Influence of van der waals interactions between the alkyl chains of surface ligands on the size and size distribution of nanocrystals prepared by the digestive ripening process - Shimpi, Jayesh R.; Thomas, Rinto; Meena, Santosh Kumar; Prasad, Bhagavatula L. V. (Langmuir, 2023)
Thermal heating of polydispersed nanocrystals (NCs) with surface-active organic ligands in a solvent leads to the formation of monodispersed NCs, and this process is known as digestive ripening (DR). Here, by performing DR on Au NCs using different-chain-length amine and thiol ligands, we evidently show that ligands with C-12 chain length result in the formation of NCs with narrow size distributions when compared to C-8, C-16, and C-20 chain length ligands. Furthermore, our findings also show that in the case of alkyl thiol, the NC size remains more or less the same, while the size distribution gets altered significantly with the chain length. On the other hand, both size and size distribution are affected significantly when the alkyl amine chain length is varied. Fourier transform infrared (FTIR) studies indicate that the van der Waals (vdW) interactions are weakest when the amine with C-12 carbon chain is used as the DR agent, while in the case of thiols, molecules with C-8 and C-12 chain lengths have nearly the same vdW interactions (with C-12 slightly weaker than C-8), which are weaker than those of C-16 and C-20. Molecular dynamics (MD) simulation results corroborate the experimental observations and suggest that due to more defects in the alkyl chain, the C-8 and C-12 (amine as well as thiol) ligands are disordered and less stable on Au(111) and Au(100) surfaces. This could result in efficient etching and redeposition, making the ligands with C-8 and C-12 chain lengths the better DR agents.

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

Interactive study of Au-20 nanocluster and methyl substituted amide linked tyrosine/tryptophan to develop representative model for studying protein-nanoparticle interaction - Sen Banerjee, Nineesha; Ghosh, Deborin; Mitra, Ishani; Paul, Somnath; Show, Bibhutibhushan; Ganguly, Tapan; Chakraborty, Madhurima (Journal of Molecular Structure, 2023)
Investigations on UV-vis, steady-state fluorescence and synchronous fluorescence properties of human hemoglobin (HHb) reveals greater spectral shifts in peaks arising due to alterations in microenvironment of Tyr-compared to Trp-during interactions with gold nanoparticle (GNP). Besides, interactions of Au-20 nanocluster with modified Tyr/Trp (possessing methyl substituted amide bonds) by quantum chemical calculations demonstrate significant role of amide bonds and the spectral shift, binding energy and alteration in bond distances appear to be higher for modified Tyr-compared to modified Trp. Moreover, close resemblance of frequency shift of modified Tyr/Trp-in presence of Au 20 is observed with respect to the experimental FT-IR study of HHb upon interaction with GNP, suggesting participation of amide bonds in both cases. Furthermore, CD DFT calculations using optimized helical stretch of HHbin presence of Au-20 and experimental CD results of HHb in presence of GNP further indicate participation amide bonds and biocompatibility of GNP. Apparently, the theoretical and experimental interactions are going in good agreement with each other. Overall, the study of interactions of modified Tyr/Trp-as representative models of protein microenvironment and Au-20 nanocluster as prototype of GNP to develop models for exploring protein nanoparticle interactions has been highlighted. (C) 2022 Elsevier B.V. All rights reserved.
Keywords: amide bonds; Au-20 nanocluster; Gold nanoparticle; Human hemoglobin; Modified Tyr/Trp

Intramolecular donor-stabilized tetra-coordinated germanium(iv) di-cations and their Lewis acidic properties - Peddi, Balakrishna; Khan, Souvik; Gonnade, Rajesh G.; Yildiz, Cem B.; Majumdar, Moumita (Chemical Science, 2023)
We report the first examples of intramolecular phosphine-stabilized tetra-coordinated germanium(iv) di-cationic compounds: [(L2Ge)-Ge-iPr][CF3SO3](2)3iPr and [(L2Ge)-Ge-Ph][CF3SO3](2)3Ph (L-iPr = 6-(diisopropylphosphanyl)-1,2-dihydroacenaphthylene-5-ide; L-Ph = 6-(diphenylphosphanyl)-1,2-dihydroacenaphthylene-5-ide). The step wise synthetic strategy involves the isolation of neutral and mono-cationic Ge(iv) precursors: [(L2GeCl)-Ge-iPr][X] (X = GeCl(3)1iPr, OTf 2iPr), [(L2GeCl2)-Ge-Ph] 1Ph and [(L2GeCl)-Ge-Ph][OTf] 2Ph. Both 3iPr and 3Ph exhibit constrained spiro-geometry. DFT studies reveal the dispersion of di-cationic charges over P-Ge-P sites. Anion or Lewis base binding occurs at the Ge site resulting in relaxed distorted trigonal bipyramidal/tetrahedral geometry. 3iPr and 3Ph activate the Si-H bond initially at the P-site. The hydride ultimately migrates to the Ge-site rapidly giving [(L2GeH)-Ge-Ph][CF3SO3] 3PhH, while sluggishly forming [(L2GeH)-Ge-iPr][CF3SO3] 3iPrH. Compounds 3iPr and 3Ph were tested as catalysts for the hydrosilylation of aromatic aldehydes. While catalytic hydrosilylation proceeded via the initial Et3Si-H bond activation in the case of 3iPr, compound 3Ph as a catalyst showed a masked Frustrated Lewis Pair (FLP) type reactivity in the catalytic cycle.

Investigation and analysis of structural and electrochemical properties of highly ionic conductive La2-xSrxSn2O7-delta electrolyte for SOFC applications - Melit, Fatima; Bounar, Nedjemeddine; Shaikh, Shabana P. S.; Deshpande, Manish; Steil, Marlu Cesar (Chemical Papers, 2023)
This study primarily focused on the investigation, synthesis and analysis of lanthanum and tin pyrochlores electrolytes for solid oxide fuel cell (SOFC) applications. Ceramic samples with diverse compositions of La2-xSrxSn2O7-delta (x = 0.05, 0.1, 0.15, 0.2, 0.25, and 0.3) were synthesized by using solid-state reaction (SSR) methods. The prepared La2-xSrxSn2O7-delta samples were characterized by using X-ray diffraction, scanning electron microscopy and electrochemical impedance spectroscopy measurements. The results were further interpreted regarding the formation of high oxygen vacancy and structural disorder in the La2-xSrxSn2O7-delta matrix. The doping of lanthanum (La3+) by strontium (Sr2+) had a beneficial and remarkable effect on the structural and electrical properties: the increase in dopant (Sr) concentration decreased the lattice parameters of the crystalline phase and enhanced the creation of oxygen vacancies, which consequently increased the ionic conductivity and decreased the activation energy. Thus, it could be understood that the studied new La2-xSrxSn2O7-delta electrolyte would be one of the potential candidates for intermediate temperature SOFC applications.
Keywords: Electrolyte; Impedance spectroscopy; Ionic conductivity; Pyrochlore; SOFC

Investigation of cold-active and mesophilic cellulases: opportunities awaited - Chavan, Sambhaji; Shete, Ashvini; Mirza, Yasmin; Dharne, Mahesh S. (Biomass Conversion and Biorefinery, 2023)
In the recent decade, the global demand and fuel prices have urged a need to track down an alternate resource. Second-generation (2G) biofuel from the lignocellulosic biomass (LCB) is trending as the fundamental alternative resource. Although LCB is the most abundantly available renewable resource, its commercialization into 2G biofuel technology is a major challenge. Efficient LCB hydrolysis requires a proper lignocellulolytic enzyme cocktail. In view to addressing this problem, several researchers are investigating for efficient enzymes to hydrolyze LCB. To date, there are very few commercial enzymes that aid in the breakdown of LCB, and these enzymes are traditionally isolated from culturable microbes. As only 1% of the microbes can be cultivated in the laboratory, the potentials of the uncultured remain under-explored. In the recent decade, advances in metagenomics using next-generation sequencing (NGS) technologies have revealed the vast diversity of hydrolytic enzymes and multiple domain proteins in the ecosystem. Aiming this, we focus our review on investigating efficient cold-active and mesophilic cellulases from the metagenome. India is an agro-based country with various climatic regions, ranging from warm and humid in the south to mild or moderate and cold or snowy in the Himalayan north; therefore, both cold-active and mesophilic cellulases are needed for LCB to ethanol. Along with downsizing, the conversion cost of LCB to fermentable sugars not only increases the enzymatic conversion but also increases the fermentation efficiency, which ultimately helps to commercialize the second-generation biofuel technology. Metagenomics is an evolving concept, and it has opened new horizons for the discovery of micro-organisms and new enzymes.
Keywords: cellulases; Glycosyl hydrolase; Lignocellulosic biomass; Metagenomics; simultaneous saccharification and fermentation

Investigation of the effect of zeolite supports and the role of W-species for one-pot catalytic conversion of cellulose to ethylene glycol: theoretical & experimental studies. - Sreekantan, Sreejith; Singh, Chandrodai Pratap; Krishnamurty, Sailaja; Marimuthu, Banu (Chemistry-An Asian Journal, 2023)
Endeavors were made to study the influence of various zeolite (HY, NaY, NaZSM-5 and HZSM-5) supports with (Al)-Ni-W metal combination catalysts for the ethylene glycol (EG) production, selectively from cellulose. From the experimental results ZSM-5 (NaZSM-5/73.3% & HZSM-5/67.7%) support is superior over HY & NaY support in selective EG production from cellulose. It was understood that W- species with oxygen vacancies (WO3-x, XPS analysis) plays an important role in producing the glycolaldehyde (GA) intermediate (via C-C cleavages), which on hydrogenation over Ni- sites selectively produce EG. Further, the studies based on the Density Functional Theory (DFT) were conducted to substantiate the involvement of the WO3-x species in the reaction. The adsorption energies and structural changes establish that the C-2-C-3 bond of the glucose elongates and thereby activates on adsorbing to WO3-x sites supporting the formation of GA. Activation of GA on Ni- sites is distinguished by an increase of 0.1 angstrom in C=O bond length, which facilitates the hydrogenation of C=O resulting in EG. The reaction pathway is explained through an analysis of CDD and DOS.
Keywords: Cellulose hydrogenolysis; DFT studies; ethylene glycol; zeolites

Ligand-free one-pot synthesis of Ru/W18O49 self-assembled hierarchical coral-like nanostructures for selective conversion of glucose into glycols - Patil, Manoj Krishnat; Gaikwad, Supriya Hanmant; Kirali, Arun Arunima Balachandran; Marimuthu, Banu; Mukherjee, Shatabdi Porel (ACS Applied Nano Materials, 2023)
In this study, we report a simple inorganic route for the synthesis of Ru/W18O49 self-assembled coral-like nanostructures, with the following advantages: It is one step and requires no surfactant or stabilizing agent; Ru loading is easily tuned, and the as-synthesized nanomaterials can be used as a catalyst without any further processing. The preliminary investigations of the catalytic performance of these as-synthesized Ru/W18O49 nanomaterials appear quite promising for converting glucose to glycols. The total glycol selectivity of 82.6% with 100% conversion of glucose was obtained over 0.03 wt % Ru loading on tungsten nanostructures, which turns out to be the lowest Ru loading% on support reported to date to achieve the highest total glycol selectivity among the previously reported catalyst based on Ru-nano/composite materials. Additionally, preliminary results show that the concentration of Ru on W18O49 significantly affects the selectivity of the glycol production. Thus, our methodology will open up a wide range of opportunities regarding the choice of metals, stoichiometric/nonstoichiometric WOx (x=1-3) as support, and the viability of further catalytic manipulations. A probable catalytic mechanism for this catalytic process is also proposed.
Keywords: glycols; Nanostructure; One-pot synthesis; ruthenium (Ru); selective conversion of glucose; tungsten oxide (W18O49)

Liquid-liquid equilibria of ternary mixtures containing Aniline plus Toluene plus water at elevated temperatures: measurements and correlation - Gaikwad, Shashank G.; Pathak, Abhishek A.; Mote, Dhananjay R.; Gogate, Parag R.; Singh, Shivani; Modhera, Bharat (Separation Science and Technology, 2023)
Liquid-liquid equilibrium (LLE) data for the ternary system, Aniline + Toluene + Water, was measured at different temperatures of 298.15 K, 313.15 K and 323.15 K under atmospheric pressure with the help of High-Performance Liquid Chromatography (HPLC) analysis and Karl-Fischer technique. The efficiency of Toluene to extract Aniline from aqueous phase was then quantified in terms of the distribution coefficient and separation factor based on the tie line data. The system showed very good separation ability quantified in terms of high values of distribution factor (average around 7) and separation factors (as high as 1000). The experimental tie line data was verified by Hand and Othmer-Tobias equations. The LLE data was also correlated using NRTL and UNIQUAC models and both of them were able to represent the behavior of the system accurately when tested against experimental results. Toluene has been demonstrated to be very efficient to extract Aniline from reaction mixture, which is typically a by-product in hydrogenation of nitrobenzene, a process commercially used to produce p-Aminophenol in industry.
Keywords: Aniline; LLE; NRTL; Tie line; Toluene; UNIQUAC

Low-temperature preferential CO oxidation in a hydrogen-rich stream over Pt-NaY and modified Pt-NaY catalysts for fuel cell application - Malwadkar, Sachin; Bera, Parthasarathi; Satyanarayana, Chilukuri V. V. (Fuel Cells, 2023)
Preferential oxidation of CO (CO-PROX) in the hydrogen-rich stream has been carried out over Pt-NaY catalysts containing various Pt loadings along with Fe, Co, and Au. Catalysts have been characterized with inductively coupled plasma-atomic emission spectroscopy, Brunauer, Emmett, and Teller surface area, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, temperature programmed reduction, and Pt dispersion. CO-PROX activities and CO oxidation selectivities are observed to increase with an increase in Pt content. Pt-NaY catalyst with 0.75 wt.% Pt loading shows maximum CO-PROX activity at low temperatures. An increase in space velocity decreases the CO and O-2 conversions, but CO oxidation selectivity increases. A decrease in activity is observed when reformat gas contains around 20% H2O. During the stability test, no change in CO and O-2 conversions is observed, but a small increase in the CO oxidation selectivity is noticed after 10 h indicating that the Pt-NaY catalyst is a promising candidate for CO-PROX reaction in a hydrogen-rich stream. The Pt-Fe-NaY catalyst shows better activity than the Pt-NaY catalyst but starts deactivating after 10 h. However, activity is observed to decrease over Pt-Co-NaY and Pt-Au-NaY catalysts. Pt-Fe-NaY catalyst with 0.75 and 0.35 wt.% Pt and Fe, respectively, shows better CO-PROX activity at a temperature of 75 degrees C.
Keywords: catalysis; CO oxidation; experimental results; flow bed; Fuel Cell Applications; Hydrogen; X-ray photoelectron spectroscopy

Made to measure squaramide COF cathode for zinc dual-ion battery with enriched storage via redox electrolyte - Kushwaha, Rinku; Jain, Chitvan; Shekhar, Pragalbh; Rase, Deepak; Illathvalappil, Rajith; Mekan, Deep; Camellus, Augastus; Vinod, Chathakudath Prabhakaran; Vaidhyanathan, Ramanathan (Advanced Energy Materials, 2023)
Aqueous rechargeable batteries are promising grid-scale energy storage devices because of their affordability, operational safety, and environmental benignity. Among these, Zn-ion batteries (ZIBs) have unfolded new horizons. Designing superior cathodes for ZIBs is crucial. Covalent organic frameworks (COFs) can be made redox active with a high storage surface. Here, for the first time, a chelating COF with redox-active ZnI2 in a ZnSO4(aq) electrolyte is combined. Including iodide harvests an approximately threefold enhancement in capacity from 208 to 690 mAh g(-1) at 1.5 A g(-1), the highest among all the COF-derived ZIBs. Remarkably, a charge-discharge curve at 1.3 V exhibits very limited dropout voltage and super-flat platform, with a remarkable capacity of 600 mAh g(-1) at 5 A g(-1) stable up to 6000 cycles, confirming that the polyiodide generation and storage are sustainable. The COF's dual-ion storage (Zn2+ and polyidode) delivers a ZIB with the highest energy density. Spectro-electrochemical measurements coupled with X-ray photoelectron spectroscopy unambiguously unveil the existence of multiple polyiodide species, with I-3(-) and IO3- ions as the prominent species. The latter gets reduced at the COF electrode under an applied potential, leaving I-3(-) as the major species stored on the COF. The prospect of COF-polyiodide((aq)) is a windfall for metal-ion batteries.
Keywords: covalent organic frameworks; flexible batteries; polyiodide; redox electrolytes; Zn ion batteries

Mechano-immunology in microgravity - Murali, Anirudh; Sarkar, Ram Rup (Life Sciences in Space Research, 2023)
Life on Earth has evolved to thrive in the Earth's natural gravitational field; however, as space technology advances, we must revisit and investigate the effects of unnatural conditions on human health, such as gravitational change. Studies have shown that microgravity has a negative impact on various systemic parts of humans, with the effects being more severe in the human immune system. Increasing costs, limited experimental time, and sample handling issues hampered our understanding of this field. To address the existing knowledge gap and provide confidence in modelling the phenomena, in this review, we highlight experimental works in mechanoimmunology under microgravity and different computational modelling approaches that can be used to address the existing problems.
Keywords: Computational modelling; Immune system; Mechano-immunology; Mechanotransduction; Microgravity

MeGen-generation of gallium metal clusters using reinforcement learning - Modee, Rohit; Verma, Ashwini; Joshi, Kavita; Priyakumar, U. Deva (Machine Learning-Science and Technology, 2023)
The generation of low-energy 3D structures of metal clusters depends on the efficiency of the search algorithm and the accuracy of inter-atomic interaction description. In this work, we formulate the search algorithm as a reinforcement learning (RL) problem. Concisely, we propose a novel actor-critic architecture that generates low-lying isomers of metal clusters at a fraction of computational cost than conventional methods. Our RL-based search algorithm uses a previously developed DART model as a reward function to describe the inter-atomic interactions to validate predicted structures. Using the DART model as a reward function incentivizes the RL model to generate low-energy structures and helps generate valid structures. We demonstrate the advantages of our approach over conventional methods for scanning local minima on potential energy surface. Our approach not only generates isomer of gallium clusters at a minimal computational cost but also predicts isomer families that were not discovered through previous density-functional theory (DFT)-based approaches.
Keywords: gallium clusters; reinforcement learning; structure generation

Metal- and photocatalyst-free, visible-light-initiated C3 a-aminomethylation of quinoxalin-2(1H)-ones via electron donor-acceptor complexes - More, Devidas A.; Shirsath, Sachin R.; Muthukrishnan, M. (Journal of Organic Chemistry, 2023)
We report a metal- and photocatalyst-free C3 a-aminomethylation of quinoxalin-2(1H)-ones with N-alkyl-N-methylanilines. The reaction proceeds through the formation of a photoactivated electron donor-acceptor complex between quinoxalin-2(1H)-ones and N-alkyl-N-methylanilines. The present method provides a mild and environmentally friendly protocol that exhibits good atom economy and excellent functional group tolerance to obtain a library of biologically significant C3 a-aminomethylated quinoxalin-2(1H)-ones in good yields.

Metal deficiency tailored by the 18-electron rule stabilizes metal-based inorganic compounds - Singh, Ashutosh Kumar; Mumbaraddi, Dundappa; Mishra, Vidyanshu; Roy, Soumyabrata; Vinod, C. P.; Peter, Sebastian C. (Chemistry of Materials, 2023)
The 18-electron (18-e(-)) rule is typicallyrestrictedto predicting the stability of transition-metal-based complexes. Herein,we report the use of the 18-e(-) to predict the stabilityin a family of intermetallics MNiSn (M = V, Cr, Fe, and Co) crystallizingin the Co1.75Ge structure type. Site deficiencies at theM site obtained from single-crystal X-ray diffraction are understoodas attaining a stable noble gas electronic configuration. The densityfunctional theory -based structure calculation confirms that the deficientstructure is more stable than the ideal occupation available at thecrystal lattice. MnNiSn, which crystallizes in the half-Heusler crystalstructure, depicts the role of covalent radii of the constituent elementsin determining the crystal structure. Using X-ray absorption spectroscopyand X-ray photoelectron spectroscopy, the local structure of the above-mentionedcompounds was also elucidated, supporting the role of deficiency tunedvalence fluctuation to attain a 18-e(-) configurationthat eventually leads to the formation of stable compounds.

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

Microporous 3D-structured hierarchically entangled graphene-supported Pt3Co alloy catalyst for PEMFC application with process-friendly features - Manna, Narugopal; Singh, Mayank; Kurungot, Sreekumar (ACS Applied Materials & Interfaces, 2023)
To improve the oxygen reduction reaction(ORR) performance in aproton-exchange membrane fuel cell (PEMFC) cathode with respect tomass activity and durability, a suitable electrocatalyst design strategyis essentially needed. Here, we have prepared a sub-three nm-sizedplatinum (Pt)-cobalt (Co) alloy (Pt3Co)-supportedN-doped microporous 3D graphene (Pt3Co/pNEGF) by usingthe polyol synthesis method. A microwave-assisted synthesis methodwas employed to prepare the catalyst based on the 3D porous carbonsupport with a large pore volume and dense micro-/mesoporous surfaces.The ORR performance of Pt3Co/pNEGF closely matches withthe state-of-the-art commercial Pt/C catalyst in0.1 M HClO4, with a small overpotential of 10 mV. The 3Dmicroporous structure of the N-doped graphene significantly improvesthe mass transport of the reactant and thus the overall ORR performance.As a result of the lower loading of Pt in Pt3Co/pNEGF ascompared to that in Pt/C, the alloy catalyst achieved 1.5 times highermass activity than Pt/C. After 10,000 cycles, the difference in theelectrochemically active surface area (ECSA) and half-wave potential(E (1/2)) of Pt3Co/pNEGF is foundto be 5 m(2) g(Pt) (-1) (Delta ECSA)and 24 mV (Delta E (1/2)), whereas, forPt/C, these values are 9 m(2) g(Pt) (-1) and 32 mV, respectively. Finally, in a realistic perspective, single-celltesting of a membrane electrode assembly (MEA) was made by sandwichingthe Pt3Co/pNEGF-coated gas diffusion layers as the cathodedisplayed a maximum power density of 800 mW cm(-2) under H-2-O-2 feed conditions with aclear indication of helping the system in the mass-transfer region(i.e., the high current dragging condition). The nature of the I-V polarization shows a progressivelylower slope in this region of the polarization plot compared to asimilar system made from its Pt/C counterpart and a significantlyimproved performance throughout the polarization region in the caseof the system made from the Pt3Co/NEGF catalyst (withoutthe microwave treatment) counterpart. These results validate the betterprocess friendliness of Pt3Co/pNEGF as a PEMFC electrode-specificcatalyst owing to its unique texture with 3D architecture and well-definedporosity with better structural endurance.
Keywords: microwave synthesis; N-doped porous 3D graphene; ORR; PEMFC; polyol synthesis; Pt3Co alloy

Mitigating dendrite formation on a Zn electrode in aqueous zinc chloride by the competitive surface chemistry of an imidazole additive - Rana, Ashutosh; Thakare, Anup; Kumar, Nikhil; Mukherjee, Buddhadev; Torris, Arun; Das, Bidisa; Ogale, Satishchandra; Banerjee, Abhik (ACS Applied Materials and Interfaces, 2023)
Electrochemical energy storage systems are critical in several ways for a smooth transition from nonrenewable to renewable energy sources. Zn-based batteries are one of the promising alternatives to the existing state-of-the-art Li-ion battery technology, since Li-ion batteries pose significant drawbacks in terms of safety and cost-effectiveness. Zn (with a reduction potential of -0.76 V vs SHE) has a significantly higher theoretical volumetric capacity (5851 mAh/cm3) than Li (2061 mAh/cm3), and it is certainly far less expensive, safer, and more earth-abundant. The formation of dendrites, hydrogen evolution, and the formation of a ZnO passivation layer on the Zn anode are the primary challenges in the development and deployment of rechargeable zinc batteries. In this work, we examine the role of imidazole as an electrolyte additive in 2 M ZnCl2 to prevent dendrite formation during zinc electrodeposition via experimental (kinetics and imaging) and theoretical density functional theory (DFT) studies. To characterize the efficacy and to identify the appropriate concentration of imidazole, linear sweep voltammetry (LSV) and chronoamperometry (CA) are performed with in situ monitoring of the electrodeposited zinc. The addition of 0.025 wt % imidazole to 2 M ZnCl2 increases the cycle life of Zn-symmetric cells cycled at 1 mA/cm2 for 60 min of plating and stripping dramatically from 90 to 240 h. A higher value of the nucleation overpotential is noted in the presence of imidazole, which suggests that imidazole is adsorbed at a competitively faster rate on the surface of zinc, thereby suppressing the zinc electrodeposition kinetics and the formation. X-ray tomography reveals that a short circuit caused by dendrite formation is the main plausible failure mechanism of Zn symmetric cells. It is observed that the electrodeposition of zinc is more homogeneous in the presence of imidazole, and its presence in the electrolyte also inhibits the production of a passivating coating (ZnO) on the Zn surface, thereby preventing corrosion. DFT calculations conform well with the stated experimental observations.
Keywords: dendrite; Density functional theory; exchange current density; Imidazole; X-ray computed tomography; zinc metal electrodeposition

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

Multi-bandgap quantum dots ensemble for near-infrared photovoltaics - Mahajan, Chandan; Dambhare, Neha V.; Biswas, Arindam; Sharma, Anjali; Shinde, Dipak Dattatray; Rath, Arup K. (Energy Technology, 2023)
Narrow bandgap quantum dots (QDs) are an important class of materials for near-infrared (NIR) optoelectronic devices owing to their size-tunable bandgap and chemical root processing. In photovoltaic applications, NIR QDs could be particularly useful to complement the sub-bandgap transmission loss of NIR solar radiation from perovskite and c-Si solar cells. However, insufficient carrier extraction thickness associated with the narrow NIR excitonic bandwidth of QDs limits the conversion efficacy of the broad NIR solar spectrum. Here, we utilize a multi-bandgap QD ensemble which widens the NIR absorption bandwidth to mimic the broad solar spectrum. A solution-phase ligand passivation strategy is used to control doping properties and energy level alignment of multi-bandgap QDs. We successfully developed bulk-heterojunction solar cells using the multi-bandgap QD ensemble, which yields higher carrier extraction thickness and broader NIR absorption. The gain from NIR absorption and carrier transport resulted in higher short-circuit current generation and power conversion efficiency (PCE) in solar cell devices. The champion device shows 8.73% PCE under 1.5 AM solar illumination and 7.44% and 5.05% PCE for the NIR photons transmitted from perovskite and c-Si layers.
Keywords: bulk-heterojunctions; multi-bandgap; near-infrared; quantum dots; solar cells; surface passivation

Nanopore sequencing of RAGE gene polymorphisms and their association with type 2 diabetes - Chaurasiya, Arvindkumar H.; Khilari, Ajinkya A.; Kazi, Rubina; Jaiswal, Meera R.; Bhoite, Gouri M.; Padwal, Meghana K.; Momin, Abdulrahaman A.; Shanmugam, Dhanasekaran; Kulkarni, Mahesh J. (ACS Omega, 2023)
The receptor foradvanced glycation end products (RAGE)is a transmembraneprotein that interacts with its ligands, advanced glycation end products(AGEs). AGEs are elevated in diabetes and diabetic complications,leading to increased oxidative stress and activation of pro-inflammatorypathways facilitated by AGE-RAGE signaling. Polymorphisms inthe RAGE gene can potentially affect AGE-RAGEinteraction and its downstream signaling, which plays a crucial rolein the progression of diabetes and its complications. In this study,we used nanopore sequencing for genotyping of RAGE polymorphism and identified a maximum number of 33 polymorphisms,including two previously unreported novel mutations in a cohort ofhealthy, type 2 diabetics without nephropathy and type 2 diabeticswith nephropathy in order to identify associations. Two novel RAGE polymorphisms in the intron 8 and 3 & PRIME;UTR regionat genomic locations 32181834 and 32181132, respectively, were detectedwith a low frequency. For four previously reported polymorphisms,cross-validation by PCR-RFLP showed 99.75% concordance with nanoporesequencing. Analysis of genotype distribution and allele frequenciesrevealed that five single nucleotide polymorphisms, i.e., rs1800625,rs3131300, rs3134940, rs2070600, and rs9391855, were associated withan increased risk for type 2 diabetes.

Nanostructured Co-doped BiVO4 for efficient and sustainable photoelectrochemical chlorine evolution from simulated sea-water - Chauhan, Inderjeet; Patra, Kshirodra Kumar; Bajpai, Himanshu; Mhamane, Nitin B.; Salgaonkar, Kranti N.; Gopinath, Chinnakonda S. (Dalton Transactions, 2023)
The co-production of hydrogen and chlorine from sea-water splitting could be a potential, sustainable and attractive route by any method. However, challenges to overcome are many, and critically, the sustainability and operating potential of the electrocatalyst are important. In this work, we report on Co-doping in the BiVO4 (Co-BV) crystal lattice and employed the same as the photoanode; Co-BV exhibits a photocurrent of 190 mu A cm(-2) at 1.1 V vs. RHE (the reversible hydrogen electrode) in the acidic sodium chloride solution (pH 2.3) under one sun illumination. The best-performing photoanode, with 0.05 mol% of Co doping (0.05 Co-BV), selectively produced active chlorine with 92% faradaic efficiency at 1.1 V vs. RHE by successfully suppressing the kinetically sluggish oxygen evolution reaction (OER) and the stability of the catalyst was demonstrated for up to 20 h. This is the lowest operating potential reported for the chlorine evolution reaction (CER), thus far. The overpotential required for CER with 0.05 Co-BV is lower than that of OER, which leads to selective CER at 1.1 V (vs. RHE). Co-doping into the BiVO4 lattice decreases the charge transfer resistance and enhances the CER kinetics due to its structural and electronic integration with the BV lattice. We demonstrate that Co-doping also improves the lifetime of the charge carrier and enhances the current density of CER and sustainability of the catalyst.

N-heterocyclic carbene-catalyzed atroposelective synthesis of N-N axially chiral 3-amino quinazolinones - Balanna, Kuruva; Barik, Soumen; Barik, Shilpa; Shee, Sayan; Manoj, Niket; Gonnade, Rajesh G.; Biju, Akkattu T. (ACS Catalysis, 2023)
Although the atroposelective synthesisof biaryls and related compoundsbearing axially chiral C-C bonds is well-known, the synthesisof axially chiral C-N bond-containing compounds is relativelyless explored, and the construction of axially chiral N-N bondshas received only scant attention. Demonstrated herein is the N-heterocycliccarbene (NHC)-catalyzed selective amidation reaction, leading to theatroposelective synthesis of N-N axially chiral 3-amino quinazolinones.The NHC-catalyzed reaction of quinazolinones containing a free N-Hmoiety with & alpha;,& beta;-unsaturated aldehydes under oxidativeconditions furnished the atropisomeric quinazolinone derivatives undermild conditions and broad scope. Preliminary studies on experimentaland density functional theory-based N-N rotational barrierdetermination are also presented.
Keywords: amino quinazolinones; asymmetriccatalysis; axial chirality; N-heterocycliccarbenes; organocatalysis

Non-Markov models of single-molecule dynamics from information-theoretical analysis of trajectories - Song, Kevin; Park, Raymond; Das, Atanu; Makarov, Dmitrii E.; Vouga, Etienne (Journal of Chemical Physics, 2023)
Whether single-molecule trajectories, observed experimentally or in molecular simulations, can be described using simple models such as biased diffusion is a subject of considerable debate. Memory effects and anomalous diffusion have been reported in a number of studies, but directly inferring such effects from trajectories, especially given limited temporal and/or spatial resolution, has been a challenge. Recently, we proposed that this can be achieved with information-theoretical analysis of trajectories, which is based on the general observation that non-Markov effects make trajectories more predictable and, thus, more ``compressible'' by lossless compression algorithms. Toy models where discrete molecular states evolve in time were shown to be amenable to such analysis, but its application to continuous trajectories presents a challenge: the trajectories need to be digitized first, and digitization itself introduces non-Markov effects that depend on the specifics of how trajectories are sampled. Here we develop a milestoning-based method for information-theoretical analysis of continuous trajectories and show its utility in application to Markov and non-Markov models and to trajectories obtained from molecular simulations.

Novel Biogenic Synthesis of Pd/TiO@BC as an electrocatalytic and possible energy storage materials - Khasim, Syed; Dastager, Syed G.; Alahmdi, Mohammed Issa; Hamdalla, Taymour A.; Panneerselvam, Chellasamy; Makandar, Mohammad Basha (Ceramics International, 2023)
The standard approach towards synthesizing nanomaterials exercising chemical or physical techniques generally costs more and necessitates using toxic chemicals, which negatively affect the environment. For the first time, an investigation of a basic green synthesis approach for Phyto fabrication of Pd/TiO@BC nanocomposite via biomass of rice husk (Oryza sativa L) is conducted to sustain the green chemistry for synthesis of less toxic chemicals. XRD analysis revealed that the structure of Phyto synthesized Pd/TiO@BC is crystalline, while UV, FTIR, SEM and EDX analyses marked the victorious nanocomposite biosynthesis. We have investigated the electrocatalytic and biomedical applications of the novel nanocomposite Pd/TiO@BC at different environmental conditions. Testing the potential electrochemical properties of Pd/TiO@BC to eliminate the Congo red (CR) dye from wastewater marked its high removal efficiency, which attained 90% owing to the higher electron efficiency. Its sensitivity for CR was also examined, and acceptable degradation activity was observed. These Pd/TiO@BC proved to be beneficial in various fields, including electrochemistry, catalysis sensors, wastewater treatment, and nano-devices, and in the transformation of hazardous particles into less harmful substances. Its great potential for use as a supercapacitor is promised by its feature, including durability and compact stability. Significant guidelines could be extracted from the results, which are helpful in material size, synthesis, selection, and configuration design for various energy storage gadgets. The synthesis of high performance and economical materials through green chemistry is a novel approach towards effective energy storage and alteration procedure operation.
Keywords: Electro catalytic; Energy storage; Oryza sativa L biochar; Pd; PdNPs and TiONPs; TiO@BC

Novel finding: 2,4-Di-tert-butylphenol from streptomyces bacillaris ANS2 effective against mycobacterium tuberculosis and cancer cell lines - Kaari, Manigundan; Joseph, Jerrine; Manikkam, Radhakrishnan; Kalyanasundaram, Revathy; Sivaraj, Anbarasu; Anbalmani, Sivarajan; Murthy, Sangeetha; Sahu, Amit Kumar; Said, Madhukar; Dastager, Syed G.; Ramasamy, Balagurunathan (Applied Biochemistry and Biotechnology, 2023)
The aim of the present study is to identify actinobacteria Streptomyces bacillaris ANS2 as the source of the potentially beneficial compound 2,4-di-tert-butylphenol, describe its chemical components, and assess its anti-tubercular (TB) and anti-cancer properties. Ethyl acetate was used in the agar surface fermentation of S. bacillaris ANS2 to produce the bioactive metabolites. Using various chromatographic and spectroscopy analyses, the potential bioactive metabolite separated and identified as 2,4-di-tert-butylphenol (2,4-DTBP). The lead compound 2,4-DTBP inhibited 78% and 74% of relative light unit (RLU) decrease against MDR Mycobacterium tuberculosis at 100ug/ml and 50ug/ml concentrations, respectively. The Wayne model was used to assess the latent/dormant potential in M. tuberculosis H37RV at various doses, and the MIC for the isolated molecule was found to be 100ug/ml. Furthermore, the molecular docking of 2,4-DTBP was docked using Autodock Vinasuite onto the substrate binding site of the target Mycobacterium lysine aminotransferase (LAT) and the grid box was configured for the docking run to cover the whole LAT dimer interface. At a dosage of 1 mg/ml, the anti-cancer activity of the compound 2,4-DTBP was 88% and 89% inhibited against the HT 29 (colon cancer) and HeLa (cervical cancer) cell lines. According to our literature survey, this present finding may be the first report on anti-TB activity of 2,4-DTBP and has the potential to become an effective natural source and the promising pharmaceutical drug in the future.
Keywords: 2; 4-Di-tert-butylphenol; anti-cancer; Anti-tubercular; Molecular docking; Streptomyces bacillaris

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

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.

Organophosphites: an addition to the arsenal of organocatalysts - Baral, Nilofar; Rani, Soniya; Saikia, Pinku; Maity, Pradip (European Journal of Organic Chemistry, 2023)
Organophosphites are nucleophilic in nature and can act as a good leaving group owing to the stability of the phosphite anion. This dual reactivity makes them good candidates for nucleophilic organocatalysis. However, phosphites were introduced only in 2004 as the umpolung catalyst for acylsilane substrates utilizing sequential Brook rearrangements. Very recently, phosphites have been reported to catalyze aza-rearrangements and radical reactions. In this review, we discuss the reactivity parameters to understand its lack of use, as well as the potential for catalysis.
Keywords: acylradical; azaacyl equivalent; cylanion; organocatalysis; phosphite

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

Palladium-catalyzed oxidative cyclization of ?-allenols in the presence of TBN: access to 3(2H)-furanones - Ghotekar, Ganesh S.; Shinde, Ravi A.; Saswade, Sagar S.; Muthukrishnan, M. (Journal of Organic Chemistry, 2023)
A new palladium-catalyzed oxidative cyclization of alpha-allenols is described. The readily accessible alpha-allenols participate in intra-molecular oxidative cyclization in the presence of TBN to grant access to multisubstituted 3(2H)-furanones, which are common motifs in several biologically important natural products and pharmaceuticals.
Keywords: Alternatively; conditions; cumbersome workup; intramolecular electrophilic; multiple reaction steps; noted examples

Parallel evolution of cannabinoid biosynthesis - Berman, Paula; de Haro, Luis Alejandro; Jozwiak, Adam; Panda, Sayantan; Pinkas, Zoe; Dong, Younghui; Cveticanin, Jelena; Barbole, Ranjit; Livne, Rotem; Scherf, Tali; Shimoni, Eyal; Levin-Zaidman, Smadar; et al. (Nature Plants, 2023)
This study reveals a cannabinoid biosynthetic pathway in Helichrysum umbraculigerum, a plant genetically distant from Cannabis, providing a potential source of new cannabinoids and metabolic engineering tools. Modulation of the endocannabinoid system is projected to have therapeutic potential in almost all human diseases. Accordingly, the high demand for novel cannabinoids stimulates the discovery of untapped sources and efficient manufacturing technologies. Here we explored Helichrysum umbraculigerum, an Asteraceae species unrelated to Cannabis sativa that produces Cannabis-type cannabinoids (for example, 4.3% cannabigerolic acid). In contrast to Cannabis, cannabinoids in H. umbraculigerum accumulate in leaves' glandular trichomes rather than in flowers. The integration of de novo whole-genome sequencing data with unambiguous chemical structure annotation, enzymatic assays and pathway reconstitution in Nicotiana benthamiana and in Saccharomyces cerevisiae has uncovered the molecular and chemical features of this plant. Apart from core biosynthetic enzymes, we reveal tailoring ones producing previously unknown cannabinoid metabolites. Orthology analyses demonstrate that cannabinoid synthesis evolved in parallel in H. umbraculigerum and Cannabis. Our discovery provides a currently unexploited source of cannabinoids and tools for engineering in heterologous hosts.

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

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.

PIDA-mediated N-N bond formation to access pyrazolidine-3,5-diones: a novel process for uricosuric agents G-25671 and sulfinpyrazone - Halder, Priyanka; Mhaske, Santosh B. (Chemical Communications, 2023)
Traditionally, toxic and expensive hydrazine building blocks are required to construct pharmaceutically important pyrazolidine-3,5-diones. Herein, we have described a novel method for their synthesis based on metal-free oxidative dehydrogenative N-N bond formation by PIDA-mediated reaction of easily accessible dianilide precursors. The developed mild reaction protocol features a good functional group tolerance and scalability. The application of this method is demonstrated by offering a unique route for the synthesis of uricosuric agents G-25671 and sulfinpyrazone from inexpensive starting material aniline via smooth functionalization of the well-designed diversity-oriented cyclopropyl key intermediate.

Polymerized stimuli-responsive microgels for the removal of organic dye from water - Pany, Biswajit; Majundar, Amrito Ghosh; Mohanty, Madhuchhanda; Fyis, K. P.; Dey, Tanima; Tripathy, Gautam; Bhat, Suresh; Yamanaka, Junpei; Mohanty, Priti S. (Journal of Molecular Liquids, 2023)
Polymerized hydrogel materials (PGM) containing uniform-sized stimuli-responsive microgel particles could be promising alternatives for solution-based microgels to remove organic dyes from water. In the current work, PGM is prepared using Poly(N-isopropylacrylamide-co-acrylic acid) based anionic microgels and their ability for uptake and release studies with an oppositely charged dye, methylene blue (MB) is carried out using UV-vis spectroscopy. The mechanism of dye adsorption is understood at a single particle level using light scattering, and zeta potential and the contributions from different molecular interactions among dye molecules and constituting entities of microgels are obtained from molecular docking studies. The maximum dye uptake by PGM is around 80 % in the swollen state (at pH 7 and 20 degrees C). In contrast, the dye release studies in the deswollen state (at pH 3 and 50 degrees C) show a decrease in the release efficiency from 87 % to 63 % of the total dye adsorbed in 4-repeated cycles. The adsorption isotherm follows a sigmoidal (S) model that has been majorly used in different multi-layer adsorption systems. Extensive dynamic and static light scattering studies demonstrate a deswelling of hydrody-namic radius and core-shell radius of microgels at low temperatures (20 degrees C) induced by dye adsorption. At higher temperatures, the dye-adsorbed microgels have a higher hydrodynamic radius than the pure microgels due to the remaining dye molecules within the microgel that do not release even in the deswollen state. Molecular docking studies show that electrostatic interaction dominates between COO- and MB and van der Waals/hydrophobic dominates for MB-NIPAM and MB-COOH docking complex respectively. Our work covering adsorption/desorption properties of the material to the single-particle level can provide a better understanding in formulating reusable smart materials for the remediation of different water pollutants.(c) 2023 Elsevier B.V. All rights reserved.
Keywords: dynamic light scattering; Molecular docking; PNIPAM microgels; Removal of organic pollutants; Stimuli -responsive microgels

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

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

Progressions in cathodic catalysts for oxygen reduction and hydrogen evolution in bioelectrochemical systems: Molybdenum as the next-generation catalyst - Mishra, Puranjan; Sudarsanam, Putla; Mahapatra, Durga Madhab; Elmekawy, Ahamad; Pant, Deepak; Singh, Lakhveer (Catalysis Reviews- Science and Engineering, 2023)
Oxygen reduction reactions (ORRs) are unanimously a key factor of system performances in bioelectrochemical systems (BESs), low-temperature fuel cells, and generally in several electrochemical platforms. Platinum (Pt)-based catalyst is the finest electrocatalyst for ORR in BESs; however, it is constrained by its low abundance, high price, and poor catalytic durability in an electrochemical setup for cathodic reaction kinetics. In recent years, significant efforts in trimming the metal-based catalyst up to nanoscale to cater high performance of ORR have been explored. Still, there are many opportunities to improve catalyst performance at cathode through proper selection of an efficient low-cost metal-based ORR catalyst. Molybdenum (Mo) with its multi-dimensional form as 2D and 3D layers and synergistic combination with other non-metals offers prospects of extraordinary performance as low-cost metal-based ORR catalyst over the Pt in delivering enhanced ORR potential. The present review throws light on current requirements of a sturdier catalyst material and thus provides a comprehensive review on the continuing efforts in exploring the possibility of Mo as a low-cost metal-based ORR catalyst. This literature analysis would enlighten the significance of ORR in BESs, followed by the electrochemistry of Mo-based cathodic catalyst, its underlying mechanism and performance limiting factors in the operation of ORR. Moreover, the extensive and systematic acumen in the context of Mo-based catalytic formulations for increased ORR potentials including nano-composite Mo-cathode catalyst; development of Mo-catalyst with varied configurations; carbon-supported Mo-catalyst; morphological changes; surface area modifications; and Mo-coupling with other transition metal and its derivatives were discussed in great detail to provide prospective application of Mo-based catalyst. Lastly, numerous opportunities and projections for future research in fabrication, juxtaposition, and implementation of Mo-based cathodic catalysts and consequent recommendations were discussed as conclusive remarks for bringing out the state-of-the-art review on this subject.
Keywords: Bioelectrochemical system; catalytic formulations; H-2-evolution reaction; Mo-based cathodic catalyst; multifunctional catalysts; oxygen reduction reaction

Promoting effect of titanium on C-O hydrogenolysis of erythritol to 1,4-butanediol over Pt/W/Ti-SBA-15 catalysts - Bhowmik, Susmita; Akula, Venugopal; Sethia, Govind; Marimuthu, Banu; Darbha, Srinivas (Applied Catalysis A-General, 2023)
The C-O hydrogenolysis of erythritol was investigated using Pt/W/Ti-SBA-15 catalysts (4 wt% Pt, 1 wt% W and Si/Ti molar ratio = 50, 33, 20 and 10). Ti-incorporation enhanced the hydrogenolysis activity and the yield of 1,4-butanediol (1,4-BDO). A catalyst with Si/Ti = 20 afforded erythritol conversion of 94 mol% with 1,4-BDO yield of 32.6 mol% and total BDOs yield of 51.7 mol% at 190 degrees C, 50 bar H2 and 12 h. For the catalyst with no titanium (Pt/W/SBA-15), a double the time was required to achieve such yield. There observed electronic connectivity amongst Ti, Pt and W. For the catalyst with Si/Ti = 20, a greater amount of interfacial Pt-O-W(Ti) sites with Pt in + 2 oxidation state was present. The enhanced catalytic performance of these catalysts was corresponded to dispersed Pt (that facilitate hydrogen activation and spillover) and acidic interfacial Pt-O-W sites (that promote the adsorption and hydrogenolysis of erythritol to diols).
Keywords: Biomass conversion; Erythritol; Hydrogenolysis; Polyols; Promotional effect of Ti; Terminal diol; Ti-SBA-15-supported Pt/W catalysts

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.

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.

Review on catalytic hydrogenation of biomass-derived furfural to furfuryl alcohol: recent advances and future trends - Racha, Arundhathi; Samanta, Chanchal; Sreekantan, Sreejith; Marimuthu, Banu (Energy & Fuels, 2023)
Biomass is one of the highly abundantrenewable resourcesavailablethat can be converted into several high-value-added products, includingchemicals, biofuels, and advanced materials. To achieve net-zero emissionsand improve biomass application, researchers around the world haverecently focused on expanding biomass processing techniques to value-addedproducts with the eventual goal of industrializing some of the products.In this review, we summarize lignocellulosic biomass derived furfural(FA) and its subsequent hydrogenation to furfuryl alcohol (FAL). Thiswork reviews the various types of hydrogenation catalysts and theirutility in the production of value-added products from FA. There willbe an increase in the demand for selective catalysts and process technologies,as well as an increase in the challenges during valorization, as theusage of biomass to achieve carbon neutrality increases. The reviewaims to provide a concise overview of the advancements in this fieldand the potential for sustainable FAL production. In this paper, wepresent a simple strategy for selecting catalyst systems and associatedprocess parameters that facilitate the highly efficient and selectivevalorization of FA to chemicals or fuel (bioadditives) for industrialuse.

Rivaroxaban eutectics with improved solubility, dissolution rates, bioavailability and stability - Shaligram, Parth S.; George, Christy P.; Sharma, Himanshu; Mahadik, Kakasaheb R.; Patil, Sharvil; Vanka, Kumar; Arulmozhi, S.; Gonnade, Rajesh G. (Crystengcomm, 2023)
Rivaroxaban (RXB) is a direct factor Xa inhibitor used for the treatment of deep vein thrombosis (DVT, a blood clot in the leg) and pulmonary embolism (PE, a blood clot in the lung) and to prevent blood clots in atrial fibrillation following hip or knee surgery. However, RXB suffers from poor solubility that hinders its broader application. Although its cocrystals are reported for solubility enhancement, the methodology used to prepare multi-component crystals is complex. Also, it uses hazardous solvents to develop cocrystals. We have prepared eutectics of RXB with caffeic acid (CAA), coumaric acid (CA), fumaric acid (FA), succinic acid (SA), mandelic acid (MA) and trimesic acid (TA) and analyzed them using hot stage microscopy (HSM), differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), and fourier transform infrared spectroscopy (FTIR) techniques. The saturation solubility and dissolution rate profiles were also obtained to investigate the effect of eutectics on these parameters. Amongst all the coformers tested, coformers CAA, CA, and FA showed significant enhancement in the solubility of RXB. The powder dissolution rate of the eutectics showed considerable enhancement compared to that of RXB. In vivo pharmacokinetic study was carried out for RXB-CAA, RXB-CA and RXB-FA in rats and compared with RXB, which showed 1.5 and 1.4 times enhancement in relative bioavailability for RXB-CAA and RXB-CA, respectively. Stability studies were carried out as per ICH guidelines for all the eutectics, which revealed excellent stability over six months under accelerated (40 degrees C and 75%) conditions and twelve months under long-term (30 degrees C and 60% RH) conditions. The DFT studies carried out using the B3LYP/TZVP level of theory revealed higher Gibbs free interaction energy (Delta G(int)) for homosynthons (drugMIDLINE HORIZONTAL ELLIPSISdrug and coformerMIDLINE HORIZONTAL ELLIPSIScoformer) than heterosynthons (drugMIDLINE HORIZONTAL ELLIPSIScoformer).

Robust zeolitic tetrazole framework for electrocatalytic dopamine detection with high selectivity - Sarfudeen, Shafeeq; Sruthi, Vadakke Purakkal; Maibam, Ashakiran; Panda, Premchand; Jhariat, Pampa; Senthilkumar, Sellappan; BabaRao, Ravichandar; Panda, Tamas (Inorganic Chemistry, 2023)
A novel zeolitic tetrazolate framework (ZTF-8) has been synthesized by solvent-free heat-assisted (70 C-degrees) mechanochemical grinding of zinc acetate and 5-methyl tetrazole in the presence of NaOH powder. The structure of ZTF-8 adopts the zeolitic sodalite (SOD) topology with uncoordinated N-heteroatom sites and resembles the structure of the well-known zeolitic imidazole framework ZIF-8. ZTF-8 is exceptionally stable in 0.1 M aqueous acid and base solutions for 60 days at 25 C-degrees. The unique structure with uncoordinated N-heteroatom active sites and exceptional stability of ZTF-8 facilitated the electrocatalytic oxidation of dopamine to dopamine quinone at neutral pH. Without any postsynthetic modification, ZTF-8 is directly used for the facile electrochemical detection of dopamine over a wide range of concentrations (5-550 mu M) with a high sensitivity (2410.8 mu A mM-1 cm-2). It also demonstrated promising selectivity over other interferents of similar oxidation potential, such as ascorbic acid and uric acid. The DFT study revealed that the ZTF-8 framework has a higher binding energy (-145.07 kJ/mol) and stronger interaction with dopamine than its isostructural ZIF-8 structure (-130.42 kJ/mol).

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.

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

Selective one pot multicomponent green synthesis of 3-[(aryl)(arylthio)methyl]-1H-indole derivatives utilizing enhanced Lewis acidic sites of Surfactant-assisted ZnO catalyst - Sangale, Vijay B. B.; Jagtap, Rohidas M. M.; Mali, Bhupendra P. P.; Gonnade, Rajesh G. G.; Pardeshi, Satish K. K. (ChemistrySelect, 2023)
Five different ZnO nanocrystallites (ZnO-1 to ZnO-5) were successfully synthesized by a surfactant-assisted hydrothermal technique using various surfactants. All the ZnO nanocrystallites are thoroughly characterized by XRD, IR, UV-DRS spectroscopy and FESEM-EDS analysis. Among the synthesized ZnO nanocrystallites, the CTAB-assisted synthesized ZnO-4 exhibited a fine disc-like morphology with a minimum crystallite size (23 nm). Subsequent to reaction optimization studies, the ZnO-4 is utilized as an efficient catalyst for one pot-three component green synthesis of 3-[(aryl)(arylthio)methyl]-1H-indoles (4a-4p) via. condensation of a variety of indoles, aromatic aldehydes and aromatic thiols at room temperature in water. The single-crystal X-ray structure of 3-[(phenyl)(phenylthio)methyl]-1H-indole (4a) is also been reported (CCDC 2170437). The Lewis acidic property of the catalyst-supported probable mechanism is well proposed subsequent to pyridine-IR studies of the ZnO catalysts. Indeed, CTAB-assisted synthesized ZnO-4 was found to be most effective and selective Lewis acid catalyst for the synthesis of a variety of 3-[(aryl)(arylthio)methyl]-1H-indole derivatives in water at ambient temperature with merits like higher yields, lower reaction time, catalyst recovery and reuse.
Keywords: 3-[(aryl)(arylthio)methyl]-1H-indole; green synthesis; Lewis acidity; Single crystal; ZnO

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

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

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 3 alkyl and 1,3-Bis(alkyl)indolizine amides from a-bromohydroxamates - Mane, Kishor D.; Bagwe, Sagar S.; More, Satish G.; Suryavanshi, Gurunath (Tetrahedron Letters, 2023)
A simple and catalyst-free method has been developed for the synthesis of hindered indolizine amide derivatives from functionalized alkyl bromides. The reaction of a variety of indolizine derivatives with azaoxyallyl cations generated in situ from a-bromoamides afforded a wide range of synthetically important mono- and di-alkylated indolizine amide derivatives in good to excellent yields.@2023 Elsevier Ltd. All rights reserved.
Keywords: a -Bromohydroxamates; Amides; HFIP; Indolizine

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

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)

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.

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

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, structure elucidation and expanded bioactivity of icosalide A: effect of lipophilicity and ester to amide substitution on its bioactivity - Dangi, Abha; Pande, Bharat; Agrawal, Sonia; Sarkar, Dhiman; Vamkudoth, Koteswara Rao; Marelli, Udaya Kiran (Organic & Biomolecular Chemistry, 2023)
The first total synthesis of icosalide A, an antibacterial depsipeptide that is unique in that it contains two lipophilic beta-hydroxy acids, has been achieved by following Fmoc solid-phase peptide synthesis in combination with solution-phase synthesis. The ambiguity in the absolute stereochemistry of icosalide A has been resolved by synthesizing the reported structures and other relevant diastereomers of icosalides and comparing their NMR data. NMR-based structure elucidation of icosalide A revealed a well-folded structure with cross-strand hydrogen bonds similar to the anti-parallel beta-sheet conformation in peptides and displayed a synergistic juxtaposition of the aliphatic sidechains. 12 analogues of icosalide A were synthesized by varying the constituent lipophilic beta-hydroxy acid residues, and their biological activities against Bacillus thuringiensis and Paenibacillus dendritiformis were explored. Most of these icosalide analogues showed an MIC of 12.5 & mu;g mL(-1) against both bacteria. Swarming inhibition by icosalides was least in B. thuringiensis (8.3%) compared to that in P. dendritiformis (33%). Furthermore, this is the first report of icosalides showing assured inhibitory action (MIC between 2 and 10 & mu;g mL(-1)) against the active stage of Mycobacterium tuberculosis and cancer cell lines such as HeLa and ThP1. This study could help optimize icosalides for anti-TB, antibacterial, and anti-cancer activities.

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

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

Understanding critical aspects of liposomal synthesis for designing the next generation targeted drug delivery vehicle - Moudgil, Aliesha; Chaudhari, Bhushan P. (Chemistryselect, 2023)
We identified process parameters of the thin film hydration technique and intrinsic factors to synthesize liposomes for drug delivery. The thin film formation step impacted the nature of the lipid layer, and we optimized 240 RPM rotation speed, 700 mm of Hg vacuum pressure, and 2 ml of chloroform as the organic solvent. The hydration step controlled the particle specifications, and we optimized 270 RPM rotation speed, PBS as the hydrating medium, and 1 h hydration time. We obtained a comparatively smaller liposomal population with a lower size distribution just after hydrating the lipid layer that required milder downsizing steps -10 extrusion passes through a single polycarbonate membrane. The intrinsic factors including the concentrations and molar ratio of lipids affected the synthesis steps and the particle specifications. Characterization of liposomes by analytical techniques confirmed the synthesis of a monodisperse population with hydrodynamic diameter<150 nm, moderate stability, spherical morphology, and high thermal and storage stability. This comprehensive study defines the role of every parameter, provides a mechanistic insight into synthesis that is supported by experimental data, and helps tune specific parameters to synthesize liposomes for drug delivery or any application with desired specifications.
Keywords: carrier system; designing and characterization; drug delivery; liposomes; targeting moiety

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.

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)

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 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

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.

Zwitterionic tetrastanna(II) cyclic crown - Sahoo, Padmini; Chibde, Purva; Das, Satyabrata; Banerjee, Subhrashis; Mali, Bhupendra P.; Vanka, Kumar; Gonnade, Rajesh G.; Yildiz, Cem. B.; Majumdar, Moumita (European Journal of Inorganic Chemistry, 2023)
A 12-membered zwitterionic tetrastanna(II) cycle 1 having a crown ether-like topology has been isolated from the deprotonation of 1,1 & PRIME;-methylenediimidazole (B) with two equivalents of Sn[N(SiMe3)(2)](2) (A). The solid-state structure and NMR analysis confirms the tetrastanna(II) cycle 1 to be comprised of two stannate(II) and two stannyliumylidene ion pairs in alternating positions of the heterocycle. Computational analysis shows greater nucleophilicity at the proximally located stannate(II) centers. Nonetheless, the tetrastanna(II) cycle 1 remains poorly reactive due to engagement of Sn-II lone pair electrons in intramolecular donor-acceptor interactions. Simple deprotonation reaction between Sn[N(SiMe3)(2)](2) (A) and N-(diisopropylphenyl)imidazole (C) in equimolar ratio has led to a stannylene 2, involving the formation of a Sn-C covalent bond with the anionic imidazol-2-yl carbon center along with the release of NH(SiMe3)(2). Compound 2 exists as a dimer, where the unsubstituted ring nitrogen atom coordinated intermolecularly to the other stannylene center.
Keywords: Deprotonation; Imidazole; Macrocycle; Sn-II cation; stannylene

1,6-Conjugate addition of in situ generated aryldiazenes to p-quinone methides - Mamale, Ajay G.; Paul, Sayantan; Gonnade, Rajesh G.; Bhattacharya, Asish K. (Organic & Biomolecular Chemistry, 2024)
Herein we report a transition-metal free, base-mediated 1,6-conjugate addition of aryldiazenes to para-quinone methides (p-QMs). Arylhydrazines were used for the in situ generation of aryldiazenes using a base-mediated protocol in the presence of air as the oxidant. The 1,6-conjugate addition of aryldiazenes to para-quinone methides via a radical mechanism is followed by an oxidative rearrangement to furnish the desired product, arylhydrazones. Interestingly, our synthetic protocol results in the formation of an aryldiazene radical, which undergoes 1,6-conjugate addition with p-QMs to furnish the arylhydrazones.

2,3-Difunctionalization of quinones: a gold-catalyzed cascade approach for trifluoromethyl-amination or sulfoximination - Sharma, Alpa; Govande, Vijaya; Mahajan, Shivangani; Sawant, Sanghapal D. (Chemical Communications, 2024)
A one-pot domino protocol employing gold(i) catalysis has been developed for the cascade trifluoromethyl-amination/sulfoximination of quinones. Togni I serves as the trifluoromethyl installing precursor, while amine or sulfoximine serves as the aminating source. Preliminary investigations suggest a mutual activation of Togni I and the amine precursor, facilitating the facile difunctionalization of quinones with excellent regioselectivity. Extensive substrate scope exploration demonstrates moderate to good yields of difunctionalized products. Application to the natural product Juglone highlights its potential for late-stage modifications in medicinal chemistry and drug discovery. A one-pot domino protocol employing gold(i) catalysis has been developed for the cascade trifluoromethyl-amination/sulfoximination of quinones.

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

Adsorption based downstream processing approach for penicillin V from a Penicillium chrysogenum BIONCL I22 culture filtrate - Mishal, Bela H.; Das, Sancharini; Mahajan, Vaishnavi N.; Dharne, Mahesh S.; Joshi, Rakesh S.; Giri, Ashok P. (ACS Omega, 2024)
Penicillin V (phenoxy methyl penicillin) is highly sought after among natural penicillins because of its exceptional acid stability and effectiveness against common skin and respiratory infections. Given its wide-ranging therapeutic uses, there is a need to establish a greener method for its maximum recovery to reduce the carbon footprint. Here, we have identified and validated optimized operational conditions for resin-based penicillin V recovery. It was observed that Amberlite XAD4 had the highest penicillin V hydrophobic adsorption capacity among the other screened resins. Kinetic and isothermal studies using linear and nonlinear regression analysis showed that the adsorption process well fitted with pseudo-second-order kinetics (R-2 = 0.9816) and the Freundlich adsorption isotherm model (R-2 = 0.9871). Adsorption equilibrium was attained within 4 h, while maximum adsorption was observed at 3 mg/mL penicillin V concentration. Furthermore, the optimized extraction protocol was compared with the conventional butyl acetate-based downstream processing. Under optimum conditions resin-based penicillin V recovery was 2-fold higher as compared to the solvent extraction method and the resin could be reused for over six cycles without compromising the yield. These findings signify substantial progress toward the development of an environmentally sustainable approach for penicillin V recovery and a potentially viable method for extractive fermentation.

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

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

Asymmetric synthesis of inositol derivatives - Patil, Nivedita T.; Sarkar, Nitai; Mysore, S. Shashidhar; Gonnade, Rajesh G. (Tetrahedron, 2024)
Both the enantiomers of racemic 4- O -tosyl-6- O -benzyl- myo -inositol-1,3,5-orthoformate ( 2 ) were isolated by preferential crystallization and used to synthesize several enantiomeric myo -inositol derivatives - natural ononitol, natural laminitol, precursors for myo -inositol phosphates and an oxabicyclo [2.2.1] heptane derivative. This work demonstrates the potential of the enantiomeric tosylates D2 and L2 to serve as versatile starting materials for the absolute asymmetric synthesis of inositol derivatives and other natural products from symmetric myo -inositol since no optically active molecular entity was required for the resolution of 2.
Keywords: Asymmetric synthesis; Carbohydrate; Cyclitol; Inositol; Natural product

Bimetallic and plasmonic Ag and Cu integrated TiO2 thin films for enhanced solar hydrogen production in direct sunlight - Mani, Sunesh S.; Rajendran, Sivaraj; Arun, Pushkaran S.; Vijaykumar, Aparna; Mathew, Thomas; Gopinath, Chinnakonda S. (Energy Advances, 2024)
<div class="abstract author" id="aep-abstract-id7" style="box-sizing: border-box; margin: 0px 0px 8px; 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;"> Plasmonic metal nanoparticle-integrated mesoporous TiO2 nanocomposites (Ag/TiO2, Cu/TiO2 and Ag–Cu/TiO2), prepared by a simple chemical reduction method, have been demonstrated to show superior activity in thin-film form for solar H2 generation in sunlight. Integration of Ag + Cu on TiO2 significantly enhances the solar H2 production due to the combined SPR effect of both metal species and the possible synergistic interaction among Cu + Ag in Ag–Cu/TiO2. TiAgCu-1 (0.75 wt% Ag and 0.25 wt% Cu on TiO2) showed the highest H2 yield of 6.67 mmol h−1 g−1 and it is 43 times higher than that of bare TiO2. The thin-film form of TiAgCu-1 shows 5 times higher solar H2 production than its powder counterpart. 1 wt% of Ag or Cu on TiO2 shows a H2 yield of 4.6 or 2 mmol h−1 g−1, respectively, which underscores the importance of combined or synergistic effects. The increase in solar H2 generation in Ag–Cu/TiO2 is attributed to factors such as the SPR effect of Cu and Ag, and strong interaction between Ag and Cu. The high photocatalytic efficiency of the TiAgCu-1 thin film is attributed to the large dispersion of metallic species with relatively high Ag/Cu surface atomic ratio, enhanced light absorption, a heterogeneous distribution of Ag and Cu species, and high double layer capacitance. The inter particle mesoporous network increases the interfacial charge transfer and reduces the mass transfer limitations. The plausible photocatalytic reaction mechanism could involve the combination of direct electron transfer from metal (Cu/Ag) to TiO2 as well as the significant field effect due to the Ag–Cu alloy, which is expected to increase the electron excitation locally. <div class="abstract graphical" id="aep-abstract-id9" style="box-sizing: border-box; margin: 0px 0px 8px; 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;"> Plasmonic metal nanoparticle integrated mesoporous TiO2 nanocomposites (Ag/TiO2, Cu/TiO2 and Ag–Cu/TiO2), prepared by a simple chemical reduction method, have been demonstrated to show superior activity in thin-film form for solar H2 generation.

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

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

Brønsted acid- and Ni(ii)-catalyzed C-H oxidation/rearrangement of cyclotriveratrylenes (CTVs) to cyclic and acyclic quinones as potential anti-cancer agents - Darole, Ratanamala S.; Choudhary, Shailendra Singh; Sharma, Himanshu; Mali, Bhupendra P.; Gopu, Booblan; Vanka, Kumar; Senthilkumar, Beeran (Organic and biomolecular chemistry, 2024)
This paper describes a simple and practical protocol for the direct synthesis of acyclic and cyclic quinone derivatives via an acid-promoted nickel(ii)-catalyzed inner rim C-H oxidation of cyclotriveratrylene (CTV) and its analogues. The cyclic quinone derivatives resulted from trimethoxy-cyclotriveratrylene (TCTV) through C-C bond formation via intramolecular ipso substitution followed by subsequent anionic rearrangement containing stereo-vicinal quaternary centers. The DFT calculations strongly support the experimental findings and reveal the role of Bronsted acids in the C-H bond activation of CTV. All the newly synthesized compounds were screened for their in vitro anti-cancer activity using colorimetric SRB assay analysis. Among them, compounds 3a, 3d, 3h, 4a, 4b, 4c and 4e exhibited moderate anticancer activity against A549, HCT-116, PC-3, MDA-MB-231, HEK-293 and SW620 human cancer cell lines.

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

C-H functionalization of imidazo[1,5-a]pyridines: a metal-free approach for methylene insertion to access C(sp2)-C(sp3)-H-C(sp2) bond formation - Mahajan, Shivangani; Sawant, Sanghapal D. (ACS Omega, 2024)
Formaldehyde has been used as a solvent and a source of carbon to insert a methylene group for bridging two imidazo[1,5-a]pyridine molecules without using any metal catalysis. This strategy has been extended on other alkyl-, aryl-, and heteroaryl aldehydes as well. This C(sp2)-C(sp3)-H-C(sp2) bond forming reaction proceeds via C(sp2)H functionalization of imidazo[1,5-a]pyridine and was applied on a wide range of substrates offering moderate to good yields of methylene-bridged/inserted bis-imidazo[1,5-a]pyridines. Most importantly, as an application, the bis-heteroarene product has been demonstrated as a ligand. The ligand-like behavior of bis-imidazo[1,5-a]pyridines has been demonstrated as an extension of current methodology. This reaction works well at the gram scale level.

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.

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

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 modeling of sodium-ion-channel-based glucose sensing biophysics to study cardiac pacemaker action potential - Mahapatra, Chitaranjan; Shanmugam, Kirubanandan; Rusho, Maher Ali (Mathematical and Computational Applications, 2024)
Elevated blood glucose levels, known as hyperglycemia, play a significant role in sudden cardiac arrest, often resulting in sudden cardiac death, particularly among those with diabetes. Understanding the internal mechanisms has been a challenge for healthcare professionals, leading many research groups to investigate the relationship between blood glucose levels and cardiac electrical activity. Our hypothesis suggests that glucose-sensing biophysics mechanisms in cardiac tissue could clarify this connection. To explore this, we adapted a single-compartment computational model of the human pacemaker action potential. We incorporated glucose-sensing mechanisms with voltage-gated sodium ion channels using ordinary differential equations. Parameters for the model were based on existing experimental studies to mimic the impact of glucose levels on pacemaker action potential firing. Simulations using voltage clamp and current clamp techniques showed that elevated glucose levels decreased sodium ion channel currents, leading to a reduction in the pacemaker action potential frequency. In summary, our mathematical model provides a cellular-level understanding of how high glucose levels can lead to bradycardia and sudden cardiac death.

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

Copper-mediated [3+2] oxidative cyclization of oxime acetate and its utility in the formal synthesis of fentiazac - Jadhao, Nitin L.; Musale, Harish B.; Gajbhiye, Jayant M.; Humne, Vivek T. (Organic and biomolecular chemistry, 2024)
A new protocol for the direct synthesis of 2-aminothiazole has been developed from oxime acetate and readily available sodium thiocyanate using a copper catalyst. The present transformation has good functional group tolerance. Various thiazoles were smoothly synthesized in good to excellent yields. The applicability of the present method has been extended to the formal synthesis of the non-steroidal and anti-inflammatory drug, fentiazac via the Sandmeyer reaction and Suzuki coupling. The direct synthesis of 2-aminothiazole has been developed from oxime acetate using a copper catalyst. The applicability of the present method is used in the formal synthesis of fentiazac.
Keywords: Biological evaluation; C-H functionalization; Vinylazides

Creep resistance in doubly crosslinked dynamic covalent networks - Mondal, Swagata; Wong, Alexander J.; Wagh, Mahendra A.; Alperstein, Lily; Sanjayan, Gangadhar J.; Sumerlin, Brent S. (POLYMER CHEMISTRY, 2024)
Vitrimers are a unique class of thermosets that demonstrate reprocessability and recyclability due to dynamic bond exchange at crosslinking sites. However, the same dynamic bond exchange predisposes vitrimers to macroscopic deformation and creep under constant stress, which limits many practical applications. Herein, we demonstrated that the incorporation of Janus-faced guanine-cytosine diamine (GCBDam) functionality within vinylogous urethane vitrimers leads to significant creep resistance due to network reinforcement via hydrogen bonding. The supramolecular associations of the GCBDam groups retarded stress relaxation at temperatures as high as 160 degrees C. Further, rheological data suggested that the cooperative nature of the bifunctional Janus-faced hydrogen bonding moieties allowed the GCBDam to act as ``stickers'' within the dynamic covalent networks. These results indicate that incorporating the bifunctional supramolecular moiety improved dimensional stability while conserving the hallmark vitrimer property of reprocessability. This work demonstrates that incorporating Janus-faced supramolecular moieties in vinylogous urethane vitrimers improved dimensional stability while conserving the hallmark vitrimer property of reprocessability.

Cu-catalyzed multicomponent reaction of arylhydrazines with β-ketoesters and TBN: one-pot access to N 2-aryl 1,2,3-triazole-1-oxides - Mujahid, Mohammad; Vara, Vijay; Arshad, Usman; Gamidi, Rama Krishna; Muthukrishnan, M. (Journal of Organic Chemistry, 2024)
We report a copper-catalyzed one-pot, multicomponent strategy for the convenient synthesis of N 2-aryl 1,2,3-triazole-1-oxides using arylhydrazines, beta-ketoesters, and tert-butyl nitrite. This mild and simple reaction proceeds in an atom-economic manner with broad substrate scope, affording a variety of N 2-aryl 1,2,3-triazole-1-oxide derivatives. Other salient features of the reaction are good functional group tolerance, scalability, and product diversification.

Design of Bi-functional mixed oxide electrodes for selective oxidative C-C cleavage of glycerol to formate and synchronized green hydrogen production - Saha, Arindam; Murugiah, Vasantharadevi; Ranjan, Ravi; Chauhan, Inderjeet; Patra, Kshirodra Kumar; Bajpai, Himanshu; Saha, Avisekh; Gopinath, Chinnakonda S. (Sustainable Energy & Fuels, 2024)
Alkaline water electrolysis is a mature method to produce green hydrogen; however, it suffers from significantly high cost as high overpotentials are required for the oxygen evolution reaction (OER). However, the OER could be avoided altogether by replacing it with kinetically favorable oxidation of abundantly available feedstock molecules at a significantly low potential to value-added product(s) together with green hydrogen generation. This is a potential method to address the high cost of green hydrogen production while converting waste to wealth. Herein, we report green, template-free hydrothermal synthesis of an electrochemically active NiCoMn mixed oxide (NCMO) electrocatalyst with multiple sites, porous structure, large surface area, and nanoneedle (NN) morphology deposited directly over Ni foam (NF). Sustainable electrocatalytic performance was demonstrated for 120 h in 0.2 M alkaline glycerol using chronoamperometry and chronopotentiometry. Highly selective formate production demonstrated an exclusive C-C cleavage with the present catalyst system. Oxides of individual metal-ions (Ni, Co, and Mn) and their bimetallic combination (NiCo, NiMn, and CoMn) exhibited lower activity and product selectivity than the trimetallic NCMO electrocatalyst. The membrane-free two-electrode electrolyzer setup with NCMO/NF at both the anode and cathode (NCMO/NF & Vert;NCMO/NF) requires 1.63 V to accomplish 100 mA cm-2 with 0.2 M glycerol, which is 296 mV less than that of 1 M KOH solution. High faradaic efficiency was observed for hydrogen (98%) with highly selective formate (90%) production. Electrocatalytic formate generation from an alkaline glycerol solution with NCMO is an energy-efficient and promising approach that also supplies carbon-negative green H2. NiCoMn oxide nanoneedles with a cactus-like morphology are shown as bifunctional electrocatalysts that selectively oxidize glycerol to HCOOH and concurrently produce H2.

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

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.

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.

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

Dynamic cellular responses to gravitational forces: exploring the impact on white blood cell(s) - Murali, Anirudh; Sarkar, Ram Rup (Biomicrofluidics, 2024)
In recent years, the allure of space exploration and human spaceflight has surged, yet the effects of microgravity on the human body remain a significant concern. Immune and red blood cells rely on hematic or lymphatic streams as their primary means of transportation, posing notable challenges under microgravity conditions. This study sheds light on the intricate dynamics of cell behavior when suspended in bio-fluid under varying gravitational forces. Utilizing the dissipative particle dynamics approach, blood and white blood cells were modeled, with gravity applied as an external force along the vertical axis, ranging from 0 to 2 g in parameter sweeps. The results revealed discernible alterations in the cell shape and spatial alignment in response to gravity, quantified through metrics such as elongation and deformation indices, pitch angle, and normalized center of mass. Statistical analysis using the Mann-Whitney U test underscored clear distinctions between microgravity (<1 g) and hypergravity (>1 g) samples compared to normal gravity (1 g). Furthermore, the examination of forces exerted on the solid, including drag, shear stress, and solid forces, unveiled a reduction in the magnitude as the gravitational force increased. Additional analysis through dimensionless numbers unveiled the dominance of capillary and gravitational forces, which impacted cell velocity, leading to closer proximity to the wall and heightened viscous interaction with surrounding fluid particles. These interactions prompted shape alterations and reduced white blood cell area while increasing red blood cells. This study represents an effort in comprehending the effects of gravity on blood cells, offering insights into the intricate interplay between cellular dynamics and gravitational forces.

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

Effect of furfural, acetic acid and 5-hydroxymethylfurfural on yeast growth and xylitol fermentation using Pichia stipitis NCIM 3497 - Bhavana, B. K.; Mudliar, Sandeep N.; Bokade, V. V.; Debnath, S. (Biomass Conversion and Biorefinery, 2024)
The valorization of C5 sugars (xylose) from hemicellulose of agro-industrial residues to xylitol, as one of the multi-products biorefinery approach, mandates the pretreatment of biomass which releases fermentable sugars along with the generation of biological inhibitors affecting xylitol fermentation. This study was therefore evaluated to understand the inhibitory kinetics of furfural, 5-hydroxymethylfurfural and acetic acid on xylitol fermentation. Xylitol fermentation was established using Pichia stipitis NCIM 3497 with xylose as a pure substrate optimized for xylitol yield and productivity of 0.48 g/g of xylose and 0.13 g/L/h, respectively. The functional relationship of yeast specific growth rate and limiting substrate (xylose) was expressed by Monod-type kinetics. The inhibition kinetics results indicated that the effect of inhibitors on xylitol fermentation was furfural > acetic acid > HMF. Furfural (500 mg/L) and acetic acid (1000 mg/L) reduced xylitol yield by 59% and 44%, respectively, with least reduction of 9.89% exhibited by HMF. The synergistic effect of 500 mg/L furfural, 500 mg/L HMF and 1000 mg/L acetic acid showed the highest reduction in xylitol yield of 67.6% as compared to the control. Kinetic studies predicted that the maximum concentration of furfural, HMF and acetic acid which inhibited P. stipitis growth was 884 mg/L, 3258 mg/L and 2922 mg/L, respectively, whereas xylitol production was completely inhibited at 1069 mg/L furfural, 3498 mg/L HMF and 3714 mg/L acetic acid. Furfural and acetic acid were found to be a competitive inhibitor, while uncompetitive inhibition was observed with HMF indicating negligible effect on xylitol fermentation.
Keywords: Acetic acid; furfural; HMF; Inhibition kinetics; Pichia stipitis; Xylitol fermentation

Effect of transition metals (Mn, Co, Ni, and Zn) in size-controlled metal ferrite nanocrystals on the electrocatalytic oxygen evolution reaction - Jeyavani, Vijayakrishnan; Manoj, Shanmugasundaram; Mukherjee, Shatabdi Porel (ACS Applied Nano Materials, 2024)
Metal ferrite (MFO) M2+Fe2O4 (M2+ = Mn, Co, Ni, and Zn) nanocrystals (NCs) with a controlled size of similar to 4 nm were synthesized using stearic acid as the capping agent via a facile solvothermal method. The as-synthesized MnFe2O4 (MnFO), CoFe2O4 (CoFO), NiFe2O4 (NiFO), and ZnFe2O4 (ZnFO) NCs were characterized by XRD, FT-IR, Raman, XPS, TGA, TEM, and HRTEM analyses. The electrocatalytic oxygen evolution reaction (OER) is significant for future renewable energy to produce pure hydrogen (H-2) fuels through H2O splitting. However, because of the complex proton-coupled multielectron transfer process, it is kinetically quite challenging. Fe-containing transition metal-based electrocatalysts are well studied since it has been observed that Fe has a significant role in enhancing OER activity. It is well-known that the size and shape of the Fe/ferrite-based nanoelectrocatalyst play a vital role in electrocatalysis reactions. However, it is also critical to understand the effect of other earth-abundant and cost-effective transition metal ions (e.g., Mn, Co, Ni, and Zn) combined with Fe/ferrite NC-based OER electrocatalytic reactions while keeping the size of NCs constant and compare their electrocatalytic properties toward the development of advanced nanoelectrocatalysts, which is rarely studied to the best of the authors knowledge. Therefore, herein, the electrocatalytic properties for OER were examined by using the as-synthesized MnFO, CoFO, NiFO, and ZnFO NCs to understand the effect of metal ions (Mn, Co, Ni, and Zn) on the Fe-based nanoelectrocatalysts by keeping the size of the nanoelectrocatalysts constant at similar to 4 nm. Additionally, the influence of different substrates, e.g., carbon paper (CP) and nickel foam (NF), on the electrocatalytic activity of MFO (MnFO, CoFO, NiFO, and ZnFO) NCs was also compared. Interestingly, as an OER nanoelectrocatalyst, the CoFO NCs on the CP substrate show better electrochemical OER activity than other MFO NCs, with a Tafel slope value of 49.4 mV dec(-1), an ECSA of 112 cm(2), and a long-term stability of 24 h, which is comparatively higher than the other as-synthesized MFO NCs. On the other hand, MnFO NCs on the NF substrate show better electrochemical OER activity than the other as-synthesized MFO NCs. Therefore, this work highlights the effect of the substrate and the influence of transition metals, e.g., Mn, Co, Ni, and Zn, on size-controlled Fe-based nanoelectrocatalysts toward developing advanced OER electrocatalysts.
Keywords: Carbonpaper; electrocatalysis; Ferrites; Nickel foam; Oxygen Evolution Reaction; Size-controlled nanocrystals

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 glycolysis of used PET bottles into a high-quality valuable monomer using a shape-engineered MnO nanocatalyst - Swapna, Bhattu; Singh, Nittan; Patowary, Suranjana; Bharali, Pankaj; Madras, Giridhar; Sudarsanam, Putla (CATALYSIS SCIENCE & TECHNOLOGY, 2024)
Keywords: Catalyst; kinetics; Nanorods; Oxidation; Oxides; POLY(ETHYLENE-TEREPHTHALATE); WASTE

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.

Electrochemically enabled (3+2) cycloaddition of unbiased alkenes and β-dicarbonyls - Suryawanshi, Sharad M.; Sahoo, Suman; Shaligram, Parth S.; Manna, Narugopal; Samanta, Ramesh C. (Chemical Communications, 2024)
A (3+2) cycloaddition between unbiased alkenes and 1,3-dicarbonyls is accomplished by judicious choice of electrode material and electrocatalyst to access dihydrofuran derivatives. A fluorinated porous carbon electrode with appropriate thickness governs unprecedented reactivity. This methodology eliminates the necessity for any stabilizing group within the alkene substrate. This is a rare example of the annulation of unbiased internal and terminal alkenes with cyclic and acyclic beta-dicarbonyls.
Keywords: 1; 3-DICARBONYL COMPOUNDS; DIHYDROFURANS; FACILE SYNTHESIS

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.

Enhancing the Catalytic Activity of Pd Nanocrystals towards Suzuki Cross-Coupling by g-C3N4 Photosensitization - Mondal, Sanjit; Sahoo, Lipipuspa; Banoo, Maqsuma; Vaishnav, Yuvraj; Prabhakaran Vinod, Chathakudath; Gautam, Ujjal (Chemnanomat, 2024)
Developing renewable means of activating molecules over traditional catalysts for C-C bond formation is desirable for industrial applications. Herein, we report a strategy to improve the efficiency of Pd nanoparticles (NPs) for the Suzuki cross-coupling reactions by visible-light irradiation using g-C3N4 nanosheets (NSs) as photosensitizer. Pd NPs mounted on g-C3N4 become electron-rich under visible-light due to generation of excited electrons in g-C3N4 and thereby accelerate the rate-determining step. Remarkable photocatalytic activity was accomplished utilizing Pd/g-C3N4 for the Suzuki cross-coupling reaction in environmentally benign aqueous settings under room temperature conditions. The activity remarkably improves (similar to 2.5 times) upon light irradiation, yielding one of the highest known turnover frequencies (TOF) of 1858 h(-1) and confirming the photosensitizer role of g-C3N4. The TOF for coupling of aryl bromides is also significantly high (similar to 356 h(-1)). We establish that the low-energy/long-lived excitons preferencially transfer to Pd, paving a way for rational designing photocatalysts for various C-C coupling reactions.
Keywords: 2D graphitic carbon nitride; C-C cross-coupling; exciton transfer; heterogeneous photocatalyst; Photosensitization

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.

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

Facile chemical synthesis of BaO:MgO nanorods for designing distinctive solid-state asymmetric supercapacitor device with activated carbon - Bobade, Rushikesh G.; Dabke, Niteen B.; Shaikh, Shoyebmohamad F.; Lokhande, Balkrushna J.; Mane, Rajaram S.; Ambare, Revanappa C. (Journal of Energy Storage, 2024)
The successive ionic layer adsorption and reaction (SILAR) technique was adapted to produce the interconnected complex network of BaO:MgO nanorods on a flexible stainless-steel (SS) substrate surface. The phase and surface morphology of the BaO:MgO electrode were examined from the X-ray diffraction and scanning electron microscopy measurements, respectively, which endowed electrochemical specific capacitance (SC) of 528.77 F/g at a 2 mV/s scan rate with great rate capability and cycling performance of 94.33 % over 5000 cyclic voltammetry cycles. Fabricated BaO:MgO//AC asymmetric solid-state supercapacitor device, using polyvinyl alcohol and potassium hydroxide gel as an electrolyte, demonstrated distinctive energy storage performance, i.e., a specific capacitance (SC) of 259.07 F/g with an energy density of 57.27 Wh/kg and a power density of 2.34 kW/kg at a current density of 4 mA/cm(2). The results demonstrated the facile method for synthesizing a spherical nanorod network of BaO:MgO and made them promising electrode materials for energy storage applications. The use of a solid-state supercapacitor device to illuminate an LED demonstrated the commercial feasibility of both the materials utilized and the design type.
Keywords: activated carbon; ASSD device; BaO:MgO; SILAR; supercapacitor

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

Facile synthesis of nanostructured Ni/NiO/N-doped graphene electrocatalysts for enhanced oxygen evolution reaction - Madampadi, Roshni; Patel, Avit Bhogilal; Vinod, C. P.; Gupta, Ritu; Jagadeesan, Dinesh (Nanoscale Advances, 2024)
Electrocatalysts containing a Ni/NiO/N-doped graphene interface have been synthesised using the ligand-assisted chemical vapor deposition technique. NiO nanoparticles were used as the substrate to grow N-doped graphene by decomposing vapours of benzene and N-containing ligands. The method was demonstrated with two nitrogen-containing ligands, namely dipyrazino[2,3-f:2 `,3 `-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile (L) and melamine (M). The structure and composition of the as-synthesized composites were characterized by XRD, Raman spectroscopy, SEM, TEM and XPS. The composite prepared using the ligand L had NiO sandwiched between Ni and N-doped graphene and showed an overpotential of 292 mV at 10 mA cm-2 and a Tafel slope of 45.41 mV dec-1 for the OER, which is comparable to the existing noble metal catalysts. The composite prepared using the ligand M had Ni encapsulated by N-doped graphene without NiO. It showed an overpotential of 390 mV at 10 mA cm-2 and a Tafel slope of 78.9 mV dec-1. The ligand-assisted CVD route demonstrates a facile route to control the microstructure of the electrocatalysts. Electrocatalysts containing a Ni/NiO/N-doped graphene interface have been synthesised using the ligand-assisted chemical vapor deposition technique.

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

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

Functionalized quinolones and isoquinolones via 1,2-difunctionalization of arynes: synthesis of antagonist agent AS2717638 and floxacin key intermediates - Mahale, Sachin D.; Prasad, Anamika; Mhaske, Santosh B. (Chemical Communications, 2024)
Quinolones and isoquinolones are privileged scaffolds in synthetic/medicinal chemistry and drug discovery due to their unique chemical structures and intrinsic properties. Herein, we reveal a transition-metal-free approach for their synthesis from the reaction of dimethyl-2-((phenylamino)methylene)malonate with aryne precursors under mild conditions. The substrate scope is broad, accommodating a wide range of functional groups. The synthetic utility of the developed protocol has been demonstrated in the total synthesis of the potent antagonist agent AS2717638 and key intermediates of floxacin congeners. The gram-scale experiments illustrate its synthetic potential.

Glory of fire retardants in Li-ion batteries: could they be intrinsically safer? - Mishra, Rajat; Anne, Mounika; Das, Sayan; Chavva, Tarunikaa; Shelke, Manjusha V.; Pol, Vilas G. (Advanced Sustainable Systems, 2024)
Lithium-ion batteries (LIBs) have dramatically transformed modern energy storage, powering a wide range of devices from portable electronics to electric vehicles, yet the use of flammable liquid electrolytes raises thermal safety concerns. Researchers have investigated several ways to enhance LIB's fire resistance. Fire retarding molecules functions through cooling effects, scavenging radicals, and forming protective barriers. Incorporating fire-suppressing molecules within the LIBs aims to delay or mitigate thermal runaway scenarios, reducing the risks of fires or explosions. Achieving an optimal balance between safety and performance is a major obstacle in the design of intrinsically safer LIBs. Therefore, it is important to consider their effects on LIB's performance, long-term stability, and environmental impact. To overcome these challenges, collaborative research efforts among academia, industry, and regulatory sectors are necessary. This article reviews state-of-the-art literature associated with LIBs safety or even fire mitigation by introducing solid-state or quasi-solid-state electrolytes as well as modified liquid electrolytes. Moreover, the effectiveness of various strategies in making LIBs intrinsically safer is critically evaluated with an emphasis on fire retardants followed by shedding some light on the remaining challenges.

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

Heterogeneous acid-base organocatalyst for cascade deacetalisation-knoevenagel condensations - Chhetri, Ashis; Maibam, Ashakiran; Maniam, Subashani; BabaRao, Ravichandar; Wilson, Karen; Lee, Adam F.; Mitra, Joyee (ChemSusChem, 2024)
Multifunctional heterogeneous catalysts are an effective strategy to drive chemical cascades, with attendant time, resource and cost efficiencies by eliminating unit operations arising in normal multistep processes. Despite advances in the design of such catalysts, the fabrication of proximate, chemically antagonistic active sites remains a challenge for inorganic materials science. Hydrogen-bonded organocatalysts offer new opportunities for the molecular level design of multifunctional structures capable of stabilising antagonistic active sites. We report the catalytic application of a charge-assisted, hydrogen-bonded crystalline material, bis(melaminium)adipate (BMA), synthesised from melamine and adipic acid, which possesses proximate acid-base sites. BMA exhibits high activity for the cascade deacetalisation-Knoevenagel condensation of dimethyl acetals to form benzylidenemalononitriles under mild conditions in water; BMA is amenable to large-scale manufacture and recycling with minimal deactivation. Computational modelling of the melaminium cation in protonated BMA explains the observed catalytic reactivity, and identifies the first demethoxylation step as rate-limiting, which is in good agreement with time-dependent 1H NMR and kinetic experiments. A broad substrate scope for the cascade transformation of aromatic dimethyl acetals is demonstrated.
Keywords: Antagonistic acid-base sites; Charge-assisted hydrogen bonding; Chemical cascade; organocatalysis; Sustainable catalysis

Hexagonal boron nitride quantum dots embedded on layer-by-layer films for peroxidase-assisted colorimetric detection of β-galactosidase producing pathogens - Majumdar, Sristi; Gogoi, Devipriya; Boruah, Purna K.; Thakur, Ashutosh; Sarmah, Priyakhee; Gogoi, Parishmita; Sarkar, Sanjib; Pachani, Priyakshi; Manna, Prasenjit; Saikia, Ratul; Chaturvedi, Vikash; Shelke, Manjusha V.; et al. (ACS Applied Materials and Interfaces, 2024)
Pathogen detection has become a major research area all over the world for water quality surveillance and microbial risk assessment. Therefore, designing simple and sensitive detection kits plays a key role in envisaging and evaluating the risk of disease outbreaks and providing quality healthcare settings. Herein, we have designed a facile and low-cost colorimetric sensing strategy for the selective and sensitive determination of beta-galactosidase producing pathogens. The hexagonal boron nitride quantum dots (h-BN QDs) were established as a nanozyme that showed prominent peroxidase-like activity, which catalyzes 3,3 `,5,5 `-tetramethylbenzidine (TMB) oxidation by H2O2. The h-BN QDs were embedded on a layer-by-layer assembled agarose biopolymer. The beta-galactosidase enzyme partially degrades beta-1,4 glycosidic bonds of agarose polymer, resulting in accessibility of h-BN QDs on the solid surface. This assay can be conveniently conducted and analyzed by monitoring the blue color formation due to TMB oxidation within 30 min. The nanocomposite was stable for more than 90 days and was showing TMB oxidation after incubating it with Escherichia coli (E. coli). The limit of detection was calculated to be 1.8 x 10(6) and 1.5 x 10(6) CFU/mL for E. coli and Klebsiella pneumonia (K. pneumonia), respectively. Furthermore, this novel sensing approach is an attractive platform that was successfully applied to detect E. coli in spiked water samples and other food products with good accuracy, indicating its practical applicability for the detection of pathogens in real samples.
Keywords: biopolymer; colorimetric; h-BN quantum dots; nanozyme; pathogens; Sensor

High-capacity V2N MXene for multivalent ion batteries: an Ab initio study - Saharan, Sunita; Ghanekar, Umesh; Shivankar, Bhavana R.; Meena, Shweta (Journal of Physical Chemistry C, 2024)
In this study, the electrochemical energy storage properties of V2N MXene as an electrode material for multivalent zinc (Zn2+) and calcium (Ca2+) ion rechargeable batteries have been studied using first-principles computations. Various properties like band structure, adsorption energy, diffusion kinetics, and open-circuit voltage are investigated using density functional theory. V2N MXene demonstrates metallic properties with a high structural stability and low diffusion barriers. Remarkably, Zn (976.4 mA h/g) and Ca (770.8 mA h/g)-adsorbed V2N MXene layers exhibit better storage capacity than the reported ones (517 mA h/g for zinc-intercalated CC@MnO2@Ti3C2TX and 598.63 mA h/g for calcium-intercalated V3C2/graphene). These findings make V2N MXene a highly promising cathode material for zinc and an anode material for calcium-ion batteries.

Hydrogen evolution via photocatalytic reforming of biomass with palladium nanoparticles decorated g-C3N4 nanosheets - Thara, Chinnu R.; Walko, Priyanka S.; Mathew, Beena (Renewable Energy, 2024)
Fossil fuel depletion and environmental toxins have made photocatalytic H2 production of paramount significance. A novel and unique technique for producing sustainable H2 and valorizing biomass using infinite solar energy is biomass photoreformation. Nevertheless, this environmentally friendly method is usually linked to severe reaction circumstances, insufficient selectivity, and restricted biomass conversion. Here, we present a novel one-pot photoreformation technique over porous g-C3N4 nanosheets surface-modified with Pd nano- particles to convert D-glucose to H2. By stacking the g-C3N4 photocatalyst into a 2D nanosheet structure, some of its inherent drawbacks can be mitigated. Furthermore, the inclusion of noble metal nanoparticles in these g-C3N4 nanosheet structures could significantly boost existing photocatalytic activity. The majority of solar radiation is composed of visible light, which makes up 45% of it, and ultraviolet light, which makes up 5%. Therefore, our focus has been on utilizing abundant visible light to facilitate biomass reformation. After 4 h of continuous irradiation, our composite photocatalyst exhibited exceptional visible light activity; its H2 evolution was 1839.84 mu molg- 1h- 1 , or about 27 times higher than that of undoped g-C3N4 nanosheets. The effectiveness of three different Pd loadings on g-C3N4 nanosheets for glucose reforming was examined. In the quest for an improved H2 evolution visible light active photocatalyst, g-C3N4 nanosheets made at various pyrolysis temperatures loaded with optimized Pd weight percentage were also examined.
Keywords: Biomass; D -glucose; g-C 3 N 4 nanosheets; Hydrogen evolution; palladium nanoparticles; Photocatalytic reforming

HyStor: an experimental database of hydrogen storage properties for various metal alloy classes - Wilson, Nikhil; Verma, Ashwini; Maharana, Piyush Ranjan; Sahoo, Ameeya Bhusan; Joshi, Kavita (International Journal of Hydrogen Energy, 2024)
In this work, we introduce the HyStor database, consisting of 1282 metal alloys along with their maximum hydrogen storage capacity (H2wt%) at a given absorption temperature. The curated HydPark database consist of 831 entries. We sourced compositions from research articles and various patent documents, resulting in addition of 451 compositions to the HydPark database. The addition is reflected in the data across all existing classes of alloys. Further, low entropy alloys (LEA), medium entropy alloys (MEA) and high entropy alloys (HEA) have been newly included classes. This has broadened the scope of the database to encompass the latest materials of interest for hydrogen storage. HyStor contains representation of 54 elements, with a temperature range of 200-800 K, and H2wt% ranging from 0.1 to 7.19. We conducted thorough checks for duplicate entries, erroneous data, and conflicting compositions within the database to ensure data quality. Furthermore, we conducted multiple tests to identify potential outlier compositions. The data curation and updation reflects into slight improved error metrics of the HYST model, reducing the Mean Absolute Error (MAE) from 0.31 to 0.29 and increasing the R2 score from 0.77 to 0.79.
Keywords: Databases; machine learning; Metal hydrides; Solid-state hydrogen storage

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.

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

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.

Integrating 3,4-Dihydro-2H-1,4-oxazine into peptides as a modification: silver triflate-catalyzed cyclization of N-Propargyl N-Sulfonyl amino alcohols for SPPS applications - Patil, Abhijit Ramchandra; Marelli, Udaya Kiran (Organic Letters, 2024)
We present a methodology yielding 3,4-dihydro-2H-1,4-oxazine by cyclization of N-propargyl N-sulfonyl amino alcohols using silver triflate as a catalyst at ambient temperature. Additionally, we showcase the applicability of this methodology in solid phase peptide synthesis (SPPS) to introduce the oxazine heterocyclic ring into short peptides containing serine and threonine. Notably, Rink amide resin supported the on-resin formation of 3,4-dihydro-2H-1,4-oxazine, while 2-CTC resin facilitated the oxazine formation in a one-pot process involving peptide cleavage, deprotection, and subsequent C-O ring formation, thus offering a versatile method for the late-stage modification of peptides.

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

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

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

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

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 Cs2AgBiCl6 double perovskite: experimental and theoretical insights into the self-trapping for optoelectronic applications - Rahane, Swati N.; Rahane, Ganesh K.; Mandal, Animesh; Jadhav, Yogesh; Godha, Akshat; Rokade, Avinash; Shah, Shruti; Hase, Yogesh; Waghmare, Ashish; Saykar, Nilesh G.; Roy, Anurag; Salgaonkar, Kranti N.; et al. (ACS Physical Chemistry Au, 2024)
Lead-free double perovskites (DPs) will emerge as viable and environmentally safe substitutes for Pb-halide perovskites, demonstrating stability and nontoxicity if their optoelectronic property is greatly improved. Doping has been experimentally validated as a powerful tool for enhancing optoelectronic properties and concurrently reducing the defect state density in DP materials. Fundamental understanding of the optical properties of DPs, particularly the self-trapped exciton (STEs) dynamics, plays a critical role in a range of optoelectronic applications. Our study investigates how Fe doping influences the structural and optical properties of Cs2AgBiCl6 DPs by understanding their STEs dynamics, which is currently lacking in the literature. A combined experimental–computational approach is employed to investigate the optoelectronic properties of pure and doped Cs2AgBiCl6 (Fe–Cs2AgBiCl6) perovskites. Successful incorporation of Fe3+ ions is confirmed by X-ray diffraction and Raman spectroscopy. Moreover, the Fe–Cs2AgBiCl6 DPs exhibit strong absorption from below 400 nm up to 700 nm, indicating sub-band gap state transitions originating from surface defects. Photoluminescence (PL) analysis demonstrates a significant enhancement in the PL intensity, attributed to an increased radiative recombination rate and higher STE density. The radiative kinetics and average lifetime are investigated by the time-resolved PL (TRPL) method; in addition, temperature-dependent PL measurements provide valuable insights into activation energy and exciton–phonon coupling strength. Our findings will not only deepen our understanding of charge carrier dynamics associated with STEs but also pave the way for the design of some promising perovskite materials for use in optoelectronics and photocatalysis.

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.

Leveraging machine learning to dissect role of combinations of amino acids in modulating the effect of zinc on mammalian cell growth - Pandey, Ujjiti; Madhugiri, Indrani; Gadgil, Chetan; Gadgil, Mugdha (BIOTECHNOLOGY PROGRESS, 2024)
Keywords: Absorption; Cytotoxicity; ENTEROCYTES; HISTIDINE

Lignocellulosic biomass analysis: acidic lignin recovery, characterisation, and depolymerisation - Singh, Sandip K.; Matsagar, Babasaheb M.; Dhepe, Paresh L. (Biomass Conversion and Biorefinery, 2024)
For the development of an effective lignocellulosic biomass conversion technology to biofuels and chemicals, the biomass composition analysis and their properties need to be characterised prior to biomass valorisation, including polysaccharide hydrolysis and lignin depolymerisation. In this work, a facile colorimetric titration method for the quantification of alpha-, beta-, and gamma-cellulose, pentosan, lignin, and silica percentages of wheat straw (WS) and two bagasse (BG I and II) samples was done. The result showed higher amounts of structural biopolymers (i.e. holocellulose and lignin (similar to 89.3%)) in BG compared to WS (81%) sample. Lignin recovery from BG (I and II) and WS samples was done by applying two-stage concentrated and dilute sulphuric acid hydrolysis, and maximum recovery (i.e. 21.5%; acid soluble +insoluble) of lignin obtained from BG II sample. Elemental and composition analysis results were represented substantial differences in lignin properties, including higher heat values (19.8 MJkg(-1)) of recovered lignin from BG II as well as high amounts of silica percentage from WS lignin. An intense Si-O-Si asymmetric stretching mode and/or C-O-C aliphatic aromatic ether (similar to 1100 cm(-1)) was characterised for lignin derived from WS. C-13 CP-MAS NMR exhibited variable intensities for dibenzodioxocin, spirodienone, and tricin moieties in recovered lignin samples. These lignin samples were processed for depolymerisation using homogeneous (1-methyl-3-(3-sulphopropyl)-imidazolium hydrogen sulphate) and heterogeneous (immobilised Bronsted acidic ionic liquid) catalysts to lower molar mass aromatic fractions and represented 89% and 92% organic solvent-soluble product yields respectively from WS-derived lignin.
Keywords: bagasse; Dibenzodioxocin; Holocellulose; Lignin depolymerisation; Spirodienone; Tricin; Wheat straw

Linear poly(lactic acid) ionomers with pendant ionic groups - Joseph, Seena; Menon, Abhijith Hari; Lele, Ashish K.; Chikkali, Samir H. (New Journal of Chemistry, 2024)
Although PLA is widely used, melt processing of this polymer is still a challenging task. In our efforts to improve the melt strength and processability of PLA, we report the synthesis of high molecular weight linear PLA ionomers. PLA copolymers (CP1-CP3) with pendant alkyne groups were synthesized by reacting L-lactide with propargylated lactide. The existence of copolymers with alkyne groups was unambiguously demonstrated, and the percentage of alkyne was found to be 3-7%. A click reaction protocol was developed to treat the resultant alkyne functionalized copolymers (CP1-CP3) with mercaptosuccinic acid (MSA) and pendant carboxylic acid group functionalized copolymers (CP1-MSA1 to CP3-MSA3) were obtained. The 1-2D NMR confirmed the formation of a major MSA bis-addition product, along with a minor mono-addition product. In the final step, the MSA functionalized copolymers were treated with sodium hydride (NaH) to obtain the corresponding linear PLA ionomers (CP1-MSA1-Na1 to CP3-MSA3-Na3). Significant improvement in thermal and melt rheological properties was observed in these ionomers, as compared to the precursor copolymer and unmodified PLA, due to the microstructural changes caused by the association of the ionic groups. Storage modulus (G `) and loss modulus (G `') values showed a substantial increase in melt elasticity of the ionomers with G ` > G `', whereas the unmodified PLA melt behaved like a viscoelastic liquid. Detailed investigation reveals that incorporating pendant ionic groups in a high molecular weight linear PLA remarkably enhances the elastic modulus from 10 to 100 000 Pa (four orders of magnitude).

LsBOS utilizes oxalyl-CoA produced by LsAAE3 to synthesize β-ODAP in grass pea - Goldsmith, Moshe; Avram, Liat; Brandis, Alexander; Mehlman, Tevie; Ben-Dor, Shifra; Peleg, Yoav; Ben-Zeev, Efrat; Barbole, Ranjit S.; Reich, Ziv (Nature Communications, 2024)

Macrocyclic peptides derived from AcPHF6*and AcPHF6 to selectively modulate the Tau aggregation - Dangi, Abha; Qureshi, Tazeen; Chinnathambi, Subashchandrabose; Marelli, Udaya Kiran (Bioorganic Chemistry, 2024)
Ten macrocyclic peptides, each comprising 14 amino acids, were designed and synthesized based on the Tau aggregation model hexapeptides AcPHF6* and AcPHF6. The design took into account the aggregation tendencies of each residue in AcPHF6* and AcPHF6, their aggregation models, while employing peptide-based structural design principles including N-methylation to promote turns and to block hydrogen bond propagation and elongation of the aggregation chain. NMR analysis supported that all these peptides adopted an antiparallel beta-sheet conformation. Self-aggregation studies characterized the aggregation properties of these peptides, identifying two peptides with the highest (P3) and lowest (P8) aggregation tendencies. In cross-aggregation studies with the parent peptides AcPHF6* and AcPHF6, P3 and P8 were found to promote and reduce aggregation, respectively. Furthermore, P3 and P8 demonstrated an enhancement and diminution effect on the aggregation of K18wt, indicating their capacity to modulate aggregation even at the macromolecular level. Thus, the two simple peptides, P3 and P8 selectively exhibit pro- or anti-aggregation effects on PHF peptides and Tau. This study, has thus developed structurally well-defined non-complex peptides, derived from AcPHF6* and AcPHF6, to modulate Tau aggregation as desired, offering applications in Tau model studies and the development of Tau aggregation inhibitors or promoters.
Keywords: Cyclic peptides; Peptide -based drug design (PBDD); Peptide conformation; PHF peptides; Tau Aggregation

Magnetic chemiresistive Fe-doped In2O3 nanocubes to Tunably detect NO2 at ppm to ppb concentrations - Rudra, Pratyasha; Dambhare, Neha V.; Srihari, Velaga; Das, Sagnik; Rath, Arup Kumar; Saha, Debdulal; Mondal, Swastik (ACS APPLIED NANO MATERIALS, 2024)
Keywords: GAS-SENSING PROPERTIES; METAL-OXIDE NANOSTRUCTURES

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.

Methanesulfonic acid-catalyzed friedel-crafts alkylation: towards sustainable synthesis of arylalkanes from donor-acceptor cyclopropane ketones - Goswami, Lakshmi; Paul, Sayantan; Mamale, Ajay G.; Gonnade, Rajesh G.; Bhattacharya, Asish K. (Asian Journal of Organic Chemistry, 2024)
We present herein Br & oslash;nsted acid-catalyzed Friedel-Crafts alkylation of phenols with Donor-Acceptor cyclopropane ketones. The presence of the 1,4-diphenyl butan-1-one and 1,3-diphenyl propane-1-one motifs in various naturally occurring biologically significant molecules inspired us to pursue the direct synthesis of these structural frameworks. Utilizing methanesulfonic acid (MeSO3H) as a catalyst, we achieved a more environmentally friendly and high-yielding synthesis, owing to its cost-effectiveness, biodegradability, transition-metal and additives free conditions. Furthermore, we have successfully extended our developed methodology to thiophenols, resulting in the production of sulfur-based butan-1-one derivatives in good yields. The presence of 1,4-diphenyl butan-1-one and 1,3-diphenyl propane-1-one motifs in various naturally occurring biologically significant molecules prompted us to develop a Br & oslash;nsted acid-catalyzed Friedel-Crafts alkylation of phenols with Donor-Acceptor cyclopropane. image
Keywords: donor-acceptor cyclopropane; Friedel-Crafts alkylation; methanesulfonic acid; Phenols; thiophenol

Mitochondrial resilience and antioxidant defence against HIV-1: unveiling the power of Asparagus racemosus extracts and Shatavarin IV - Jadaun, Pratiksha; Harshithkumar, R.; Seniya, Chandrabhan; Gaikwad, Shraddha Y.; Bhoite, Shubhangi P.; Chandane-Tak, Madhuri; Borse, Swapnil; Chavan-Gautam, Preeti; Tillu, Girish; Mukherjee, Anupam (FRONTIERS IN MICROBIOLOGY, 2024)
Keywords: IN-SILICO; INHIBIT HIV-1

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

Multifunctional metabolites of Streptomyces kunmingensis BS19 from bamboo rhizosphere soil - Sangeetha, Murthy; Sasirekha, Sivakumar; Mahendran, Jaganathan; Sivarajan, Anbalmani; Radhakrishnan, Manikkam; Manigundan, Kaari; Dastager, Syed G.; Sengottuvelu, Singaravel; Balagurunathan, Ramasamy (International Microbiology, 2024)
A pigmented bioactive molecule from Streptomyces kunmingensis BS19 was isolated, characterized, and evaluated for anti-infective, antiproliferative, and wound-healing properties. The yellow–red pigment produced from the strain BS19 showed promising activity against methicillin-resistant Staphylococcus aureus (MRSA) and Mycobacterium tuberculosis. Extracellular bioactive pigment from the strain BS19 was produced by agar surface fermentation and purified through bioassay guided preparative HPLC-based purification. Based on the results of UV, FT-IR, GC–MS, 1H NMR, and 13C NMR spectral analyses, the purified pigment was identified as a chromopeptide class of molecule with phenoxazinone chromophore. Its molecular weight was determined as the chemical formula C64H90N12O16 and molecular weight 1283 g/mol. It exhibited promising antimicrobial activity against Staphylococcus aureus (ATCC 1720) and antiproliferative activity against 14 types of human cancer cell lines. It showed good in vivo wound-healing activity in the rat model. The present study explored Streptomyces kunmingensis as a newly added source for the isolation of chromopeptide antibiotics for antimicrobial, wound-healing, and anticancer applications.

Multi-site red-edge excitation shift reveals the residue-specific solvation dynamics during the native to amyloid-like transition of an amyloidogenic protein - More, Sonal R.; Jha, Santosh Kumar (Journal of Physical Chemistry B, 2024)
Changes in water-protein interactions are crucial for proteins to achieve functional and nonfunctional conformations during structural transitions by modulating local stability. Amyloid-like protein aggregates in deteriorating neurons are hallmarks of neurodegenerative disorders. These aggregates form through significant structural changes, transitioning from functional native conformations to supramolecular cross-beta-sheet structures via misfolded and oligomeric intermediates in a multistep process. However, the site-specific dynamics of water molecules from the native to misfolded conformations and further to oligomeric and compact amyloid structures remain poorly understood. In this study, we used the fluorescence method known as red-edge excitation shift (REES) to investigate the solvation dynamics at specific sites in various equilibrium conformations en route to the misfolding and aggregation of the functional domain of the TDP-43 protein (TDP-43tRRM). We generated three single tryptophan-single cysteine mutants of TDP-43tRRM, with the cysteines at different positions and tryptophan at a fixed position. Each sole cysteine was fluorescently labeled and used as a site-specific fluorophore along with the single tryptophan, creating four monitorable sites for REES studies. By investigating the site-specific extent of REES, we developed a residue-specific solvation dynamics map of TDP-43tRRM during its misfolding and aggregation. Our observations revealed that solvation dynamics progressively became more rigid and heterogeneous to varying extents at different sites during the transition from native to amyloid-like conformations.

Nanotrap infused ultrathin hybrid composite material for rapid and highly selective entrapment of 99TcO4- - Mandal, Writakshi; Fajal, Sahel; Majumder, Dipanjan; Sengupta, Arijit; Let, Sumanta; Urkude, Rajashri R.; Shirolkar, Mandar M.; Torris, Arun; Ghosh, Sujit K. (CHEMICAL SCIENCE, 2024)
Keywords: Adsorption; CAPTURE; EFFICIENT; Metal-organic framework; Removal; TECHNETIUM

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.

New record of larval-pupal endoparasitoid Exorista deligata parasitising Indian Tea looper Hyposidra talaca from India - Sharma, Pooja V.; Das, Tamal; Mukherjee, Susmita; Pathan, Ejaj K.; Rahman, Azizur; Gathalkar, Ganesh B. (Phytoparasitica, 2024)
This is the first record of Exorista deligata (Pandell & eacute;, 1896) (Diptera: Tachinidae) as a parasitoid of Hyposidra talaca (Walker, 1860) (Lepidoptera: Geometridae) from India. H. talaca is a major and new emerging defoliator of the Tea plant Camellia sinensis (L) Kuntze (Theaceae). It completes multiple generations per year without diapause on C. sinensis, resulting in heavy crop loss. The field-collected larvae/pupa of H. talaca were checked for parasitoid infestations and reared until either the host or parasitoid emerged. The parasitoid was identified as E. deligata with morphological characteristics and confirmed by the mitochondrial cytochrome oxidase subunit-I (COX-CO1) gene sequencing technique. The parasitoid is infrequent with unexplored parasitic biology. It parasitises the larva and completes its lifecycle inside the developing H. talaca by entirely devouring the host. The mean percent parasitisation caused by E. deligata studied herein was 25.4% (range 5.88%-57.69%). Based on its parasitisation ability, we suggest the species could be a potential biological control agent to address the damage mitigation caused by the tea looper pest, H. talaca.
Keywords: Biocontrol; Exorista deligata; Hyposidra talaca; Invasive pest; Parasitisation

N-terminal domain of polypyrimidine-tract binding protein is a dynamic folding platform for adaptive RNA recognition - Damberger, Fred F.; Krepl, Miroslav; Arora, Rajika; Beusch, Irene; Maris, Christophe; Dorn, Georg; Sponer, Jiri; Ravindranathan, Sapna; Allain, Frederic H-T (NUCLEIC ACIDS RESEARCH, 2024)
Keywords: CHEMICAL-SHIFT ANISOTROPY; NMR; ROTATING-FRAME RELAXATION; TIME-SCALE DYNAMICS

One-pot catalytic conversion of sucrose to 1,2-propanediol over titania supported Ni-Ce metal catalyst under milder reaction conditions - Sreekantan, Sreejith; Sreedharan, Sarath; Kirali, Arun Arunima Balachandran; Yadav, Parmeshwar; Marimuthu, Banu (Biomass Conversion and Biorefinery, 2024)
The increased energy demand and decreasing fossil resources have driven the research community to look into a sustainable, green process to meet the energy demands. India being one of the top producers of sugarcane derived sucrose, and conversion of surplus sucrose to value chemicals is always an advantage. 5%Ni-15%Ce/TiO2 catalyst is found to produce high yield of 1,2-PDO (similar to 74%) under very mild reaction condition of 180 degrees C, 30 bar H-2 for 3-h reaction time. The characterization of the catalyst by using various physicochemical methods indicates the synergy between Ni-Ce bimetal which enhances the selective production of glycol. The low temperature and pressure requirement and the advantage of being the one-pot process will always attract the future scope of commercialization.
Keywords: Glycol; Low pressure; Low temperature; Ni-Ce catalyst; Sucrose; titania

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

One-pot synthesis of pyrazoles from sulfonyl hydrazides and alkynyl ketones using environmentally benign sulfonium iodate (I) reagent - Mishra, Akanksha; Talukdar, Mrinal; Krishna, Gamidi Rama; Begari, Eeshwaraiah (ChemistrySelect, 2024)
Pyrazole is an omnipresent moiety in many natural products and pharmaceutically active compounds. Here, we have developed a simple and dynamic method for one-pot synthesis of substituted pyrazoles through the intramolecular cyclization of hydrazides and alkynyl ketones, using a novel sulfonium saltbased iodate (& Iukcy;) reagent system. This method has the advantage that it proceeds in a one-pot, without isolating a less stable hydrazone intermediate. Hypervalent iodine-based reagents are an environmentally benign and greener option to toxic metal oxidants; they have an extensive application in metal-catalyst-free reactions, and this reaction proceeds in less time with high yields.
Keywords: Deprotonation; One-pot reaction; Oxidative iodination; Pyrazole; S(N)2-type cyclization

Performance of Li exchange hierarchical X zeolite for CO2 adsorption and H2 separation - Shrotri, Aadesh R.; Birje, Amit R.; Niphadkar, Prashant S.; V. Bokade, Vijay; Mali, Nilesh A.; Nandanwar, Sachin U. (Journal of Industrial and Engineering Chemistry, 2024)
Li exchange hierarchical X zeolite (Li-H-X) was prepared by decationization of X zeolite by NH4Cl solution followed by Li exchange and subsequent calcination. NH4-X and Li-X were prepared to compare the results of LiH-X. XRD, FE-SEM, EDS, N2 adsorption-desorption, and micro-/mesoporous volume were performed. The higher mesoporosity was confirmed in Li-H-X due to the framework dealumination during decationization. Static and dynamic sorption capacity of sorbents was evaluated to identify the performance of sorbent. The CO2 and H2 equilibrium adsorption capacity of Li-H-X was found to be 9.6 mmol g-1 and 0.78 mmol g-1, respectively, at 298 K and 20 bar, which was 25 % (CO2) and 30 % (H2) higher than Li-X. Static experimental data were validated using the Langmuir, Freundlich, and Sips models. The CO2 & H2 dynamic sorption capacity of Li-H-X sorbent for binary gas (CO2/H2, 25/75 %) was 4.145 mmol g-1 and 0.258 mmol g-1 at 303 K and 10 bar. The higher sorption capacity of Li-H-X was obtained due to large micro-/mesoporous volume of sorbent, which may allow to access unoccupied sites at higher pressure. This result reveals that micro-/mesoporous structure of zeolite adsorbs significantly higher CO2 from binary gas stream, which can use to separate pure H2 from gas stream.
Keywords: Adsorption; Carbon dioxide; Hydrogen; Microporous-mesoporous; Separation

Polymer nanocomposites with UiO-derived zirconia fillers for energy generation and pressure-sensing devices: the role of crystal structure and surface characteristics - Mukherjee, Gargi; Verma, Ankur; Madhu, Arjun Hari; Prasad, Bhagavatula L. V.; Karumuthil, Subash Cherumannil (ACS Applied Nano Materials, 2024)
Piezoelectric energy harvesting and pressure sensing using polymer nanocomposites have opened up promising avenues in the field of flexible electronics. Herein, the influence of varying crystal structures of zirconia nanoparticles on a piezoelectric energy-generating zirconia-poly(vinylidene difluoride) (PVDF) composite is investigated, and the fabrication of a security alert pavement unit using the material with an optimized composition is demonstrated. More specifically, two metal-organic frameworks, UiO-66 and UiO-67, were employed to synthesize four different types of zirconia nanoparticles with precise control of the monoclinic and tetragonal phases. Polymer nanocomposite with monoclinic zirconia nanoparticles derived from UiO-66 (ZrO2-66m) performed better than other derivatives with 61% enhancement in the beta phase with respect to pure PVDF. It was hypothesized that the stable crystalline structure of the monoclinic phase might act as a better nucleating agent, and among monoclinic derivatives, ZrO2-66m was found to be more hydrophobic, probably enabling a better interaction with PVDF. Subsequently, a prototype device with a PVDF-ZrO2-66m (P/66m) film was made and tested for its energy generation. The maximum output voltage generated by the device under an irregular biomechanical hand tapping force of 8-9 N was 80 V, while the maximum open circuit current was found to be 65 mu A. The prototype displayed a power of 2162.24 mu W at a load resistance of 1 M Omega. A laboratory scale demonstration was executed with the prototype as an energy-generating and security alert pavement unit. A wireless, Bluetooth-based security alert system supported by an Android application was developed and demonstrated as a promising application with the fabricated prototype. The results and demonstrations validate that the PVDF-monoclinic ZrO2 nanoparticle nanocomposites will be an excellent value addition for flexible, durable energy generation and pressure-sensing applications.
Keywords: energy generation and pressure sensing; piezoelectric materials; PVDF/ZrO2 polymernanocomposite; self-powered devices; wearable electronics

Polymeric PEI/PEG coated optical fiber fabry-perot interferometer for CO2 detection - Pawar, Dnyandeo; Lo Presti, Daniela; Lemma, Enrico D.; Rainer, Alberto; Kumar, Ajay; Kanawade, Rajesh; Silvestri, Sergio; Schena, Emiliano; Massaroni, Carlo (IEEE Sensors Journal, 2024)
Monitoring carbon dioxide (CO2) gas is essential for numerous applications, but the detection of CO2 in miniaturized devices presents significant challenges. In this study, a polyethyleneimine/poly(ethylene glycol) (PEI/PEG) coated optical fiber Fabry-Perot interferometer (FPI) and its charge transfer process toward CO2 are investigated. Scanning electron microscopy and Fourier transform infrared spectroscopy were used to analyze the surface morphology and vibration bands of the PEI/PEG composite. The PEI/PEG composite Fabry-Perot (FP) cavity of length similar to 13 mu m is coated at the distal end of the single-mode fiber using a dip coating technique. A highly sensitive optical and low-cost FPI probe fabrication has displayed a linear sensitivity of 17.10 nm/% in the range of 0.31%-1.25% CO2 gas. The response and recovery times of the sensor are in a few tens of seconds. The enhanced performance of the sensor is primarily due to the protonation and charge transfer between CO2 gas molecules and PEI/PEG composite. Due to low-cost fabrication and high sensitivity, this FPI sensor can be used in a range of potential applications in bioprocessing, healthcare, and environmental monitoring.
Keywords: dip coating; Fresnel's reflection; Interference; monitoring; Optical fiber sensors; Optical fibers; polymer composite; Polymers; refractive index; sensitivity; Sensor phenomena and characterization; sensors; swelling; Temperature sensors

Polymerized stimuli-responsive microgel hybrids of silver nanoparticles as efficient reusable catalyst for reduction reaction - Pany, Biswajit; Majumdar, Amrito Ghosh; Bhat, Suresh; Si, Satybrata; Yamanaka, Junpei; Mohanty, Priti S. (Heliyon, 2024)
We have showcased the potential of polymerized hydrogels (PGMs) with uniform -sized stimuliresponsive microgel particles as promising alternatives to prevent aggregation in solution based nanoparticle systems. In the current work, we implemented the PGM concept by embedding anionic stimuli -responsive microgels (PNIPAM-co-AAc)-silver (Ag) hybrids within a hydrogel matrix. These PGM@AgNP hybrid materials are used as catalysts for the reduction of 4-nitrophenol (4 -NP) to 4-aminophenol (4 -AP) in the presence of sodium borohydride. UV-VIS spectroscopy is used for studying catalytic activity. In the solution based system, the complete reduction of 4NP to 4 -AP took 30 minutes with pure Ag nanoparticles, 24 minutes with PNIPAM-Ag hybrid (Neutral) microgels and 15 minutes with PNIPAM-co-AAc-Ag (Anionic) hybrid microgels. In contrast PGM containing PNIPAM-co-AAc-Ag hybrids achieved full reduction in just 15 minutes, along with a 3 -minute induction period. For pure Ag nanoparticles, the first -order rate constant is found to be 0.25 min - 1, for PNIPAM-Ag hybrid (Neutral), it is 0.21 min- 1 and for PNIPAM-coAAc-Ag (Anionic), it is 0.5 min- 1 where as for PGM containing anionic microgel hybrids it is found to be 0.8 min - 1. Furthermore, the reusability of the PGM-Ag (anionic) materials for catalytic activity remains unaltered even after several washings. In summary, our study highlights the effectiveness of PGM@AgNP materials as efficient catalysts for the reduction of 4-nitrophenol to 4-aminophenol, indicating their versatile potential in various catalytic applications.
Keywords: Light scattering; Microgel-metal hybrids; Nanomaterial catalysts; PNIPAM microgels; Polymerized hydrogel matrix(PGM; Stimuli-responsive microgels

Probing the energy landscape of the lipid interactions of the serotonin 1A receptor - Mohole, Madhura; Naglekar, Amit; Sengupta, Durba; Chattopadhyay, Amitabha (Biophysical Chemistry, 2024)
G protein-coupled receptors (GPCRs) are lipid-regulated transmembrane proteins that play a central role in cell signaling and pharmacology. Although the role of membrane lipids in GPCR function is well established, the underlying GPCR-lipid interactions have not been thermodynamically characterized due to the complexity of these interactions. In this work, we estimate the energetics and dynamics of lipid association from coarse-grain simulations of the serotonin1A receptor embedded in a complex membrane. We show that lipids bind to the receptor with varying energetics of 1-4 kT, and timescales of 1-10 mu s. The most favorable energetics and longest residence times are observed for cholesterol, glycosphingolipid GM1, phosphatidylethanolamine (PE) and phosphatidylserine (PS) lipids. Multi-exponential fitting of the contact probability suggests distinct dynamic regimes, corresponding to ps, ns and mu s timescales, that we correlate with the annular, intermediate and nonannular lipid sites. The timescales of lipid binding correspond to high barrier heights, despite their relatively weaker energetics. Our results highlight that GPCR-lipid interactions are driven by both thermodynamic interactions and the dynamical features of lipid binding.
Keywords: GPCR-lipid interactions; Lipid energetics; Lipid residence time; Molecular dynamics simulations; Serotonin 1 a receptor

Purification of waste-generated biogas mixtures using covalent organic framework's high CO2 Selectivity - Paul, Ratul; Maibam, Ashakiran; Chatterjee, Rupak; Wang, Wenjing; Mukherjee, Triya; Das, Nitumani; Yellappa, Masapogu; Banerjee, Tanmay; Bhaumik, Asim; Venkata Mohan, S.; BabaRao, Ravichandar; Mondal, John (ACS APPLIED MATERIALS & INTERFACES, 2024)
Keywords: CAPTURE; CARBON-DIOXIDE; Efficiency; Energy; Hydrogen; STORAGE

Pyridazine-Based Aggregation Induced Emission Active Conjugates: Synthesis, Single Crystal XRD Analysis, and Self-Assembly Assessment - Waghchoure, Aishwarya P.; Sangale, Vijay B.; Shaligram, Parth S.; Lambud, Sushil; Pardeshi, Satish K.; Gonnade, Rajesh G.; Bandaru, Sateesh; More, Sandeep; Reddy, J. Prakasha; Bhosale, Rajesh S. (CHEMISTRYSELECT, 2024)
Keywords: AIE; Pyridazine; Self-assembly; Single crystal

Rational design of zero-dimensional manganese(II) halide hybrids with suppressed melting temperatures - Singh, Shivangi; Marayathungal, Jumana Hasin; Das, Deep Kumar; Khan, Akram Aadil; Bakthavatsalam, Rangarajan; Hathwar, Venkatesha R.; Kundu, Janardan (JOURNAL OF PHYSICAL CHEMISTRY C, 2024)
Keywords: ORGANIC-INORGANIC PEROVSKITES; TRANSITION

Reactive distillation configuration for the production of ethyl acrylate - Gore, Jayram I.; Mahajani, Sanjay M.; Mali, Nilesh A. (CHEMICAL ENGINEERING AND PROCESSING-PROCESS INTENSIFICATION, 2024)
Keywords: ACETIC-ACID; CYCLOHEXYL ACETATE; Design; Dimethyl carbonate

Reconstituting the microstructural properties and ionic conductivity of copper - doped yttria-stabilized zirconia via mechanochemical synthesis for intermediate-temperature solid oxide fuel cell applications - Momin, Naeemakhtar; Manjanna, J.; Kobayashi, Satoru; Aruna, S. T.; Kumar, S. Senthil; Ahmad, Tokeer; Nayaka, G. P.; Mubeen, B.; Sabale, Sandip; Kangralkari, Mrunal V.; Keri, Rangappa S. (CERAMICS INTERNATIONAL, 2024)
Keywords: ELECTRICAL-PROPERTIES; OPTICAL-PROPERTIES; THERMAL-STABILITY; TRANSITION-METAL

Reduced graphene oxide/tungsten oxide (rGO/WO3): a versatile nanocomposite for enhanced detection of acetone - Patil, Abhijeet P.; Gaikwad, Mayur A.; Nadargi, Jyoti D.; Shaikh, Hamid; Alam, Mohammad Asif; Tamboli, Mohaseen S.; Kim, Jin Hyeok; Mulla, Imtiaz S.; Suryavanshi, Sharad S. (Journal of Materials Science-Materials In Electronics, 2024)
In this study, we report a straightforward method for synthesizing semi-cubical nanostructures of tungsten trioxide (WO3) loaded with reduced graphene oxide (rGO) via a hydrothermal approach. Furthermore, the systematic investigations were made towards the improved gas sensing capabilities of these nanostructures for acetone. The use of semi-cubical rGO/WO3 nanostructures demonstrate the provision of efficient gas diffusion routes via a meticulously arranged mesoporous framework. Hence, it leads to a significant improvement in the sensing response towards acetone. The analysis of the sensing capabilities demonstrates that the response of the sensor is influenced by variations in operating temperature and gas concentration. It is seen that the inclusion of rGO not only enhances the sensing response but also gives quick response and recovery, which are measured to be 12 and 33 s, respectively. The WO3 sensor loaded with 0.1 wt% rGO demonstrates a discerning reaction to acetone, exhibiting a high response of 93.60% than that of the unmodified WO3 sensor (76.30%). The gas sensing properties are explained through the role of rGO and the structural and morphological properties of the developed nanostructures.

Regio- and stereoselective construction of 1,3,5-triaroylcyclohexanes via KO t Bu-mediated cyclotrimerization of aryl vinyl ketones - Mahale, Sachin D.; Yadav, Vinita; Gonnade, Rajesh G.; Mhaske, Santosh B. (Journal of Organic Chemistry, 2024)
Herein, we disclose a simple one-pot method for an efficient regio- and stereoselective synthesis of 1,3,5-triaroylcyclohexanes from aryl vinyl ketones using potassium tert-butoxide. The developed protocol allows the construction of various symmetrically substituted cyclohexanes in good to excellent yields. The major product 2 also can be converted to the product 3 (all equatorial) conveniently by acid catalysis. This protocol features a good substrate scope and functional group compatibility.

Remarkable SO2 and H2S resistant ability on CO oxidation by unique Pd/WO3 3D hollow sphere nanocatalyst: correlating structure-activity relationships on SO2 exposure - Jeyavani, Vijayakrishnan; Kondhekar, Deepali; Bhati, Meema; Dev, Sahil; Joshi, Kavita; Devi, R. Nandini; Mukherjee, Shatabdi Porel (ACS Applied Energy Materials, 2024)
We report a simple inorganic route for synthesizing a Pd/WO3 3D hollow sphere nanocatalyst, where Pd nanoparticles are encapsulated and well distributed on porous tungsten oxide nanospheres. The synthesis protocol has advantages, as it requires no surfactant or stabilizing agent, Pd loading is easily tuned, and the as-synthesized nanomaterials can be directly used as catalysts for the CO oxidation reaction. The synthesized nanocatalyst exhibited 100% CO to CO2 conversion efficiency at 260 degrees C. In addition, the nanocatalyst demonstrated remarkable SO2 (3 ppm) tolerance during the CO oxidation reaction for prolonged SO2 sulfation of 1-21 h at 260-400 degrees C. This represents the longest SO2 exposure time reported to date based on a single metal Pd/support-based nanocatalyst. No decrement in CO conversion efficiency was observed even after SO2 (3 ppm) treatment for 21 h for the first time based on a single metal Pd-based nanocatalyst. Moreover, the synthesized nanocatalyst shows H2S (4 ppm), even in situ H2S tolerance during the CO oxidation reaction at 260 degrees C for 1-3 h and exhibited less sensitivity to prolonged and stringent sulfur exposure, with the highest H2S concentration and maximum 100% CO to CO2 conversion efficiency obtained after H2S treatment for the first time based on a Pd-based nanocatalyst to the best of our knowledge. The composition and structure of the R-Pd/WO3 nanocatalyst were not much influenced, even after the prolonged SO2 and H2S exposure during the CO oxidation reaction, as verified from spent catalyst analysis. Finally, our DFT-based model provides insights into understanding the observed sulfur resistance on Pd/WO3 by analyzing the underlying electronic structure. Therefore, our strategic synthesis methodology will open up many opportunities to select Pd/metal oxide-based nanomaterials for designing highly efficient, stable, and SO2/H2S-resistant nanocomposite catalyst.
Keywords: CO oxidation; DFT calculation; nanocatalyst; palladium (Pd); SO2 andH(2)S resistant ability; structure-activityrelationships; tungstenoxide (WO3)

Renewable synthesis of MoO3 nanosheets via low temperature phase transition for supercapacitor application - Sankar, K. N. Amba; Kesavan, Lokesh; Saha, Bikash; Jyolsnaraj, M. K.; Mohan, S.; Nandakumar, P.; Mohanta, Kallol; Kvarnstroem, Carita (SCIENTIFIC REPORTS, 2024)
Keywords: alpha-MoO3; h-MoO3; Mixed phases (h and alpha) of MoO3; Renewable green synthesis; Very low temperature phase transition

Resorcinol-Azodianiline Covalent Organic Framework Supported FeOOH Quantum Dot-Catalyzed Electrochemical Ammonia Synthesis under Ambient Conditions - Shekhar, Pragalbh; Kosugi, Kento; Singh, Himan Dev; Kushwaha, Rinku; Rase, Deepak; Matsuzaki, Takumi; Jain, Chitvan; Singh, Piyush; Singh, Yashraj; Vinod, Chathakudath Prabhakaran; Kondo, Mio; Masaoka, Shigeyuki; et al. (CHEMISTRY OF MATERIALS, 2024)
Keywords: conversion; nitrogen; Recent Progress; reduction

Review on the recent advances in the design and structure–activity relationship of TiO2-based photocatalysts for solar hydrogen production - Mani, Sunesh S.; Rajendran, Sivaraj; Mathew, Thomas; Gopinath, Chinnakonda (Energy Advances, 2024)
The major issues that determine the efficiency of photocatalyst composite materials for solar hydrogen production, with or without a sacrificial agent, are efficient visible light harvesting properties, efficient separation of charge carriers and their utilization of redox sites, and stability. Thus, significant efforts have been devoted in the past few decades to modify the above characteristics by integrating constituent components of composites using different approaches. In the present review, we aim to summarize the recent advances, predominantly, in the area of TiO2-based photocatalyst composites for solar hydrogen production. Firstly, we present the recent progress in material integration aspects by discussing the integration of TiO2 with different categories of materials, including noble/3d metals, metal oxides/sulphides/selenides, other low bandgap semiconductors, C-based materials, and dye sensitizers. Furthermore, we discuss how material integration helps in tailoring the electronic and optical properties for activity tuning in solar H2 production. Subsequently, critical changes in the physico-chemical and electronic properties of composites with respect to their preparation methods, morphology, crystallographic facets, particle size, dopant, calcination temperature, and structure–activity relationship to solar hydrogen production are addressed in detail. Moreover, we discuss the importance of fabricating a photocatalyst in a thin film form and performing solar hydrogen production in different reactor set-ups for enhancing its photocatalytic performance, while addressing device scalability. Despite the significant advancements made in this field, solar-to-hydrogen conversion efficiency still needs to be improved to realise the practical application of solar hydrogen production. In this case, the direct conversion of water to hydrogen via overall water splitting and renewable H2 production from wastewater or biomass components by employing suitable photocatalysts are some possible ways to improve the energy efficiency, and continuous research in the above directions is highly desirable.

Robust spin liquidity in 2D metal-organic framework Cu3 (HHTP)2 with S=1/2 kagome lattice - Ninawe, Pranay; Jain, Anil; Sangole, Mayur; Anas, Mohd; Ugale, Ajay; Malik, Vivek K.; Yusuf, Seikh M.; Singh, Kirandeep; Ballav, Nirmalya (Chemistry- a european journal, 2024)
On one hand electron or hole doping of quantum spin liquid (QSL) may unlock high-temperature superconductivity and on the other hand it can disrupt the spin liquidity, giving rise to a magnetically ordered ground state. Recently, a 2D MOF, Cu-3(HHTP)(2) (HHTP - 2,3,6,7,10,11-hexahydroxytriphenylene), containing Cu(II) S = 1/2 frustrated spins in the Kagome lattice is emerging as a promising QSL candidate. Herein, we present an elegant in situ redox-chemistry strategy of anchoring Cu-3(HHTP)(2) crystallites onto diamagnetic reduced graphene oxide (rGO) sheets, resulting in the formation of electron-doped Cu-3(HHTP)(2)-rGO composite which exhibited a characteristic semiconducting behavior (5 K to 300 K) with high electrical conductivity of 70 S . m(-1) and a carrier density of similar to 1.1 x 10(18) cm(-3) at 300 K. Remarkably, no magnetic transition in the Cu-3(HHTP)(2)-rGO composite was observed down to 1.5 K endorsing the robust spin liquidity of the 2D MOF Cu-3(HHTP)(2). Specific heat capacity measurements led to the estimation of the residual entropy values of 28 % and 34 % of the theoretically expected value for the pristine Cu-3(HHTP)(2) and Cu-3(HHTP)(2)-rGO composite, establishing the presence of strong quantum fluctuations down to 1.5 K (two times smaller than the value of the exchange interaction J).
Keywords: 2D Metal-organic Framework; Electron doping; Reduced graphene oxide; Spin Liquid; Spin-frustration

Role and significance of virus-bacteria interactions in disease progression - Pokhrel, Vatsala; Kuntal, Bhusan K.; Mande, Sharmila S. (Journal of Applied Microbiology, 2024)
Understanding disease pathogenesis caused by bacteria/virus, from the perspective of individual pathogen has provided meaningful insights. However, as viral and bacterial counterparts might inhabit the same infection site, it becomes crucial to consider their interactions and contributions in disease onset and progression. The objective of the review is to highlight the importance of considering both viral and bacterial agents during the course of coinfection. The review provides a unique perspective on the general theme of virus-bacteria interactions, which either lead to colocalized infections that are restricted to one anatomical niche, or systemic infections that have a systemic effect on the human host. The sequence, nature, and underlying mechanisms of certain virus-bacteria interactions have been elaborated with relevant examples from literature. It also attempts to address the various applied aspects, including diagnostic and therapeutic strategies for individual infections as well as virus-bacteria coinfections. The review aims to aid researchers in comprehending the intricate interplay between virus and bacteria in disease progression, thereby enhancing understanding of current methodologies and empowering the development of novel health care strategies to tackle coinfections.
Keywords: Bacteria; coinfections; infections; virus; virus-bacteria interactions

Ru-catalyzed asymmetric transfer hydrogenation of racemic /3-keto γ-lactams via dynamic kinetic resolution - Malekar, V. Pushpa; More, V. Ganesh; Ramana, V. Chepuri (Tetrahedron, 2024)
The enantioselective transfer hydrogenation of racemic /3-keto gamma-lactams via dynamic kinetic resolution using a chiral Ru(II) catalyst has been developed for the synthesis of optically active /3-hydroxyl lactams with excellent conversion (up to 99 %), high diastereomeric ratio (dr dr 93:07) and enantiomeric selectivity (89 % ee ). The reaction proceeded by using HCO2H/Et3N 2 H/Et 3 N as hydrogen donor and features mild, additive free reaction conditions, fast crystallization, broad substrate scope, and an operationally simpler setup than that for molecular hydrogenation.
Keywords: (R)-1-((R)-Pyrrolidin-3-yl)ethan-1-ol; /3-keto gamma-lactams; Asymmetric transfer hydrogenation; Dynamic kinetic resolution; Fluroquinolone antibiotics

Safety enhanced novel polymer electrolytes for lithium-ion battery: Anomalous output performance with long term cycling stability by doping and polymer blending - Balakrishnan, Neethu T. M.; Melepurakkal, Amrutha; Das, Akhila; Kenz, K. T. Mohammed; Subramaniam, Mohanapriya; Shelke, Manjusha; Pullanchiyodan, Abhilash; Raghavan, Prasanth (MATERIALS TODAY CHEMISTRY, 2024)
Keywords: Blend polymers; Ceramic fillers; Gel polymer electrolytes

Simultaneously mechanically flexible, photobending, and acidochromic cyanostilbene molecular crystals - Parthasarathy, Thiyagaraj; Mishra, Manish Kumar; Bhattacharya, Biswajit; Emmerling, Franziska; Ghosh, Soumyajit (Crystal Growth & Design, 2024)
Molecular crystals that respond to multiple stimuli are gaining significant attention for their potential in smart materials like actuators and sensors. However, imparting multiple stimuli-responsive properties to a single crystal remains a major challenge. Herein, we report two cyanostilbene derivative-based crystals 1 and 2, with various responses to stimuli such as mechanical stress, light, acid vapors, etc. Both crystals 1 and 2 demonstrated mechanical flexibility and reversible acidochromism. Additionally, crystal 1 also exhibited light-induced photobending, which is ascribed to Z to E photoisomerization. Detailed structure-property correlation was established to unravel distinct mechanical responses. The development of these multitasking crystals may find applications in multitasking actuators, anticounterfeiting materials, and more.

Solution-phase ligand engineering for all-quantum-dot near-infrared light-emitting diodes - Biswas, Arindam; Mitra, Anurag; Sharma, Ashish; Shinde, Dipak Dattatray; Dambhare, V. Neha; Sharma, Anjali; Mahajan, Chandan; Rath, Arup K. (ACS Applied Nano Materials, 2024)
Strong emission over a wide near-infrared (NIR) region makes lead sulfide quantum dots (QDs) a preferred material in building NIR light-emitting diodes (NIR-LEDs) for numerous applications. Narrow-bandgap emitter QDs blended in the matrix of high-band gap QDs offer a simple yet powerful architectural platform for building high-performance NIR-LEDs. So far, the all-QD-based blend architecture has been realized using a poorly controlled solid-state ligand exchange approach. Advanced solution-phase ligand exchange, which offers greater control over surface passivation, is yet to be realized in all-QD LED device construction. We observe that the solution-phase ligand exchange from the optimized lead halide and thiol ligand combination, used in high-performing QD solar cell construction, is inefficient in realizing efficient all-QD LEDs, which could have restricted the adoption of the solution-phase ligand exchange thus far. Here, we introduce an innovative dual-ligand strategy to build all-QD-based NIR-LEDs using an advanced solution-phase ligand exchange approach. Through ligand engineering of matrix QDs, we managed to improve photoluminescence quantum yield (40%), reduce trap density (10(14) cm(-3)), and prolong carrier lifetime (832 ns). The LED devices benefit from improved electronic properties and balanced carrier injection to yield 6% EQE and 7.7% PCE, which are six times higher than those of state-of-the-art ligands.
Keywords: electroluminescence; lead sulfide; ligand passivation; light-emitting diodes; near-infrared; quantumdots

Static and dynamic properties investigation of modified polyethersulfone membrane for direct methanol fuel cell applications - Shah, Mumtaj; Mesfer, Mohammed K. Al; Nagar, Harsha (JOURNAL OF POWER SOURCES, 2024)
Keywords: Cross-link membranes; Direct methanol fuel cell; Molecular modelling

Structural basis for a two-dimensional flexible pharmaceutical solvate crystal: indomethacin methanol - Bhowmik, Aritra; Bamane, Sanjivani; Mishra, Manish Kumar (CrystEngComm, 2024)
We report the first two-dimensionally (2D) elastically bendable and twistable pharmaceutical-solvate crystal, indomethacin methanol. Its flexibility is due to interlocked packing and a structural buffer acting like isotropic interactions. For the first time, we utilized Raman spectroscopy on the two elastic faces of a bent crystal region, revealing the inhomogeneous molecular distribution in the crystal structure during bending and validating the mechanistic model of the 2D elastic crystal. We present the first 2D elastic pharmaceutical-solvate crystal and utilized Raman spectroscopy to reveal inhomogeneous lattice distribution during bending.

Surface electronic properties-driven electrocatalytic nitrogen reduction on metal-conjugated porphyrin 2D-MOFs - Maibam, Ashakiran; Orhan, Ibrahim B.; Krishnamurty, Sailaja; Russo, Salvy P.; BabaRao, Ravichandar (ACS Applied Materials and Interfaces, 2024)
Two-dimensional (2D) metal organic framework (MOF) or metalloporphyrin nanosheets with a stable metal-N-4 complex unit present the metal as a single-atom catalyst dispersed in the 2D porphyrin framework. First-principles calculations on the 3d-transition metals in M-TCPP are investigated in this study for their surface-dependent electronic properties including work function and d-band center. Crystal orbital Hamiltonian population (-pCOHP) analysis highlights a higher contribution of the bonding state in the M-N bond and antibonding state in the N-N bond to be essential for N-N bond activation. A linear relationship between Delta G(max) and surface electronic properties, N-N bond strength, and Bader charge has been found to influence the rate-determining potential for nitrogen reduction reaction (NRR) in M-TCPP MOFs. 2D Ti-TCPP MOF, with a kinetic energy barrier of 1.43 eV in the final protonation step of enzymatic NRR, shows exclusive NRR selectivity over competing hydrogen reduction (HER) and nitrogenous compounds (NO and NO2). Thus, Ti-TCPP MOF with an NRR limiting potential of -0.35 V in water solvent is proposed as an attractive candidate for electrocatalytic NRR.
Keywords: Density Functional Theory (DFT); electrocatalytic nitrogen reductionreaction; kinetic energy barrier; limitingpotential; Metalloporphyrin; NRR selectivity

Switchable molecular electrocatalysis - Dutt, Shifali; Kottaichamy, Alagar Raja; Dargily, Neethu Christudas; Mukhopadhyay, Sanchayita; Nayak, Bhojkumar; Devendrachari, Mruthyunjayachari Chattanhali; Vinod, Chatakudhath Prabakaran; Kotresh, Harish Makri Nimbegondi; Thotiyl, Musthafa Ottakam (CHEMICAL SCIENCE, 2024)
Keywords: CO2 reduction; COBALT PHTHALOCYANINE; NANOPOROUS GOLD; oxygen reduction

Synergistic effects of the substrate-ligand interaction in metal-organic complexes on the de-electronation kinetics of a vitamin C fuel cell - Parmar, Muskan; Mukhopadhyay, Sanchayita; Mondal, Ritwik; Nayak, Bhojkumar; Dargily, Neethu Christudas; Kotresh, Harish Makri Nimbegondi; Vinod, Chathakudath Prabhakaran; Ottakam Thotiyl, Musthafa (Dalton Transactions, 2024)
The rising demand for portable energy conversion devices has spurred the advancement of direct liquid fuel cells (DLFCs) employing fuels such as alcohol, ammonia, hydrazine, and vitamin C. In these devices, various precious metal platforms have been explored to increase the de-electronation kinetics and reduce catalyst poisoning, but with substantial cost implications. We demonstrate the crucial role of ligands in non-precious organometallic complexes in influencing the de-electronation kinetics of fuel molecules through a unique substrate-ligand synergistic interaction. This unique chemistry imparts electron deficiency at the catalytic metal center while simultaneously populating the ligand with an extensive proton charge assembly. This distinct substrate-ligand interaction enhances the DLFC performance by coulombically dragging the substrate with a distinct amplification in its de-electronation kinetics. By integrating this approach with a ferricyanide/ferrocyanide half-cell reaction, a precious metal-free vitamin C fuel cell is developed, which is capable of generating an open circuit voltage of similar to 950 mV, a peak power density of similar to 97 mW cm-2 at a peak current density of similar to 215 mA cm-2 with the performance metrics nearly 1.7 times higher than a precious metal based DLFC. This highlights the potential of the substrate-ligand synergy in the design of efficient molecular catalysts for energy conversion applications. A precious metal-free biomass fuel cell through substrate-ligand interactions.

Synergistic humidity-responsive mechanical motion and proton conductivity in a cationic covalent organic framework - Das, Gobinda; Shinde, Dhanraj B.; Melapurakkal, Amrutha; Shelke, V, Manjusha; Garai, Bikash; Bazin, Philippe; Blal, Abdelhafid Ait; Benyettou, Farah; Prakasam, Thirumurugan; Halim, Rasha Abdul; Ibrahim, Fayrouzabou; Sharma, Sudhir Kumar; et al. (CHEM, 2024)
Keywords: ACTUATORS; Crystalline; DRIVEN; SOFT

Synthesis and antimicrobial evaluation of novel 2'-aryl-4-aryl-2,4'-Bisthiazole and 2'-aryl-4-Pyridyl-2,4'-bisthiazole derivatives as potential antibacterial agents - Nalawade, Jitendra; Shinde, Abhijit; Abhale, Yogita K.; Nandurkar, Yogesh; Bobade, Vivek D.; Sarkar, Dhiman; Mhaske, Pravin C. (Polycyclic Aromatic Compound, 2024)
In continuation of our research work to explore bisthiazole derivatives as potential antimicrobial agents, herein we reported the synthesis of a series of novel 2'-aryl-4-aryl-2,4'-bisthiazole (7a-t) and 2'-aryl-4-pyridyl-2,4'-bisthiazole (9a-l) by cyclocondensation of 2-aryl thiazole-4-carbothioamide 5a-d with 2-bromo-1-arylethanone (6a-e) and bromo-1-(pyridin-2/3/4-yl)ethanone (8a-c), respectively. These novel candidates were evaluated in vitro for their antibacterial potential against four pathogenic bacteria, Escherichia coli (NCIM 2576), Pseudomonas flurescence (NCIM 2059), Staphylococcus aureus (NCIM 2602), and Bacillus subtilis (NCIM 2162). The synthesized compounds were also screened for their in vitro antifungal activity against Candida albicans (NCIM 3100). Among them, compounds 7b, 9d, 9 g, 9i, and 9 l exhibited excellent antibacterial activity with MIC 2.1 to 12.3 mu g/mL against all tested strains. Most of the compounds reported moderate antifungal activity. The pyridine ring-substituted bisthiazole reported good to excellent antibacterial activity as compared to phenyl ring-substituted bisthiazole. The potential antibacterial activity suggested that bisthiazole derivatives could assist in the development of lead compounds to treat microbial infections.
Keywords: 24'-bisthiazole; antibacterial activity; Antifungal activity; cyclocondensation

Synthesis and processing strategy for high-bandgap PbS quantum dots: a promising candidate for harvesting high-energy photons in solar cells - Shinde, Dipak Dattatray; Sharma, Anjali; Dambhare, Neha V.; Mahajan, Chandan; Biswas, Arindam; Mitra, Anurag; Rath, Arup K. (ACS Applied Materials & Interfaces, 2024)
The wide tunability of the energy bandgap of colloidal lead sulfide (PbS) quantum dots (QDs) has uniquely positioned them for the development of single junction and tandem solar cells. While there have been substantial advancements in moderate and narrow bandgap PbS QDs-ideal for single junction solar cells and the bottom cell in tandem solar cells, respectively; progress has been limited in high-bandgap PbS QDs that are ideally suited for the formation of the top cell in tandem solar cells. The development of appropriate high bandgap PbS QDs would be a major advancement toward realizing efficient all-QD tandem solar cells utilizing different sizes of PbS QDs. Here, we report a comprehensive approach encompassing synthetic strategy, ligand engineering, and hole transport layer (HTL) modification to implement high-bandgap PbS QDs into solar cell devices. We achieved a greater degree of size homogeneity in high-bandgap PbS QDs through the use of a growth retarding agent and a partial passivation strategy. By adjusting the ligand polarity, we successfully grow HTL over the QD film to fabricate solar cells. With the aid of an interface modifying layer, we incorporated an organic HTL for the realization of high-performance solar cells. These solar cells exhibited an impressive open-circuit voltage of 0.824 V and a power conversion efficiency of 10.7%, marking a 360% improvement over previous results.
Keywords: charge transport; lead sulfide; ligand passivation; quantum dots; solar cell

Synthesis, crystal growth, physicochemical study of 1,3-dihexyl-2-me-thyl-1H-benzo[d]imidazol-3-ium bromide and in silico nonlinear optical property determination - Siddiqui, Zahir Ali; Gamidi, Rama Krishna; Sekar, Nagaiyan; More, Sandeep (Journal of Molecular Structure, 2024)
This study encompasses the synthesis and characterization of 1,3-dihexyl-2-methyl-1H-benzo[d]imidazol-3-ium bromide (DHBIB) using techniques such as NMR, IR, and HRMS. The study also explores the influence of different solvents, specifically water and acetonitrile, on the growth of single crystals. An intriguing observation is the transformation of crystal packing from orthorhombic to monoclinic when solvent conditions change, illustrating the pivotal role of the cation in controlling the crystal structure of DHBIB salts. The analysis of its electronic properties reveal a deep -lying LUMO (-3.73 eV), suggesting DHBIB's electron -accepting characteristics. Furthermore, the study records absorption maxima ( lambda max ) at 279 nm and 282 nm in various solvents, demonstrating that DHBIB lacks absorption in the visible range (400-800 nm), making it promising for non-linear optical (NLO) applications. Analysis of the natural bond orbital (NBO) stabilization energies 50.87, 42.12, and 45.33 kcal/mol along pi(C3-C4) -> pi*(C6-C8), pi(C3-C4) -> pi*(C10-C12), and pi (C10-C12) -> pi*(C6-C8) reveal a preference for intramolecular charge transfer in DHBIB. Enhanced first and second -order hyperpolarizabilities ( beta ; 13.47x10 -30 esu, gamma ; 75.36x10 - 36 esu) compared to benzimidazole and benzimidazolium salicylate salt further supports its potential for NLO applications.
Keywords: DHBIB; Hyperpolarizability; Monoclinic; NBO; Orthorhombic

Synthesis of benzofuran-6-carboxylic acid, an intermediate of lifitegrast with low-carbon footprints - Zade, Vishal M.; Athawale, Paresh R.; Kopperi, Harishankar; Mohan, S. Venkata; Reddy, D. Srinivasa (ACS SUSTAINABLE CHEMISTRY & ENGINEERING, 2024)
Keywords: benzofuran-6-carboxylicacid; dry eye disease; life cycle; lifitegrast; process development

Synthesis of Hofmann-based metal-organic frameworks incorporating a bis-pyrazole linker for various gas separations - Matthews, Brooke L.; Harvey-Reid, Nathan C.; Jangodaz, Elnaz; Scott, Victoria-Jayne; Polson, Matthew I. J.; Maibam, Ashakiran; BabaRao, Ravichandar; Telfer, Shane G.; Kruger, Paul E. (JOURNAL OF MATERIALS CHEMISTRY A, 2024)
Keywords: acetylene; C2H2/CH4; Ni; Purification; SPIN-CROSSOVER BEHAVIOR

Synthesis of Ti1-xWx solid solution MAX phases and derived MXenes for sodium-ion battery anodes - Ratzker, Barak; Favelukis, Bar; Baranov, Mark; Rathod, Yugal; Greenberg, Avia; Messer, Or; Goldstein, Dor A.; Upcher, Alexander; Ezersky, Vladimir; Maman, Nitzan; Biran, Ido; Natu, Varun; et al. (ADVANCED FUNCTIONAL MATERIALS, 2024)
Keywords: Behavior; CARBIDE MXENE; INTERCALATION MECHANISM; TI

Synthesized novel chromogenic reagent and sensor: detection and identification of dichlorvos - Gedam, Ashwin D.; Katiya, Manish M.; Dhonde, Madhukar G.; Ganorkar, Kapil S.; Thakare, Vijay J.; Mandlik, Prashant R.; Jadhao, Nitin L.; Gajbhiye, Jayant M.; Kumar, Ravi; Vaval, Nayana (Heliyon, 2024)
We developed a novel chromogenic reagent and sensor by selective approach, for the detection and identification of dichlorvos, which we tested with the thin layer chromatography method. For the first time, we reported in situ-generated glyoxal as a hydrolysis product, which then interacts with isoniazid to produce a yellow-colored cyclic compound. We used well-known spectroscopic techniques to confirm the chemical identity of the final product. We initially investigated the reaction using a variety of approaches, followed by attempts to establish the reaction mechanism using Density Functional Theory by Gaussian software.
Keywords: DFT analysis; Dichlorvos; Gloyxal; Hydrazone; Isoniazid

Synthetic layered double hydroxide on biodegradable support: an efficient adsorbent for defluoridation of water - Mayadevi, S.; Kirandas, M. D.; Manilal, A. M.; Roshini, N.; Mandal, Sujata (Indian Journal of Chemical Technology, 2024)
Fluoride concentrations in drinking water above permissible levels and incidences of fluorosis among people have been reported from many parts of the world including India. Low-cost and biodegradable adsorbents are the preferred choice for the removal of fluoride from an aqueous medium. In the present study, zinc-aluminium layered double hydroxide (LDH) supported on sugarcane bagasse (raw and acid-treated) has been synthesized, characterized, and investigated for the defluoridation of water. The SEM micrographs of the supported adsorbents show good dispersion of the LDH particles on the support material. The defluoridation capacity of the LDH is enhanced by supporting it on bagasse. The adsorption capacity of supported adsorbents increased by 3-fold than the unsupported LDH adsorbent. The adsorption data have been well fitted to the Freundlich isotherm model indicating physical and multi-layer adsorption. The maximum fluoride adsorption capacity has been found to be 8.85 mg/g with 76.3% fluoride removal when the initial fluoride concentration is 11-12 mg/L. The pseudo-second-order kinetic model has been found suitable to explain the fluoride adsorption kinetics on the supported LDH adsorbents. The present study reveals that the bagasse-supported LDH adsorbent has a high potential for defluoridation of water.
Keywords: adsorption kinetics; Fluoride adsorption; Layered double hydroxide; Sugarcane bagasse

Systemic review on fitness and survival of salmonella in dynamic environment and conceivable ways of its mitigation - Sutar, Ajit A.; Dashpute, Rohit S.; Shinde, Yashodhara D.; Mukherjee, Srestha; Chowdhury, Chiranjit (Indian Journal of Microbiology, 2024)
Gastroenteritis caused by non-typhoidal Salmonella still prevails resulting in several recent outbreaks affecting many people worldwide. The presence of invasive non-typhoidal Salmonella is exemplified by several characteristic symptoms and their severity relies on prominent risk factors. The persistence of this pathogen can be attributed to its broad host range, complex pathogenicity and virulence and adeptness in survival under challenging conditions inside the host. Moreover, a peculiar aid of the ever-changing climatic conditions grants this organism with remarkable potential to survive within the environment. Abusive use of antibiotics for the treatment of gastroenteritis has led to the emergence of multiple drug resistance, making the infections difficult to treat. This review emphasizes the importance of early detection of Salmonella, along with strategies for accomplishing it, as well as exploring alternative treatment approaches. The exceptional characteristics exhibited by Salmonella, like strategies of infection, persistence, and survival parallelly with multiple drug resistance, make this pathogen a prominent concern to human health.
Keywords: Antibiotic resistance; Gastroenteritis; Non-typhoidal Salmonella; pathogenesis; Plant-derived metabolites; Salmonella pathogenicity islands; Type III secretion system

Temperature-controlled hydrothermal synthesis of α-MnO2 nanorods for catalytic oxidation of cyclohexanone - Jha, Ratnesh Kumar; Manikandan, Marimuthu; Prabu, Marimuthu; Vineeth, Nidhi R.; Dharmalingam, Praveen; Archana, Ramakrishnan; Harsha, Murudappa; Shankar, Sonu Ram; Bhatte, Kushal; Raja, Thirumalaiswamy (CHEMPLUSCHEM, 2024)
Keywords: Adipic Acid; conversion; MANGANESE OXIDES

Template-asisted visible light-induced [2+2] photodimerization in a pseudopolymorphic binary solid: topotactic transformation vs photoinduced crystal melting - Ahsan, Mollah Rohan; Varma, Harshit; Mishra, Manish Kumar; Mukherjee, Arijit (CRYSTAL GROWTH & DESIGN, 2024)
Keywords: CATION-PI INTERACTIONS; SINGLE-CRYSTAL; STATE PHOTODIMERIZATION; Supramolecular

Total synthesis and revision of stereochemistry of a natural benzo[g]isochromene stereodiad isolated from rubia philippinensis - Choudhury, Rahul; Miriyala, Satya Ravi Teja; Resmi, K. R.; Sridhar, Balasubramanian; Kasa, S. R. Krishna Murthy; Reddy, D. Srinivasa (Organic Letters, 2024)
This study presents a total synthesis and revision of the stereochemical configuration of the conformationally flexible natural product benzo[g]isochromene stereodiad alongside its diastereomeric counterparts. The highlights of the synthesis are the TiCl4-mediated diastereoselective aldol reaction, Pd-catalyzed lactonization, and Schmidt glycosidation. Our efforts using total synthesis disclosed herein proved that a previously assigned structure required revision.

Transfer semi-hydrogenation of terminal alkynes with a well-defined iron complex - Chowdhury, Deep; Goswami, Souvik; Krishna, Gamidi Rama; Mukherjee, Arup (Dalton Transaction, 2024)
The synthesis and characterization of a bis-iron(ii) complex was accomplished upon treatment of a phosphine free NNN-pincer ligand (L) with FeCl2 center dot 4H2O under ambient conditions. The deep greenish colored iron(ii) complex (Fe-1) was characterized by a single-crystal X-ray diffraction study along with IR spectroscopy, UV-Vis spectroscopy, mass spectrometry, and elemental analysis. The Fe-1 complex was tested for the transfer semi-hydrogenation of terminal alkynes to the corresponding alkenes through the dehydrogenation of dimethyl amine-borane. This procedure enables the conversion of various structurally different terminal alkynes to alkenes under mild conditions. Control experiments were performed to shed light on the possible intermediates generated during the present protocol. A bench stable iron(ii) complex with the pincer ligand backbone was synthesized and characterized. The well-defined iron complex was successfully utilized for the dehydrogenation of DMAB and subsequent transfer semi-hydrogenation of terminal alkynes.

Transient Electro-Graphitization of MOFs Affecting the Crystallization of Ruthenium Nanoclusters for Highly Efficient Hydrogen Evolution - Karim, Golam Masud; Patra, Amalika; Deb, Sujit Kumar; Upadhya, Hemanta; Das, Snehasish; Mukherjee, Priyam; Ahmad, Waleed; Barman, Narad; Thapa, Ranjit; Dambhare, V, Neha; Rath, Arup Kumar; Das, Jaysri; et al. (ADVANCED FUNCTIONAL MATERIALS, 2024)
Keywords: amorphous ruthenium; crystallization control; graphitic nanostructure

Trapping an elusive Fe(IV)-superoxo intermediate inside a self-assembled nanocage in water at room temperature - Gera, Rahul; De, Puja; Singh, Kundan K.; Jannuzzi, Sergio A. V.; Mohanty, Aisworika; Velasco, Lucia; Kumar, Pankaj; Marco, J. F.; Nagarajan, Kalaivanan; Pecharroman, Carlos; Rodriguez-Pascual, P. M.; DeBBeer, Serena; et al. (JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2024)
Keywords: CATALYTIC EPOXIDATION; DIOXYGEN ACTIVATION; NONHEME IRON; X-RAY-ABSORPTION

Trehalase inhibition in Helicoverpa armigera activates machinery for alternate energy acquisition - Tellis, Meenakshi; Mohite, Sharada; Joshi, Rakesh (JOURNAL OF BIOSCIENCES, 2024)
Keywords: Energy metabolism; glucose; Metabolomics; Transcriptomics; trehalase; validamycin A