andreas; Krautscheid, Harald (INORGANIC CHEMISTRY, 2024)
Keywords: Separation; spectroscopy; TRIAZOLYL

Exploring novel cocrystals of milrinone: a cardioprotective drug combined with nutraceuticals and an NSAID - Kenguva, Gowtham; Rekha Rout, Smruti; Shaikh, Tabrez R.; Baidya, Debjani; Shelke, Nikita; Sanphui, Palash; Dandela, Rambabu (CrystEngComm, 2024)
Milrinone is a bipyridine phosphodiesterase (PDE) inhibitor of the second generation. It's a PDE-III antagonist that raises cAMP levels to support heart function and acts as a systemic vasodilator in chronic decongested cardiovascular illness. It is categorised as class II in the Biopharmaceutics Classification System (BCS), indicating that it exhibits poor aqueous solubility and high permeability. Three new cocrystals of the cardioprotective drug milrinone (MR) with two nutraceuticals, e.g. sesamol (SES) and resveratrol (RES), and an anti-inflammatory drug, e.g. niflumic acid (NIF), were successfully synthesised using mechanochemical and solution crystallisation techniques. Thermal analysis (DSC and TGA) and diffraction tools (PXRD and SCXRD) were used to obtain structural insights into all the cocrystals. Their crystal structures indicate that the dimeric interactions in MR are preserved in the crystal structures in addition to carboxylic acid/phenol & ctdot;pyridine heterosynthons. Among the three synthesized molecular solids, MR.SES was more soluble than the native drug. The solubility of the cocrystals was correlated with polar surface contacts, the solubility of the coformer and melting points (inversely). We believe that the new MR.SES cocrystal offers a novel approach to enhance the drug's solubility, which may have a positive impact on its synergistic cardioprotective effects.

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

Exploring thermocatalytic pyrolysis to derive sustainable chemical intermediates from plastic waste; role of temperature, catalyst, and reactor conditions - Venkataraghavan, R.; Bhure, Arvind; Khan, Tufeil Sartaj; Shikare, Dipak; Devi, R. Nandini; Dhepe, Paresh Laxmikant (Journal of the Indian Institute of Science, 2024)
Plastic waste is a growing concern globally on account of the increasing use of plastic worldwide, compounded by single-use applications, poor waste collection and management practices, and its consequent leakage into the environment. In addition, plastics are derived from non-renewable fossil resources, and their growing demand is also partly responsible for greenhouse gas emissions and climate change. The aim of this paper is to explore the potential of plastic waste as a material resource, and thermocatalytic pyrolysis as a recycling process, to produce aliphatic and aromatic hydrocarbons, which are important chemical intermediates for various industries. We show that plastic pyrolysis can achieve a high yield of liquid hydrocarbons (similar to 80%) with a suitable distribution of aliphatic and aromatic compounds, by using different pyrolysis conditions and a catalyst. Specifically, this paper demonstrates the possibility of deriving two key classes of hydrocarbons, i.e., aliphatic (C10-C20 hydrocarbons) and aromatic hydrocarbons (xylene, toluene and benzene derivatives) with a yield of similar to 80% liquid hydrocarbons via catalytic pyrolysis. We also briefly discuss the challenges and opportunities, and the environmental and economic implications.

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

Extrusion 3D printing of intrinsically fluorescent thermoplastic polyimide: revealing an undisclosed potential - Kothavade, Premkumar; Kafi, Abdullah; Dekiwadia, Chaitali; Kumar, Viksit; Sukumaran, Santhosh Babu; Shanmuganathan, Kadhiravan; Bateman, Stuart (POLYMERS, 2024)
Keywords: Additive manufacturing; functional extrusion; high-performance polymers; thermoplastic polyimide

Fabrication and evaluation of a spatially resolved fiber-optic probe for diffuse reflectance measurement for noninvasive diabetic foot ulcer diagnosis perspective - Kumar, Ajay; Hattale, Gangadhar; Pawar, Dnyandeo; Kanawade, Rajesh (Optical Engineering, 2024)
Timely diagnosis and monitoring of wound progression or healing are key to improving the long-term outcome of diabetic foot ulcers (DFU). Diffuse reflectance spectroscopy (DRS) has the potential to noninvasively diagnose the DFU in real time, as it detects changes in local blood volume fraction and oxygenation state level that occur when tissue becomes diseased or ulcerated. Since foot soles have a thicker epidermis and deeper blood vessels/capillaries than other parts of the body, a spatially resolved fiber-optic probe (SRFP) is needed to detect the optimal spatially resolved diffuse reflectance (SRDR) signal from the local site of the ulcer for DFU diagnosis. Therefore, herein, an SRFP consisting of a linear array of seven 400-mu m fibers with detector-source (D-S) fiber separation (rho) ranging from 0.8 to 4.8 mm was designed, fabricated, tested, and evaluated for SRDR measurement from a standard reflectance plate of barium sulfate (BaSO4) and foot sole of 27 healthy human subjects. The variation in SRDR spectra for each detector and source fiber pair measured with BaSO4 was found to be less than 1.6%. In-vivo measurements from the foot sole demonstrate that the fabricated probe has the ability to spatially resolve and distinguish the SRDR spectra from sites, namely, the fifth metatarsal, ball of great joint, calcaneum, and great toe. Experimentally and theoretically, the detector and source fiber pair of rho=1.6 and 2.4 mm were optimal for SRDR measurements from a human foot. To evaluate and validate the performance of SRFP in a context relevant to DFU diagnosis, further SRDS measurements were performed on the solid tissue phantoms that mimic the optical properties of the normal and diabetic foot sole, and their results are statistically found different. Preliminary results suggest that developed SRFP can be explored for DRS measurement from foot ulcer patients to confirm its potential clinical applicability.
Keywords: diabetic foot ulcer; diffuse reflectance spectroscopy; foot sole; spatially resolved fiber-optic probe; tissue phantom

Facile microwave synthesis of Zinc Ferrite@NCDs for photocatalytic degradation of fluoroquinolone antibiotics - Kaushal, Neha; Sarraf, Sonu; Basu, Aviru Kumar; Mishra, Sunita; Saha, Avishek (Materials Chemistry and Physics, 2024)
Zinc ferrite (ZnFe2O4) composites have attracted growing interest in photocatalytic water purification. Herein, the hybrids of zinc ferrite and nitrogen-doped carbon dots (ZnF@x%NCDs) were synthesized via facile micro-wave synthesis. X-ray diffraction and Raman characterization confirm the formation of the spinel structure, and elemental composition has been analyzed by X-ray photoelectron spectroscopy. The photocatalytic activity of ZnF@x%NCDs was evaluated via the decomposition of ciprofloxacin and norfloxacin under visible light illumination. We noted that 20 % weight loading of NCDs led to the highest (similar to 79.2 %) ciprofloxacin (CIP) degradation. Diffuse reflectance measurements demonstrate the reduction of the band gap in composites ZnF@20%NCDs (1.91 eV) compared with bare ZnF (2.03 eV); moreover, the hybridization of zinc ferrites with NCDs results in enhanced photocurrent density and surface area. The effect of experimental parameters, including the role of photocatalyst dosage, pH value, and initial concentration of pollutants on the degradation of CIP, have also been investigated.
Keywords: Carbon dots; Ciprofloxacin degradation; Norfloxacin degradation; Photocatalysis; Zinc Ferrite

Far-red active unsymmetrical squaraine dyes containing N-arylated indoline donors for dye sensitized solar cells - Jadhav, Avinash P.; Singh, Ambarish Kumar; Pandya, Rinu; Vanka, Kumar; Krishnamoorthy, Kothandam; Jayaraj, Nithyanandhan (Photochemistry and Photobiology, 2024)
Squaraine dyes possess sharp far-red active transition with high extinction coefficient and form aggregates on TiO2 surface. Aggregation of dyes on TiO2 has been considered as a detrimental factor for DSSC device performance, which can be controlled by appending alkyl groups to the dye structures. Hence by integrating alkylated (alkyl groups with both in-plane and out-of-plane) aryl group with indoline moiety to make it compatible with other electrolytes and for controlling the dye-aggregation, a series of squaraine acceptor-based dyes SQA4-6 have been designed and synthesized. SQA4-6 dyes showed absorption between 642 and 653 nm (lambda max), photophysical and electrochemical studies indicated that the HOMO energy levels of this sets of dyes are well aligned with the potentials of I-/I3-\$\$ {\textbackslashmathrm{I}}_3<\^>{-} \$\$ and [Co(bpy)3]2+/3+ redox shuttles for better dye regeneration process. DSSC device efficiency of 3% has been achieved for SQA5 dye with iodolyte (I-/I3-\$\$ {\textbackslashmathrm{I}}_3<\^>{-} \$\$) electrolyte in the presence of 0.3 mM of chenodeoxycholic acid (CDCA). The IPCE profile of DSSC device fabricated with SQA4-6 dyes indicated the contribution of aggregated structures for the photocurrent generation. Dye-sensitized solar cell (DSSC) device efficiency of 3% (Jsc 5.72 mA cm-2, Voc 662 mV and ff 79%) has been achieved for an unsymmetrical squaraine dye, SQA5 with iodolyte electrolyte and the incident photon to current efficiency (IPCE) profile indicates the contribution of aggregated structures for the photocurrent generation.*image
Keywords: aggregation of dye; arylation on N-atom of indoline donor; dye-sensitized solar cell; squaraine dye

F-doped nickel cobalt oxide-carbon composite electrocatalysts paired with mechanically robust anion-conducting chitosan membranes for flexible and rechargeable zinc-air batteries - Kurian, Maria; Ranganath, Suresha P.; Vijayakumar, Vidyanand; Sivadasan, Sneha; Kurian, Rachna Maria; Badiger, Manohar V.; Kurungot, Sreekumar (ACS Applied Energy Materials, 2024)
High-performing, cost-effective electrocatalysts and anion-conducting polymer electrolyte membranes are essential for realizing commercially affordable zinc-air batteries (ZABs). In this context, the present work deals with the development of a bifunctional electrocatalyst and an anion-exchange quasi-solid-state electrolyte membrane (based on quaternary ammonium group-grafted chitosan) for demonstrating flexible and rechargeable ZABs. The electrocatalyst composed of NiCoO2 nanoparticles supported on a carbon framework showcased substantial advancements in its ability to catalyze both oxygen reduction and evolution reactions (ORR and OER) due to the heteroatom doping by fluorine. For instance, the optimized electrocatalyst (F-NCO-ADC-600) exhibited an onset potential of 0.96 V vs RHE with a half-wave potential of 0.83 V vs RHE for ORR, a comparable performance with the state-of-the-art Pt/C (1.0 and 0.86 V vs RHE, respectively). On a similar note, the same catalyst also displayed an overpotential of 340 mV vs RHE for OER at a current density of 20 mA cm(-2), close to that of a standard RuO2 catalyst (337 mV vs RHE). In the context of polymer electrolytes, the quaternary ammonium-group-grafted chitosan membrane depicted superior ionic conductivity, liquid electrolyte uptake, and mechanical properties, thereby proving to be an efficient anion-conducting polymer electrolyte membrane. The realistic application of the developed electrocatalyst and the polymer electrolyte membrane is demonstrated in the ZAB prototypes. The assembled rechargeable ZAB (RZAB) delivered a power density of 207 mW cm(-2) and maintained high-rate capability and cycling stability, notably in a flexible configuration (f-RZABs). Thus, this work provides a strategy for the rational design of anion-exchange membranes and bifunctional electrocatalysts for f-RZABs.
Keywords: anion-conducting polymer electrolytemembrane; F-doping; flexible and rechargeable zinc-air batteries(f-RZABs); oxygen evolution reaction(OER); oxygen reduction reaction (ORR)

Ferric oxide nanocatalyst: synthesis, characterization, and application in the one-pot three-component synthesis of 3,4,5-trisubstituted isoxazole derivatives - Totre, Ganesh; Shinde, Dnyaneshwar; Shirsath, Sachin; Patil, Prakash; Kulkarni, Pramod (Monatshefte Fur Chemie, 2024)
In this study, we have focused on the preparation and application of a nano-ferric oxide catalyst as a heterogeneous catalyst in the one-pot, three-component synthesis of isoxazole derivatives. The ferric oxide catalyst was synthesized using a simple precipitation method and thoroughly characterized using techniques such as FT-IR, XRD, SEM, EDX, and BET. The effectiveness of the ferric oxide catalyst as a heterogeneous catalyst was investigated in the synthesis of 3,4,5-trisubstituted isoxazole. The results of the synthesis demonstrated that the catalyst exhibited high efficiency in facilitating the three-component, one-pot synthesis of 3,4,5-trisubstituted isoxazole derivatives. The synthesis route employed in this study offers several advantages, including its simplicity, ease of workup, and environmental friendliness. Furthermore, the catalyst was successfully recovered and reused for five cycles without experiencing a significant loss in catalytic activity. This finding highlights the excellent stability and promising potential of the catalyst for organic transformations. Overall, our study showcases the successful preparation and application of the nano-ferric oxide catalyst in the synthesis of isoxazole derivatives, providing valuable insights into its catalytic performance and potential for future applications in organic chemistry.
Keywords: Ferric oxide nanoparticles; heterogeneous catalyst; Isoxazole; Multicomponent reaction

Fictibacillus fluitans sp. nov., isolated from freshwater pond - Yadav, Amit; Maurya, Akanksha; Bhavsar, Yash; Teware, Ruchi; Bhatt, Agrima; DaCosta, Elaine; Thorat, Vipool; Kirdat, Kiran; Dastager, Syed G. (Archives of Microbiology, 2024)
A Gram-positive, aerobic, rod-shaped, spore-forming bacterium, designated NE201(T), was isolated from a freshwater pond in Village Nerur, India. Growth was observed in the range of 15-45 degrees C temperature with optimum at 30 degrees C, pH range of 5-9 (optimum at 7.0), and at concentrations of NaCl ranging between 0 and 14% (optimum 0%, w/v). The 16S rRNA gene sequence showed the highest similarity with Fictibacillus enclensis NIO-1003(T) (JF893461) at 99.01% followed by F. rigui WPCB074(T) (EU939689) at 98.9% and F. solisalsi CGMCC 1.6854(T) (EU046268) at 98.66%. The digital DNA-DNA hybridization (dDDH) and orthoANI values for strain NE201(T) against F. enclensis NIO-1003(T) (GCA_900094955.1) were 33.7% and 87.68%, respectively. The phylogenetic analysis based on the 16S rRNA gene, 92 core genes derived from the genome, and 20 proteins involving over 20,236 amino acid positions revealed the distinct phylogenetic position of strain NE201(T) and the formation of a clearly defined monophyletic clade with F. enclensis. The strain NE201(T) showed a unique carbon utilization and assimilation pattern that differentiated it from F. enclensis NIO-1003(T). The major fatty acids were anteiso -C-15:0 (51.42%) and iso-C-15:0 (18.88%). The major polar lipids were phosphatidylglycerol (PG), phosphatidylethanolamine (PE, and diphosphatidylglycerol (DPG). The antiSMASH analyzed genome of NE201(T) highlighted its diverse biosynthetic potential, unveiling regions associated with terpene, non-ribosomal peptide synthetases (NRPS), lassopeptides, NI-siderophores, lanthipeptides (LAP), and Type 3 Polyketide Synthases (T3PKS). The overall phenotypic, genotypic, and chemotaxonomic characters strongly suggested that the strain NE201(T) represents a novel species of genus Fictibacillus for which the name Fictibacillus fluitans sp. nov. is proposed. The type strain is NE201(T) (= MCC 5285 = JCM 36474).
Keywords: Bacillus; Fictibacillus; Freshwater bacteria

First-principles simulation of active site selectivity for CO2 and H2 adsorption on Mg(OH)+/Mg2+ and Ca(OH)+/Ca2+ zeolites - Samal, Pragnya Paramita; Krishnamurty, Sailaja (Journal of Physical Chemistry C, 2024)
One very effective strategy for addressing global warming and transitioning to sustainable energy sources is selective CO2 separation over H-2. Porous materials, particularly zeolites, have demonstrated enormous potential for energy-efficient separation techniques combined with storage. By altering interactions at cation-binding sites, zeolite's gas adsorption characteristics toward carbon capture can be improved. In this study, Mg and Ca are assessed as extra-framework cations in divalent (Ca2+, Mg2+) and monovalent states (Ca(OH)(+), Mg(OH)(+)) in faujasite and chabazite zeolites for CO2 capture over H-2. The study also explores the impact of mixed cations, viz., a combination of both Ca2+ and Mg2+ in the framework, on their selective adsorption potential. This study uses DFT with dispersion corrections to calculate adsorption energies, enthalpies, and Gibb's free energies of adsorbed CO2 and H-2 molecules. Among the dispersion parameters evaluated, viz., D4, TS/HI, and MBD, D4 approaches experimental accuracy. In general, the adsorption trend obtained for CO2 is Mg FAU > Ca FAU > Mg CHA > Ca CHA > Mg(OH)(+) FAU > Ca(OH)(+) FAU > Mg(OH)(+) CHA > Ca(OH)(+) CHA. The heats of adsorption using PBE+D4 for CO2 are -46 kJ/mol for Ca FAU and -10 kJ/mol for Ca(OH)(+) FAU, respectively. These values closely align with the experimental results of -45 and -6 kJ/mol, respectively, within a chemical accuracy limit of +/- 4 kJ/mol. The relative adsorption energies suggest that for both FAU and CHA, there exists a minimum difference of 26 kJ/mol in adsorption energies between CO2 and H-2. Hence, this piece of work highlights that FAU with Ca and Mg as extra-framework cations in a six-membered cage can be a viable substitute to replace, the current best candidate in literature, viz., Li+, for selective CO2 capture.

From digital blueprint to chemical reality: methanol to formaldehyde at ambient conditions - Mehta, Shweta; Kasabe, Mirabai; Umbarkar, Shubhangi B.; Joshi, Kavita (Applied Surface Science, 2024)
Partial oxidation of methanol to value added product presents an intriguing yet challenging process. Among these products, formaldehyde is the simplest and one of the most vital aliphatic aldehydes, which has extensive application across various domains. Industrially, silver and iron-molybdenum oxides are used as catalysts for the conversion of methanol to formaldehyde at elevated temperatures (600 degrees C and 250-400 degrees C, respectively). However, in this computational and experimental study, we have demonstrated the efficacy of ZnO as a catalyst. Notably, in the presence of ZnO, methanol readily converts to formaldehyde even under ambient conditions. We employed periodic density functional theory (DFT) to explore (10 1 1) facet of ZnO to elucidate its interaction with methanol. Our comprehensive analysis identified the most active facet (10 1 1) involved in the spontaneous conversion of methanol to formaldehyde. Subsequently, experimental validation supported our theoretical findings, demonstrating the conversion of methanol to formaldehyde with 100% selectivity at room temperature and atmospheric pressure in the presence of ZnO. This study exemplifies the pivotal role of theory in catalyst design.
Keywords: DFT; Formaldehyde; MeOH; ZnO

Fuel from waste: electrosynthesizing ammonia directly from agricultural digestate through ligand isomerization - Mendhe, Rahul Mahadeo; Mondal, Ritwik; Kottaichamy, Alagar Raja; Haridas, Akshay; Kotresh, Harish Makri Nimbegondi; Vinod, Chathakudath Prabhakaran; Thimmappa, Ravikumar; Thotiyl, Musthafa Ottakam (Green Chemistry, 2024)
We demonstrate that the catalytic metal centre for ammonia production can be selectively activated with only a slight alteration in ligand isomerization (alpha and beta isomers), making it practical and effective even for agricultural effluents. With almost 90% faradaic efficiency, the beta isomer generates approximately 0.64 mg h-1 cm-2 of ammonia. Energy-efficient ammonia recovery is made possible by the interfacial proton charge assembly that beta-isomerization creates, which attracts the reacting nitrate and repels the competing hydronium ions. With minimal energy consumption, this isomerization approach can interconvert agricultural effluents into ammonia fuel, reaching up to 84% of its theoretical yield and maintaining stability over 100 hours of continuous electrolysis. Ligand isomerization driven ammonia electrosynthesis from agricultural waste water.

Fuel-influenced nanorod-to-nanosphere transformation of vanadium-doped ZnO and its performance in dye-sensitized solar cells - Kuppusamy, Sasikumar; Mohan, Theanmozhi; Gnana Kumar, G.; Gopinath, Chinnakonda S.; Saha, Arindam; Michael, Robin Jude Vimal (NEW JOURNAL OF CHEMISTRY, 2024)
Keywords: Nanoparticles; Nanowires; Photoanode; Thin-films

Green synthesis of silver and gold ultra nanocomposites from silk fibroin and their application for treatment of endodontic infections - Pramod C.; Pawar, Jayant; Mane, Deepali P.; Khadase, Ashok N.; Chaudhari, Aditya R.; Ughade, Supriya P.; Chaudhari, Ravindra D.; Agawane, Sachin B. (Emergent Materials, 2024)
The present study is designed to investigate the antibacterial efficacy of B. mori silk fibroin based silver and gold ultra bio-nanocomposites (SF-AgUNC and SF-AuUNC) against Enterococcus faecalis for endodontic disinfection. The SF-AgUNC and SF-AuUNC based irrigant solution was tested in- vitro against Enterococcus faecalis (ATCC: 29212). In this direction, SF-AgUNC and SF-AuUNC synthesized by silk fibroin are very important as they are economically cheap and easy to biosynthesize. The synthesis of SF-AgUNC and SF-AuUNC was accomplished by dissolving 1 mM silver nitrate and 0.5 mM auric chloride respectively in 10 ml of fibroin as precursors. The structural and morphological analysis was executed by UV-Vis Spectroscopy, X-ray diffraction (XRD), Fourier transform infrared spectroscopic analysis (FTIR), Field Emission Scanning Electron Microscopy (FESEM), Transmission electron microscopy (TEM), Energy-dispersive X-ray spectroscopy (EDAX) and X-ray photoelectron spectroscopy (XPS). The qualitative antimicrobial activity of SF-AgUNC and SF-AuUNC were performed against inoculum of Enterococcus faecalis containing 1⨯105 CFU/ ml. The same solutions were tested on dentine specimens inoculated with bacterial cultures and found remarkable biofilm reduction. The structural and morphological analysis reveals the formation of SF-AgUNC and SF-AuUNC having quasi-spherical morphology. The average particle size for SF-AgUNC and SF-AuUNC was same (~ 8 nm). The XRD study confirms that, both SF-AgUNC and SF-AuUNC were crystalline in nature. The bacterial growth inhibition and significant biofilm reduction was observed on dentine specimens treated with SF-AgUNC, SF-AuUNC and positive control. In antibacterial study, at 30 μg/well concentration of SF-AgUNC and SF-AuUNC, 3.13 ± 0.22 and 1.13 ± 0.22 cm of zone of inhibition was noted respectively. Moreover, growth of Enterococcus faecalis was completely inhibited at 20 μg/ml and 30 μg/ml when treated with SF-AgUNC and SF-AuUNC respectively. Hence, the present study concludes that SF-AgUNC and SF-AuUNC can be used as an effective intracanal medicament for the treatment of dental problems with no cyto toxicity.

Harnessing the potential of Achromobacter sp. M1 to remediate heavy metals from wastewater: genomic insights and environmental applications - Mahale, Mithil; Samson, Rachel; Dharne, Mahesh; Kodam, Kisan (Journal of Hazardous Materials, 2024)
Lead, mercury, and cadmium are classified as toxic under the toxic Substances' Priority List by CDC-ATSDR (Center for Disease Control-Agency for Toxic Substances and Disease Registry). This toxic trio is capable of disrupting the one-health harmony due to its human, animal, and environmental hazards. The present study aimed in removing the toxic trio within 24 h using a novel Achromobacter sp. M1. Atomic absorption spectroscopic evaluation for removal efficiency of Pb, Hg, and Cd by M1 was 68.8 +/- 0.9%, 82.7 +/- 1.9%, and 94.9 +/- 1.2 %, respectively, within 24 h. Lab-scale evaluation of strain M1 with wastewater showed the removal of the toxic trio together with the reduction in TSS from 140 to 118 ppm, BOD from 100 to 58 ppm, and COD from 381 to 222 ppm. Furthermore, strain M1 was capable of mitigating heavy metal stress and promoting plant growth, evidenced through chlorophyll, malondialdehyde, and proline estimation, together with the production of indole acetic acid (23.84 mu g/mL), siderophore (85 %), and solubilization of silica (39.66 mu g/mL). Whole genome sequencing revealed an ANI of 89 %, indicating a novel species of Achromobacter genus. A total of 23 putative genes for Cd, Hg, and Pb resistance were identified through genome mining.
Keywords: Achromobacter sp. M1; Metal biosorption; Metal transporters; Toxic trio; Whole genome

Highly electrostrictive salt cocrystal and the piezoelectric nanogenerator application of its 3D-printed polymer composite - Sahoo, Supriya; Panday, Rishukumar; Kothavade, Premkumar; Sharma, Vijay Bhan; Sowmiyanarayanan, Anirudh; Praveenkumar, Balu; Zareba, Jan K.; Kabra, Dinesh; Shanmuganathan, Kadhiravan; Boomishankar, Ramamoorthy (ACS Applied Materials and Interfaces, 2024)
Ionic cocrystals with hydrogen bonding can form exciting materials with enhanced optical and electronic properties. We present a highly moisture-stable ammonium salt cocrystal [CH3C6H4CH(CH3)NH2][CH3C6H4CH(CH3)NH3][PF6] ((p-TEA)(p-TEAH)PF6) crystallizing in the polar monoclinic C2 space group. The asymmetry in (p-TEA)(p-TEAH)PF6 was induced by its chiral substituents, while the polar order and structural stability were achieved by using the octahedral PF6- anion and the consequent formation of salt cocrystal. The ferroelectric properties of (p-TEA)(p-TEAH)PF6 were confirmed through P-E loop measurements. Piezoresponse force microscopy (PFM) enabled the visualization of its domain structure with characteristic ``butterfly'' and hysteresis loops associated with ferro- and piezoelectric properties. Notably, (p-TEA)(p-TEAH)PF6 exhibits a large electrostrictive coefficient (Q(33)) value of 2.02 m(4) C-2, higher than those found for ceramic-based materials and comparable to that of polyvinylidene difluoride. Furthermore, the composite films of (p-TEA)(p-TEAH)PF6 with polycaprolactone (PCL) polymer and its gyroid-shaped 3D-printed composite scaled-up device, 3DP-Gy, were prepared and evaluated for piezoelectric energy-harvesting functionality. A high output voltage of 22.8 V and a power density of 118.5 mu W cm(-3) have been recorded for the 3DP-Gy device. Remarkably, no loss in voltage outputs was observed for the (p-TEA)(p-TEAH)PF6 devices even after exposure to 99% relative humidity, showcasing their utility under extremely humid conditions.
Keywords: 3D printing; cocrystals; energy harvesting; ferroelectricity; Piezoelectricity

Highly selective C-N and C-S dual functionalization of 1,3-dicarbonyl derivatives using TBHP as an oxidant - Bagad, Pooja K.; Darole, Ratanamala S.; Krishna, G. Rama; Senthilkumar, Beeran (Journal of Organic Chemistry, 2024)
A direct electrosynthesis/photocatalyst-free, atom-economical, and efficient method for the selective synthesis of (E)-3-amino-2-thiocyanato-alpha,beta-unsaturated carbonyl compounds is described through a given protocol. The present approach features the use of inexpensive ammonium thiocyanate to achieve dual functionalization of 1,3-dicarbonyl compounds using TBHP as an oxidant, providing a rapid and practical route to the selective formation of both C-N and C-S bonds via a radical process. This method offers a broad substrate scope with excellent yield and allows for further exploration of the products to construct heterocyclic compounds and other functionalities.

Highly stereoselective diels-alder-based strategy for the synthesis of 3-epi-formicin A and 1-epi-formicin B - Khamkar, Sunil L.; Handore, Kishor L.; Shinde, Harish M.; Reddy, D. Srinivasa (Organic Letters, 2024)
The first enantioselective approach based on a highly stereoselective Diels-Alder reaction for the synthesis of 3-epi-formicin A and 1-epi-formicin B with rare N-acetylcysteamine-containing indenone thioesters is reported. The strategy utilizes a key Diels-Alder reaction to form the core hydrindane system with three contiguous stereocenters in very high levels of diastereo- and regioselectivity and one-pot oxidation/isomerization/dehydrogenation. The scope of this method was tested with different substrates to give cycloadducts in a highly diastereoselective manner.

High-performance photodetector from p-n junction of vertically aligned SnS2 and reduced graphene oxide - Das, Chayan; Kumar, Suresh; Dambhare, Neha V.; Kumar, Mahesh; Rath, Arup K.; Sahu, Satyajit (ACS Applied Electronic Materials, 2024)
Semiconducting 2D transition metal dichalcogenides (TMDC) became very popular in photodetection due to their high mobility and high rate of generating electron and hole pairs. Over the past decade, MoS2 and WS2 became the most popular TMDC for several applications. On the other hand, due to the complex synthesis process compared to MoS2 and WS2, SnS2 became a less popular 2D material for photodetection. We synthesized vertically aligned SnS2 flakes by a chemical vapor deposition (CVD) process with three temperature zones with controlled argon (Ar) gas flow. Pristine SnS2-based devices are not very suitable for photodetection applications because of their low photo-to-dark current ratio (I ph /I (dark) ), high response time, and low stability. So, they need to be decorated with oppositely doped materials. We decorated pristine SnS2-based devices with rGO nanoparticles, which significantly increased the device's performance. We found a high responsivity (R) of 1.33 A/W, detectivity (D) of 6.95 x 10(11) Jones, I ph /I dark of 102, and a rise time of 0.241 ms (fall time of 1.318 ms) with the rGO decorated SnS2-based device.
Keywords: 2D-SnS2; CVD; p-njunction; photodetector; rGO

High-voltage symmetric supercapacitor electrodes via in situ synthesized multiwalled carbon nanotube-doped perylenebisimide-based donor-acceptor conjugate polymer P(PDI2OD-T2) - Wavhal, Aryan Anurath; Dilwale, Swati; Puthiyaveetil, Priyanka Pandinhare; Kakde, Navnath R.; Prakash, Medha; Kurungot, Sreekumar; Asha, S. K. (Journal of Physical Chemistry C, 2024)
This study presents the design and synthesis of a donor-acceptor pi-conjugated polymer composite P(PDI2OD-T2)/MWCNT tailored for high-voltage symmetric supercapacitor applications. The synthesis of P(PDI2OD-T2)/MWCNT was expedited by adopting a novel in situ polymerization technique that modifies the traditional Stille polymerization process. Incorporating approximately 33% by weight of multiwalled carbon nanotubes (MWCNT) into the polymer matrix, referred to as P-2, significantly enhances its conductivity, surface area, and porosity. These improvements in the material properties contribute to the superior electrochemical performance of the composites by promoting efficient electrolyte ion transport across the electrode-electrolyte interfaces. The symmetric supercapacitor devices fabricated with P-2 electrodes employing both liquid organic (LE-P-2||P-2) and quasi-solid-state gel (QSS- P-2||P-2) electrolytes demonstrate capacitance values of 85.4 and 84.2 F g(-1), respectively, at a current density of 0.25 A g(-1), while operating at a high-voltage window of 3.1 V. Moreover, these devices exhibit robust cycling stability, maintaining approximately 70% of their initial capacitance over 45,000 cycles with a coulombic efficiency of 96%. The successful demonstration of a quasi-solid-state symmetric supercapacitor underscores the potential of flexible energy storage solutions, as evidenced by a PMMA LiClO4 gel electrolyte prototype. This flexible device not only maintains structural integrity but also achieves an impressive power density of 18,600 W kg(-1) and an energy density of 112.4 Wh kg(-1), indicating its practical viability for real-world applications.

Hybrid silylene-Pd catalyst: efficient C-N cross-coupling of sterically bulky amines and chiral amines - Kaulage, Sandeep H.; Parvin, Nasrina; Khopade, Kishor V.; Khan, Shabana (Chemical Communications, 2024)
Herein, we report a catalytic system with N-heterocyclic silylene (NHSi)-phosphine-based hybrid bidentate ligands [PhC(NtBu)2SiN(PR2)(2,6-iPr2-C6H3)] and Pd(dba)2, which serves as an effective catalyst for C-N cross-coupling of a wide range of sterically bulky amines and optically active amines, which is challenging otherwise. Herein, we report a hybrid silylene-based bidentate ligand (SiNP)-Pd(0) catalytic system, which performs the C-N coupling of difficult substrates, e.g., sterically bulky amines and chiral amines.

Hydrogenation of furfural to tetrahydrofurfuryl alcohol over nickel-supported on organoclay catalyst - Kamble, Paresh A.; Vinod, C. P.; Rathod, Virendra K.; Kantam, Mannepalli Lakshmi (Applied Catalysis A-General, 2024)
Nickel supported on organoclay prepared by the impregnation method provides excellent catalytic activity for the hydrogenation of furfural to tetrahydrofurfuryl alcohol. The relative amount of metal and acidic sites influences the hydrogenation reaction. Additionally, by varying the temperature and the H-2 pressure, we can regulate the interaction of furfural with the active sites. And this may decide the fate of the reaction whether it will undergo a two-step hydrogenation to form tetrahydrofurfuryl alcohol or a rearrangement reaction to form cyclopentanone/cyclopentanol. Water was found to be the best solvent for the selective formation of tetrahydrofurfuryl alcohol. Even though alcohols inhibited rearrangement reaction, the hydrogenation of furfural was more selective towards furfuryl alcohol. Ni/O-clay30A under the optimum conditions of 120 degrees C, 4.0 MPa, and in 1 h offered complete conversion of furfural to tetrahydrofurfuryl alcohol.
Keywords: furfural; Hydrogenation; Nickel; organoclay; Tetrahydrofurfuryl alcohol

Hydrogenation of glucose to sorbitol by using nickel hydroxyapatite catalyst - Kamble, Paresh A.; Vinod, Chathakudath P.; Rathod, Virendra K.; Lakshmi Kantam, Mannepalli (Chemcatchem, 2024)
A series of nickel hydroxyapatite catalysts were synthesized by the co-precipitation method followed by calcination and reduction. These catalysts were employed for the aqueous phase hydrogenation of glucose to sorbitol. The Ni-HAP catalyst with comparatively high surface area and acid-base strength gave high sorbitol selectivity in 1 h. Ni-HAP-4 catalyst with moderate Ni (3.5 wt. %) content having smaller and highly dispersed nickel particles gives an excellent yield of sorbitol, 97 % in 1 h. The Ni-HAP-4 catalyst works well with other polar protic solvents. Different characterization techniques like XRD, TEM, SEM-EDS, BET, NH3-TPD, and CO2-TPD were employed to analyze the Ni-HAP-4 catalyst. A facile hydrogenation of glucose to sorbitol has been reported with Ni-HAP catalyst using water as a solvent. The excellent yield of sorbitol, 97 % in 1 h is possible due to the high surface area and high acid-base strength of the Ni-HAP-4 catalyst. image
Keywords: glucose; Hydrogenation; Hydroxyapatite (HAP); Nickel; Sorbitol

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

Implications of natural 3′-5′- linkages in the loop region of isomeric 2′-5′-linked thrombin-binding aptamer - Aher, Manisha; Kumar, Vaijayanti A.; Fernandes, Moneesha (Chemistryselect, 2024)
The backbone modification of the thrombin-binding aptamer (TBA) in the TT and TGT loop regions by isomeric 2 `-5 `-linkages was found to impose additive destabilizing effects on the thermal stability of the G-quadruplex structure. In contrast, the thermal stability of isomeric 2 `-5 `-linked TBA, i. e., isoTBA, was significantly improved by isomeric 3 `-5 `-phosphodiester linkages. The isoTBA, when modified with 3 `-5 `-linkages in both lateral TT loops (isoTBA202), exhibited higher thermal stability and enzymatic stability in comparison to other oligomers in the present study, and TBA202 showed higher antithrombin activity than other loop-modified TBA oligomers.
Keywords: 2 `-5 `-linked-linked DNA; DNA-isoDNA chimera; isoDNA; loop-modification; thrombin-binding aptamer

Improved protein dynamics and hydration in the martini3 coarse-grain model - Kharche, Shalmali; Yadav, Manjul; Hande, Vrushali; Prakash, Shikha; Sengupta, Durba (Journal of Chemical Information and Modelling, 2024)
The Martini coarse-grain force-field has emerged as an important framework to probe cellular processes at experimentally relevant time- and length-scales. However, the recently developed version, the Martini3 force-field with the implemented Go model (Martini3Go), as well as previous variants of the Martini model have not been benchmarked and rigorously tested for globular proteins. In this study, we consider three globular proteins, ubiquitin, lysozyme, and cofilin, and compare protein dynamics and hydration with observables from experiments and all-atom simulations. We show that the Martini3Go model is able to accurately model the structural and dynamic features of small globular proteins. Overall, the structural integrity of the proteins is maintained, as validated by contact maps, radii of gyration (Rg), and SAXS profiles. The chemical shifts predicted from the ensemble sampled in the simulations are consistent with the experimental data. Further, a good match is observed in the protein-water interaction energetics, and the hydration levels of the residues are similar to atomistic simulations. However, the protein-water interaction dynamics is not accurately represented and appears to depend on the protein structural complexity, residue specificity, and water dynamics. Our work is a step toward testing and assessing the Martini3Go model and provides insights into future efforts to refine Martini models with improved solvation effects and better correspondence to the underlying all-atom systems.

Indazole-5-amine (AIA) as competing corrosion coating to Benzotriazole (BTAH) at the interface of Cu: A DFT and BOMD case study - Samal, Pragnya Paramita; Singh, Chandrodai Pratap; Tiwari, Shivani; Shah, Vaishali; Krishnamurty, Sailaja (Computational and Theoretical Chemistry, 2024)
This study compares three organic compounds-benzotriazole (BTAH), imidazole (IM), and indazole-5-amine (AIA)-as corrosion inhibitors for copper substrates. Using Density Functional Theory (DFT) and Born-Oppenheimer Molecular Dynamics (BOMD) calculations, it identifies AIA as a promising and cost-effective alternative to the toxic BTAH. The adsorption strength on Cu(1 0 0) surfaces is ranked AIA>BTAH>IM for both neutral and deprotonated forms. These findings are supported by electronic parameter studies, including Bader charge analysis, density of states (DOS), charge density differences (CDD), and frontier molecular orbital analysis. AIA shows the best adsorption in a parallel orientation at the top site. Packing studies reveal that hydrogen bonding stabilizes the interaction energies within self-assembled AIA aggregates. Organometallic complexation studies reveal that deprotonated BTAH exhibits higher interaction energy with a single Cu atom compared to AIA when bonded through the carbon end, consistent with the findings from BOMD studies. However, on periodic Cu surfaces, AIA outperforms BTAH molecules as seen from adsorption energies. This investigation highlights AIA's potential as a superior and more economical corrosion inhibitor for copper.
Keywords: Adsorption; Born-Oppenheimer molecular dynamics; Corrosion inhibition; Density functional theory; Indazole derivatives

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

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

Integrated genomic and functional analysis of Streptomyces sp. UP1A-1 for bacterial wilt control and solanaceae yield increase - Kaari, Manigundan; Manikkam, Radhakrishnan; Joseph, Jerrine; Krishnan, Sakthivel; Annamalai, Kishore Kumar; Khan, Abujunaid; Rajput, Vinay; Dastager, Syed Gulam; Dharne, Mahesh S.; Umar, Md; Venugopal, Gopikrishnan; Alexander, Balamurugan (Gene Reports, 2024)
<em style="box-sizing: border-box; margin: 0px; padding: 0px; color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;">Ralstonia solanacearum<span style="color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;"> is one of the most destructive soil-borne pathogen, causing bacterial wilt to the solanaceae vegetables. <em style="box-sizing: border-box; margin: 0px; padding: 0px; color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;">Streptomyces<span style="color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;"> sp. UP1A-1 isolated from healthy solanaceae rhizosphere soil, exhibited the lowest disease incidence and increased fruit yield of solanaceae vegetables. However, the genomic and functional properties of UP1A-1 are unclear. Therefore, we conducted the present study to elucidate the genomic characteristics of UP1A-1 by whole genome sequencing. The results indicate that the genome of <em style="box-sizing: border-box; margin: 0px; padding: 0px; color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;">Streptomyces<span style="color: rgb(31, 31, 31); font-family: ElsevierGulliver, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif, sans-serif; font-size: 16px;"> sp. UP1A-1 consists of 8,252,902 bp and contains 72.42 % G + C. We identified the genes that confer plant growth promoting (PGP) function, which include those involved in siderophore production, indole-3-acetic acid biosynthesis, phosphate solubilization, nitrogen metabolism, and potassium metabolism. We also identified several other genes, such as chitinase, peroxidase, superoxide dismutase, catalase, proline biosynthesis, and glucose dehydrogenase, which are believed to be involved in the control of wilt disease. These genes revealed that the strain UP1A-1 has physiologically adapted to varied environmental conditions and could potentially control both abiotic and biotic stresses.

Interface-centric strategies in kesterite solar cells: addressing challenges, solutions, and future directions for efficient solar-harvesting technologies - Jagadish, Kusuma; Rahane, Ganesh K.; Kumar, Boddeda Sai; Borkar, Durgesh R.; Chordiya, Kalyani; Kavanagh, Sean R.; Roy, Anurag; Debnath, Tushar; Kolekar, Sadhu; Kahaly, Mousumi Upadhyay; Mali, Sawanta S.; Pal, Shovon; et al. (SMALL, 2024)
Keywords: band engineering; Defects; interface loss mechanism; kesterites; recombination control; solar energy

Interlayer space engineering-induced pseudocapacitive zinc-ion storage in holey graphene oxide-bearing vertically oriented MoS2 nano-wall array cathode for aqueous rechargeable Zn metal batteries - Babu, Athira; Dilwale, Swati; Kurungot, Sreekumar (Small, 2024)
Transition metal dichalcogenides, particularly MoS2, are acknowledged as a promising cathode material for aqueous rechargeable zinc metal batteries (ARZMBs). Nevertheless, its lack of hydrophilicity, poor electrical conductivity, significant restacking, and restricted interlayer spacing translate into inadequate capacity and rate performance. Herein, the unique porous structure and additional functional groups present in holey graphene oxide (hGO) are taken advantage of to dictate the vertical growth pattern of oxygen-doped MoS2 nanowalls (O-MoS2/NW) over the hGO surface. Compared to conventional graphene oxide (GO), the presence of nano-pores in hGO facilitates the homogeneous dispersion of Mo precursors and provides stronger interaction sites, promoting the uniform vertical alignment of O-MoS2/NW. The synergistic interaction between O-MoS2-NW and hGO translates to enhanced electron conductivity, efficient electrolyte penetration, enhanced interlayer spacing, reduced restacking, and enhanced surface area. As a consequence of precise control of various factors that decide the overall battery performance, a high discharge capacity (227 mAh g(-1) at 100 mA g(-1)) cathode material with significantly lower charge transfer resistance (66 Omega) compared to pristine O-MoS2 (153 Omega) is developed. These findings underscore the potential of hGO as a multifunctional platform for nanoengineering high-performance cathode materials for the next generation of efficient and durable ARZMBs.
Keywords: aqueous rechargeable zinc metal battery; holey graphene oxide; hydrophilicity tuning; interlayer space engineering; oxygen-doped MoS2; transition metal dichalcogenide; vertical nanowall

Investigation of cathinone analogs targeting human dopamine transporter using molecular modeling - Shivankar, Bhavana R.; Bhandare, Vishwambhar Vishnu; Joshi, Krati; Patil. Vishal S.; Dhotare, Priyanka Shrikant; Sonawane, Kailas Dasharath; Krishnamurty, Sailaja (Journal of Biomolecular Structure & Dynamics, 2024)
In a step towards understanding the structure–property relationship among Synthetic Cathinones (SCs), a combined methodology based on Density Functional Theory (DFT), Administration, Distribution, Metabolism, Excretion, and Toxicity (ADMET) predictions, docking and molecular dynamics simulations have been applied to correlate physicochemical descriptors of various SCs to their biological activity. The results from DFT and molecular docking studies correlate well with each other explaining the biological activity trends of the studied SCs. Quantum mechanical descriptors viz. polarizability, electron affinity, ionization potential, chemical hardness, electronegativity, molecular electrostatic potential, and ion interaction studies unravel the distinguishingly reactive nature of Group D (pyrrolidine substituted) and Group E (methylenedioxy and pyrrolidine substituted) compounds. According to ADMET analysis, Group D and Group E molecules have a higher probability of permeating through the blood–brain barrier. Molecular docking results indicate that Phe76, Ala77, Asp79, Val152, Tyr156, Phe320, and Phe326 constitute the binding pocket residues of hDAT in which the most active ligands MDPV, MDPBP, and MDPPP are bound. Finally, to validate the derived quantum chemical descriptors and docking results, Molecular Dynamics (MD) simulations are performed with homology-modelled hDAT (human dopamine transporter). The MD simulation results revealed that the majority of SCs remain stable within the hDAT protein’s active sites via non-bonded interactions after 100 ns long simulations. The findings from DFT, ADMET analysis, molecular docking, and molecular dynamics simulation studies complement each other suggesting that pyrrolidine-substituted SCs (Group D and E), specifically, MPBP and PVN are proven potent SCs along with MDPV, validating various experimental observations.

Ionic liquid assisted green synthesis of quinoxaline based bisspirooxindoles: anticancer evaluation and molecular dynamics - Kanchrana, Madhu; Krishna, Gamidi Rama; Dey, Biswajit; Pandey, Nandita; Guru, Santosh Kumar; Sangolkar, Akanksha Ashok; Pawar, Ravinder; Basavoju, Srinivas (CHEMISTRYSELECT, 2024)
Keywords: Cycloaddition; spirooxindoles

Iron in organometallic transformations: a sustainable substitute for noble metals - Kumar, Rohit; Tewari, Tanuja; Chikkali, Samir H. (ChemCatChem, 2024)
Transition metal catalysis plays a pivotal role in chemical synthesis. Noble metals often grab significant attention in organometallic catalysis due to their high reactivity. However, the serious issues associated with these metals such as low abundance, toxicity, geopolitical limitations, and volatile prices are driving the scientific community to discover sustainable alternatives. In this context, iron appears to be the first choice as an alternative metal due to its unique properties, including a range of stable oxidation states, Lewis acidity, high abundance in the earth's crust, and low toxicity. Over the past two decades, substantial progress has been made in iron catalysis. This overview examines the recent developments in iron-catalyzed industrially relevant transformations such as hydroformylation, olefin isomerization, hydrosilylation, hydrophosphination, carbonylation, Wacker-type oxidation, and plastic depolymerization. As witnessed throughout this review, the performance of iron can be significantly altered by suitable ligand selection and by tailoring the electronic and steric properties of the iron center. While noble metals remain the industry work-horse, iron is inching closer and with extensive scientific understanding, it may replace noble metals in the near future. Late transition metals catalyze several reactions and have been the industry work-horse for decades. While, earth abundant metals are rarely used in industrially relevant transformations. In this overview, we examine the recent development in iron-catalyzed industrially relevant reactions such as hydroformylation, olefin isomerization, hydrosilylation, hydrophosphination, carbonylation, Wacker-type oxidation, and plastic depolymerization. Iron is inching closer and may replace noble metals in near future. image
Keywords: Alkene Isomerization; alkyne; Carbonylation; depolymerization; Hydrophosphination; Hydrosilylation; iron catalysis

Iron salicylaldehydate conjugated metal-organic framework for quasi solid-state supercapacitor - Mohammed, Abdul Khayum; Pandikassala, Ajmal; Sanchez, Pilar Pena; Gaber, Safa Abdullah; Canossa, Stefano; Kurian, Maria; Xavier, Gigi; He, Yao; Gandara, Felipe; Kurungot, Sreekumar; Shetty, Dinesh (CHEMICAL ENGINEERING JOURNAL, 2024)
Keywords: Carbon; conductivity; ELECTROLYTE CONCENTRATION; performance; ROBUST

Iron-catalyzed C-C and C-N bond-forming tandem amidation offering access to 3-amino-3-aminomethyl-2-oxindole frameworks - Ankade, Shidheshwar B.; Pradhan, Chandini; Samal, Pragnya Paramita; Gonnade, Rajesh G.; Krishnamurty, Sailaja; Punji, Benudhar (Advanced Synthesis & Catalysis, 2024)
An iron-catalyzed protocol for the synthesis of 3-amino-3-aminomethyl-2-oxindole heterocyclic structures is disclosed employing isatins and non-nucleophilic N-methoxybenzamides. This reaction class is associated with broad scope and tolerates numerous functionalities, such as fluoro, chloro, bromo, iodo, trifluoromethyl, nitrile, ester, ether, and alkenyl, including heteroaryl - thiophene, benzothiophene, carbazolyl, indolyl, eugenol, and polycyclic cholesterol moieties. Detailed mechanistic investigations reveal that the reaction proceeds via iron-catalyzed N-O bond cleavage in N-methoxybenzamides, generating formaldehyde and benzamide, and through the intermediacy of isatin-ketimines and N-(hydroxymethyl)benzamides. Overall, this amidation reaction involves one C-C and two C-N bond-forming tandem processes, providing a range of beta-amino-aminomethyl-oxindoles (45 examples) in up to 88% yields. image
Keywords: benzamide; iron; Isatin; tandem amidation; tetrasubstituted carbon stereocenter

Iron-catalyzed (E)-selective hydrosilylation of alkynes: scope and mechanistic insights - Sen, Anirban; Tewari, Tanuja; Kumar, Rohit; Vinod, C. P.; Sharma, Himanshu; Vanka, Kumar; Chikkali, Samir H. (Catalysis Science and Technology, 2024)
Iron-catalyzed hydrosilylation of internal alkynes has been rarely reported. Even in these rare cases, additives have been used for the success of the reaction, which often creates a problem for the functional group tolerance of the reaction. Herein, we report an additive-free iron-catalyzed (E)-selective hydrosilylation of internal alkynes in the presence of a phosphine ligand. A low-valent Fe(0) complex [Fe(CO)(3)(BDA)] {[Fe-1]} catalyzed the hydrosilylation of alkynes at 60 to 120 degrees C, exhibited a broad substrate (24 substrates) scope and tolerated different functional groups. The synthetic utility of the reaction was demonstrated by a gram scale experiment, preparing alkenes, and by chemo-selective hydrosilylation. The modus operandi of the reaction has been investigated by i) homogeneity test, ii) radical trapping experiments, iii) X-ray photoelectron spectroscopy, and iv) by preparing a Fe(II) complex as catalyst control. These mechanistic investigations revealed a two-electron pathway for the hydrosilylation of alkynes. In addition, kinetic investigations were undertaken to shed light on the rates of the reaction. Kinetic studies suggest the absence of an induction period, and the reaction is first order with respect to the concentration of iron catalyst [Fe-1] and zeroth order with respect to the substrate (alkyne). The Hammett plot suggests that strongly electron-withdrawing groups on the alkyne favour the hydrosilylation reaction. Meanwhile Eyring analysis suggests that the rate-determining step likely involves an associative pathway. Based on the findings of the mechanistic and kinetic investigation, a plausible Chalk-Harrod-type mechanism is likely to be operative. The proposed mechanism is substantiated by computational investigations, which suggested that the Chalk-Harrod mechanism is kinetically more favored by 15.8 kcal mol(-1) over the modified Chalk-Harrod mechanism.

Kinetic model of hydrogenation of glucose to sorbitol on a Ni/Bentonite catalyst - Pandya, Harmitkumar; Vinod, Chathakudath Prabhakaran; Rathod, Virendra; Kantam, Mannepalli Lakshmi (Industrial and Engineering Chemistry Research, 2024)
In the present work, we studied the hydrogenation of glucose to sorbitol using a nickel/bentonite catalyst. The Ni/bentonite catalyst was prepared by the wet impregnation method and characterized by different methods to understand the catalyst surface morphology, surface area, metal content, pore size, etc. Different reaction parameters such as temperature, hydrogen pressure, metal loading, catalyst loading, and agitation speed were studied to achieve a glucose conversion of 96.8% and a sorbitol selectivity of 95.3%. The reusability test was performed to examine the stability of the catalyst. The kinetic models such as the Eley-Rideal and Langmuir-Hinshelwood-Hougen-Watson models were used to study the hydrogenation of glucose and activation energy required for the reaction.

Lanthanide mimicking by magnesium for oxazolidinone synthesis - Kumar, Rohit; Mahata, Biplab; Gayathridevi, S.; Raj, K. Vipin; Vanka, Kumar; Sen, Sakya S. (Chemistry- a european journal, 2024)
In the last decade, magnesium complexes have emerged as a viable alternative to transition-metal catalysts for the hydrofunctionalization of unsaturated bonds. However, their potential for advanced catalytic reactions has not been thoroughly investigated. To address this gap, we have developed a novel magnesium amide compound (3) using a PNP framework that is both bulky and flexible. Our research demonstrates that compound 3 can effectively catalyze the synthesis of biologically significant oxazolidinone derivatives. This synthesis involves a tandem reaction of hydroalkoxylation and cyclohydroamination of isocyanate using propargyl alcohol. Furthermore, we conducted comprehensive theoretical calculations to gain insights into the reaction mechanism. It is important to note that these types of transformations have not been reported for magnesium and would significantly enhance the catalytic portfolio of the 7th most abundant element. A monomeric magnesium compound was employed as a catalyst for the cascade cyclization of propargylic alcohol and isocyanate, resulting in the formation of pharmaceutically significant oxazolidinone derivatives. This transformation, previously attributed solely to transition metals or lanthanides, signifies a noteworthy advancement.image
Keywords: catalysis; Magnesium; oxazolidinone; pincer ligand; Sustainability

Lead-free low-dimensional tetraalkylammonium manganese- and copper-based hybrid organic–inorganic perovskites for visual fluorometric Pb2+ ion detection - Kour, Prachi; Sahu, Pragati; Dambhare, Neha V.; Rath, Arup Kumar; Mukherjee, Shatabdi Porel (ACS Applied Optical Materials, 2024)
For the first time, we have synthesized lead (Pb)-free manganese (Mn)- and copper (Cu)-based hybrid organic–inorganic perovskite (HOIP) compounds, compound 1, (TEA)2MnBr4, compound 2, (TBA)2MnBr4, compound 3, (TEA)2CuBr4, and compound 4, (TBA)CuBr2 (where TEA is tetraethylammonium and TBA is tetrabutylammonium), under ambient conditions via mechanochemical synthesis methodology using a Kakuhunter-made planetary mixer. The compounds are characterized as 2D except for (TBA)CuBr2, which has crystallized in the 0D lattice. The synthesized compounds are phase pure and show a stable solid-state emission at room temperature. The Mn-based perovskite compound 1 showed excellent environmental photostability for over a month and reasonable stability under a relative humidity of 70–80%. The nanoparticle (NP) dispersions of compounds 1 and 2 were used further for fluorescence titration studies using various heavy metal cations, including transition metals and lanthanides (e.g., Y3+, Nb3+, Co2+, Ni2+, Ag+, Zn2+, Cd2+, Pb2+, Gd3+, and Dy3+), where they showed good fluorescence switching by the Pb2+ ion. Compound 1 demonstrated excellent fluorescence switching performance with Pb2+ titration with a Pb2+ detection limit of 2.43 × 10–8 M and hence can be used to fabricate a Pb2+ calorimetric sensor. A preliminary visual thin film-based sensor using NPs of compound 1 was fabricated to test the change in emission from blue to green in correlation with the results obtained in the NP solution during Pb2+ ion sensing. A fascinating in situ ion-exchange-based mechanism for the sensitivity of NPs of compound 1 is confirmed. This study reveals the ability of Pb-free Mn-based HOIPs to detect an oxidizing metal cation, Pb2+, efficiently and quantitatively.

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

Ligand-free MnBr2-catalyzed chemo- and stereoselective hydroboration of terminal alkynes - Pawar, Rameshwar B.; Karmur, Mital H.; Punji, Benudhar (Chemistry-an asian jounrnal, 2024)
Developing simple and benign protocols for synthesizing alkenylboronates is crucial as they are synthetically valuable compounds in various organic transformations. In this work, we report a straightforward ligand-free protocol for synthesizing alkenylboronates via atom-economical hydroboration of alkynes with HBpin catalyzed by a manganese salt. The reaction shows a high level of chemo and regioselectivity for the terminal alkynes and exclusively produces E-selective alkenylboronates. The hydroboration scope is vast, with the resilience of a range of synthetically beneficial functionalities, such as halides, ether, alkenyl, silyl and thiophenyl groups. This reaction proceeds through the involvement of a metal-hydride intermediate. The developed alkenylboronate can be smoothly converted to useful C-C, C-N and C-I bond-forming reactions.
Keywords: alkenylboronates; alkyne; Hydroboration; manganese; stereoselectivity

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

Metal-free one-pot domino synthesis of oxazolidinethione derivatives of quaternary amino acids from α-amino esters and aldehydes using CS2 - Shinde, Dinesh R.; Krishna, Gamidi Rama; Marelli, Udaya Kiran (Journal of Organic Chemistry, 2024)
We present a streamlined, metal-free, one-pot domino approach to efficiently synthesize oxazolidinethione derivatives containing substituted quaternary amino acids. This method employs alpha-amino esters, aldehydes, and CS2 under mild conditions, constructing three new bonds (C-N, C-C, and C-O) to produce oxazolidinethione compounds featuring a quaternary center and a beta-hydroxy derivative in high yields. This scalable protocol enables the creation of libraries of biologically significant, intricate amino acid derivatives using amino esters and aldehydes.

Metal-organic frameworks for enhanced hydrogen generation from syngas: a density functional theory approach - Gopalsamy, Karuppasamy; Singh, Chandrodai Pratap; Krishnamurty, Sailaja; BabaRao, Ravichandar (CHEMPLUSCHEM, 2024)
Keywords: carbon capture; H-2 separation; Metal organic; Porous coordination network (PCN-250); Syngas

Microbial production of N-acetyl-D-glucosamine (GlcNAc) for versatile applications: biotechnological strategies for green process development - Das, Sancharini; Chowdhury, Chiranjit; Kumar, S. Pavan; Roy, Debasis; Gosavi, Suresh W.; Sen, Ramkrishna (Carbohydrate Research, 2024)
N-acetyl-D-glucosamine (GlcNAc) is a commercially important amino sugar for its wide range of applications in pharmaceutical, food, cosmetics and biofuel industries. In nature, GlcNAc is polymerised into chitin biopolymer, which is one of the major constituents of fungal cell wall and outer shells of crustaceans. Sea food processing industries generate a large volume of chitin as biopolymeric waste. Because of its high abundance, chitinaceous shellfish wastes have been exploited as one of the major precursor substrates of GlcNAc production, both in chemical and enzymatic means. Nevertheless, the current process of GlcNAc extraction from shellfish wastes generates poor turnover and attracts environmental hazards. Moreover, GlcNAc isolated from shellfish could not be prescribed to certain groups of people because of the allergic nature of shell components. Therefore, an alternative route of GlcNAc production is advocated. With the advancement of metabolic construction and synthetic biology, microbial synthesis of GlcNAc is gaining much attention nowadays. Several new and cuttingedge technologies like substrate co-utilization strategy, promoter engineering, and CRISPR interference system were proposed in this fascinating area. The study would put forward the potential application of microbial engineering in the production of important pharmaceuticals. Very recently, autotrophic fermentation of GlcNAc synthesis has been proposed. The metabolic engineering approaches would offer great promise to mitigate the issues of low yield and high production cost, which are major challenges in microbial bio-processes industries. Further process optimization, optimising metabolic flux, and efficient recovery of GlcNAc from culture broth, should be investigated in order to achieve a high product titer. The current study presents a comprehensive review on microbe-based eco-friendly green methods that would pave the way towards the development of future research directions in this field for the designing of a cost-effective fermentation process on an industrial setup.
Keywords: Genetic engineering; GlcNAc applications; Market status; Microbial bioprocess; N-acetyl-D-glucosamine; synthetic biology

Model predicted optimization of experimental set-up and process conditions for microwave-assisted synthesis of silver nanowires - Sonawane, Jayesh R.; Kulkarni, Amol A. (Chemical Engineering Journal, 2024)
This work presents simulations led optimization of choice of a reactor for an experimental set-up for the continuous production of silver nanowires with certain constraints in terms of yield, reaction time, and dimensions of nanowires. The choice of reactors based on the simulations of reaction kinetics for nucleation and growth phases of driving the optimization of an experimental set-up and subsequent optimization of process conditions to maximize the yield of nanowires of desired dimensions. The optimized reactor configuration is dictated by the reaction kinetics and using a microwave in continuous mode becomes unavoidable. This makes the approach highly reproducible as well as scalable. The integration of conventional and microwave heating is simulated and subsequently optimized experimentally to attain a significant increase in nanowire yield under steady-state conditions with less than 15 min of residence time. The precise control over the rate in different reactor configurations governing nucleation, accelerated growth followed by slow growth to complete the conversion of precursor enables higher selectivity of nanowires with controllable dimensions resulting in 100 gm production per day using simple set-up. We systematically examined key reaction parameters, including the concentration of metal ions, residence time, and different reactor configurations. Our approach successfully yielded AgNWs with 40-60 nm diameter and 15 mu m length. The cost associated with this process for synthesizing AgNWs is less than 10\$ per gram. This study highlights the potential of continuous, high-throughput processes for controlling nanowire size and yield through advanced reactor engineering.
Keywords: Continuous synthesis; Microwave; Reactor design; Silver Nanowires

MOFite: a high-density lithiophilic and scalable metal-organic framework anode for rechargeable lithium-ion battery - Gaber, Safa; Mohammed, Abdul Khayum; Javaregowda, Bharathkumar H.; Martinez, Jose Ignacio; Sanchez, Pilar Pena; Gandara, Felipe; Krishnamoorthy, Kothandam; Shetty, Dinesh (ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2024)
Keywords: conjugated MOF; Energy storage; lithium ion battery; Metal-organic framework; scalable synthesis

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

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

New binary adducts of panobinostat with different carboxylic acid based NSAIDs: structural analysis and physicochemical properties investigation - Kenguva, Gowtham; Rout, Smruti Rekha; Kar, Ananya; Giri, Lopamudra; Shaikh, Tabrez R.; Jadab, Madhusmita; Pal, Satyanarayan; Dandela, Rambabu (ChemistrySelect, 2024)
Adoption of multitarget, cost-effective fixed-dose medication combinations can help lower the pill load without increasing the risk of adverse events. In this study, three new 1:1 drug-drug binary solid forms of panobinostat (PNB) and nonsteroidal anti-inflammatory drugs (NSAIDs) were effectively synthesized by liquid-assisted grinding and slow evaporation crystallization techniques. The obtained solid forms were extensively characterized by various analytical techniques. The structural investigation revealed that all molecular adducts formed salt with a comparable R42\${\textbackslashmathrm{R}}_4<\^>2\$(10) graph set pattern created by heteromeric interactions formed between PNB and corresponding salt formers. To determine the dissolving behavior of the newly developed adducts, solubility tests were performed at various pH levels (pH 1.2 and pH 7), and the results indicated that the solubility of all forms is increased at pH 7.0, particularly PNB.NIF has a solubility of 0.195 mg/mL, which is seven times higher than the parent drug. Furthermore, PXRD was used to assess the stability of the synthesized adduct at varied temperature and humidity levels and it was found that all the adducts are stable. Based on the findings, we hope that the newly found PNB drug-drug binary adducts have possible potential to broaden the use of drug combinations without changing the chemical structures.
Keywords: Drug-drug salts; Heteromeric interactions; Hydrogen bond; Non-steroidal anti-inflammatory drugs; Panobinostat

New insights into the composition and catalytic performance of VOx-Ga/γ-Al2O3 for the oxidative dehydrogenation of propane to propene - Kandasamy, Prabu; Gawali, Sheetal; Venugopalan, Aswathy Thareparambil; Manikandan, Marimuthu; Mekala, Siva Prasad; Shelke, Ankita; Ajithkumar, Thalasseril G.; Bhatte, Kushal; Raja, Thirumalaiswamy (New Journal of Chemistry, 2024)
Oxidative dehydrogenation (ODH) of propane is a promising alternative route for propene production. In this work, we developed a series of vanadium and gallium oxides supported on gamma-Al2O3 catalysts by an incipient wetness impregnation method. Among the employed catalysts, the VGA-2 showed superior catalytic activity, and the catalyst was demonstrated for longevity in ODH of propane with a stable activity using a continuous flow fixed bed reactor at 400 degrees C. H-2-TPR and UV-visible spectra showed the presence of highly dispersed monomeric VOx species with tetrahedral coordination geometry, which influences product selectivity. The characterization results also conferred that the redox nature of vanadium (V5+ and V4+) oxide and higher V5+ content on the surface of the VGA-2 catalysts are more favourable for C-H activation. In addition, the pyridine-FTIR and Ga-71 solid-state NMR studies further substantiated the presence of Lewis acid sites and tetrahedrally coordinated Ga3+Ox species that are highly responsible for the ODHP activity, respectively. Furthermore, in situ-DRIFTS studies conferred that the propane adsorption at ambient temperature showed the formation of intermediate propoxide species with the evolution of sigma-bonds and with further increase in the temperature to 325 degrees C; the stretching vibrations of the =C-H and -C-H bonds in the propylene molecule were observed. The spent catalysts were also analyzed by thermogravimetric analysis, where the optimized catalyst (VGA-2) showed the least coke deposition.

Normal and diabetic foot sole skin mimicking tissue phantom fulfillment for spectroscopic-based DFU diagnostics perspective - Kumar, Ajay; Hattale, Gangadhar; Hinge, Sarika; Kulkarni, Gauri; Late, Dattatray J.; Kanawade, Rajesh (AIP ADVANCES, 2024)
Keywords: OPTICAL-PROPERTIES; STATE

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

Novel molecular adducts of an anti-cancer drug vandetanib with enhanced solubility - Bandaru, Ravi Kumar; Giri, Lopamudra; Krishna, Gamidi Rama; Dandela, Rambabu (Crystengcomm, 2024)
The solubility, permeability, and dissolution rate of an active pharmaceutical ingredient (API) are critical factors in determining its pharmacokinetic performance in oral dosage forms. Modifying these properties can potentially enhance the drug's pharmacokinetics. Vandetanib (VDTB), classified as a class II anti-cancer drug in the biopharmaceutical classification system (BCS), suffers from low solubility (0.008 mg mL-1) and an extended pharmacokinetic half-life (19 days), necessitating the administration of high doses, which leads to undesirable side effects. To address this issue, we have employed a crystal engineering approach to enhance the solubility of VDTB. We employed the liquid-assisted grinding (LAG) method followed by the slow evaporation technique to prepare novel solid forms of VDTB by incorporating various aliphatic dicarboxylic acids, including succinic acid (SUA), adipic acid (ADA), pimelic acid (PIA), azelaic acid (AZA), and sebacic acid (SBA). These newly obtained solid forms were characterized by SC-XRD, PXRD, TGA, and DSC experiments. The crystal structure analyses revealed a proton transfer between the carboxylic acid group of aliphatic acids and the N-methyl piperidine moiety of VDTB, confirming salt/adduct formation. Additionally, all of the molecular salts were stabilized by charge-assisted N+-HMIDLINE HORIZONTAL ELLIPSISO- hydrogen bonds, while the parent VDTB crystal structure is stabilised by N-HMIDLINE HORIZONTAL ELLIPSISN interactions. Moreover, the solubility and dissolution rate of these new solid forms were assessed in a pH 7.4 phosphate buffer medium, with the results indicating that all of the solid forms, except for VDTB:SBA, exhibited higher solubility compared to pure VDTB. These findings offer promising prospects for the development of an improved VDTB formulation with enhanced pharmacokinetic properties. Successful attempt to improve the solubility and dissolution rate of Vandetanib - an anti-cancer drug, by crystal engineering approach.
Keywords: Amorfization; hydrate; Parameters; Salt; Thyroid-Cancer