Intrinsic charge polarization in Bi19S27Cl3 nanorods promotes selective C-C coupling reaction during photoreduction of CO2 to ethanol - Das, Kousik; Das, Risov; Riyaz, Mohd; Parui, Arko; Bagchi, Debabrata; Singh, Ashutosh Kumar; Singh, Abhishek Kumar; Vinod, Chathakudath P.; Peter, Sebastian C. (Advanced Materials, 2023)
Obtaining multi-carbon products via CO2 photoreduction is a major catalytic challenge involving multielectron-mediated C-C bond formation. Complex design of multicomponent interfaces that are exploited to achieve this chemical transformation, often leads to untraceable deleterious changes in the interfacial chemical environment affecting CO2 conversion efficiency and product selectivity. Alternatively, robust metal centers having asymmetric charge distribution can effectuate C-C coupling reaction through the stabilization of intermediates, for desired product selectivity. However, generating inherent charge distribution in a single component catalyst is a difficult material design challenge. Here, a novel photocatalyst, Bi19S27Cl3, is presented which selectively converts CO2 to a C-2 product, ethanol, in high yield under visible light irradiation. Structural analysis through transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy reveals the presence of charge polarized bismuth centers in Bi19S27Cl3. The intrinsic electric field induced by charge polarized bismuth centers renders better separation efficiency of photogenerated electron-hole pair. Furthermore, charge polarized centers yield better adsorption of CO* intermediate and accelerate the rate determining C-C coupling step through the formation of OCCOH intermediate. Formation of these intermediates is experimentally mapped by in situ Fourier-transform infrared spectroscopy and further confirmed by theoretical calculation.
Keywords: C-C coupling; charge polarization; CO2 reduction; Ethanol; Photocatalysis

Investigation of Al2O3 induced variations in the structural parameters in strontium borosilicate glasses using solid state NMR - Illath, Kavya; Ojha, Prasanta K.; Rath, Sangram K.; Ajithkumar, T. G. (Physical Chemistry Chemical Physics, 2023)
The physical properties of oxide glasses are crucially dependent on the atomistic structural speciation. In this study, we investigate the variation in the local ordering in the glass network of strontium borosilicate glasses (34.82 SrO, 51.84 B2O3, 13.34 SiO2 in mol%) with a progressive substitution of B2O3 by Al2O3 and estimate the structural parameters: the oxygen packing fraction, and the average network coordination number. The coordination of the network forming cations at various glass compositions is determined using B-11, Al-27, and Si-29 solid-state nuclear magnetic resonance (SSNMR). The SSNMR reveals that at the higher substitution of B2O3 by Al2O3 in the glass composition, the coordination network of Al3+ exists predominantly in the 4 coordinated state, the network forming B3+ cations transform from a tetrahedral BO4 to a trigonal BO3 structure, and the Q(4) form of silicates is dominant. The average coordination number and the oxygen packing fraction were calculated using the parameters obtained from the SSNMR results, and it is observed that the average coordination number decreases, and the oxygen packing fraction increases on incorporating Al. It is interesting to note that some of the thermophysical properties of these compositions closely follow the pattern shown by the average coordination number and the oxygen packing fraction.

Lead-free solid state mechanochemical synthesis of Cs2NaBi1-XFeXCl6 double perovskite: reduces band gap and enhances optical properties - Udavant, Rohini; Thawarkar, Sachin; Rondiya, Sachin; Shelke, Ankita; Aher, Rahul; Ajithkumar, Thalasseril G.; Cross, Russell W.; Dzade, Nelson Y.; Jadkar, Sandesh (Inorganic Chemistry, 2023)
Efficient and stable lead-free halide double perovskites (DPs) have attracted great attention for the future generation of electronic devices. Herein, we have developed a doping approach to incorporate Fe3+ ions into the Cs2NaBiCl6 crystal unit and reveal a crystallographic and optoelectronic study of the Cs2NaBi1-xFexCl6 double perovskite. We report a simple solid-state mechanochemical method that has a solvent-free, one-step, green chemistry approach for the synthesis of Cs2NaBi1-xFexCl6 phosphor. The analysis of powder X-ray diffraction (XRD) data determines the contraction of the lattice due to the incorporation of Fe3+ cations, and this effect is well supported by X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), Raman spectroscopy, and solid-state nuclear magnetic resonance spectroscopy (ss-NMR). The band gap is reduced with increasing Fe content owing to the strong overlap of the Fe-3d orbitals with Cl-3p orbitals and shift of the valence band maxima (VBM) toward higher energies, as confirmed by ultraviolet photoelectron spectroscopy (UPS) and density functional theory (DFT) analyses. Photoluminescence (PL) studies of Cs2NaBi1-xFexCl6 phosphors exhibit a large Stokes shift, broadband emission, and increased PL intensity more than ten times for 15% of Fe content phosphor with enhancement in the average decay lifetimes (up to 38 ns) compared to pristine Cs2NaBiCl6 DP. These results indicate that the transition of dark self-trapping of excitons (STEs) into bright STEs enhances yellow emission. XRD, UV, and thermo-gravimetric analysis (TGA) confirmed that the Cs2NaB1-xFexCl6 DPs have good structural and thermal stabilities. Our findings indicate that the doping of Fe3+ cations into the Cs2NaBiCl6 lattice is a constructive strategy to enhance significantly the optoelectronic properties of these phosphors.

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

Mapping time dependent disulfide bond formation during in-vitro refolding of recombinant peptibody: a Fc-fusion protein - Kumthekar, Rupali; Rana, Sunil; Ughade, Santosh; Bhambure, Rahul (Biochemical Engineering Journal, 2023)
Disulfide bonds are commonly found in covalent interactions, which play a vital role in establishing the three-dimensional structure of proteins and maintaining their biological activity. This investigation is focused on time dependant mapping of intra and inter-disulfide bonds during in-vitro refolding of recombinant peptibody using LC-ESI-MS/MS. The selected recombinant peptibody is a homodimeric, aglycosylated Fc-fusion protein expressed in E. coli. The amino acid sequence in the disulfide bond containing peptides was confirmed at MS/MS level using the CID-based fragmentation approach. During in-vitro refolding of peptibody, a peptide with inter -chain disulfide bond is observed post 4 h, with low area intensity, and it reached a maximum in 96 h. How-ever, maximum area intensity was reached for the intra-chain disulfide bond in 72 h. Since cysteine residues responsible for intra-chain disulfide bonds are present in complex part of the Fc domain, formation of intra-chain disulfide bonds may be an overall rate-limiting step in recombinant Romiplostim refolding. Proper folding and contributions by non-covalent interactions will be required to form intra-chain disulfide bond. Monitoring time -based formation of such non-covalent interactions was carried out using intrinsic fluorescence during protein refolding. Observations from intrinsic fluorescence show that 4-6 h is most crucial time for domain formation. Observations from this study will help characterize structural integrity and quality during process and product development for consistent product quality.
Keywords: Disulfide bond formation; In -vitro refolding; Intrinsic fluorescence; Mass spectroscopy; Peptibody; Time based mapping

Mechanistic insights on anserine hydrolyzing activities of human carnosinases - Pandya, Vaibhav Kumar; Shankar, S. Shiva; Rajesh, S.; Rathore, Rajeshwari; Kumaran, Sangaralingam; Kulkarni, Mahesh J. (Biochemica ET Biophysica Acta- General Subjects, 2023)
Anserine and carnosine represent histidine-containing dipeptides that exert a pluripotent protective effect on human physiology. Anserine is known to protect against oxidative stress in diabetes and cardiovascular diseases. Human carnosinases (CN1 and CN2) are dipeptidases involved in the homeostasis of carnosine. In poikilothermic vertebrates, the anserinase enzyme is responsible for hydrolyzing anserine. However, there is no specific anserine hydrolyzing enzyme present in humans. In this study, we have systematically investigated the anserine hydrolyzing activity of human CN1 and CN2. A targeted multiple reaction monitoring (MRM) based approach was employed for studying the enzyme kinetics of CN1 and CN2 using carnosine and anserine as substrates. Surprisingly, both CN1 and CN2 can hydrolyze anserine effectively. The observed catalytic turnover rate (Vmax/[E]t) was 21.6 s-1 and 2.8 s-1 for CN1 and CN2, respectively. CN1 is almost eight-fold more efficient in hydrolyzing anserine compared to CN2, which is comparable to the efficiency of the carnosine hydrolyzing activity of CN2. The Michaelis constant (Km) value for CN1 (1.96 mM) is almost three-fold lower compared to CN2 (6.33 mM), representing higher substrate affinity for anserine-CN1 interactions. Molecular docking studies showed that anserine binds at the catalytic site of the carnosinases with an affinity similar to carnosine. Overall, the present study elucidated the inherent promiscuity of human carnosinases in hydrolyzing anserine using a sensitive LCMS/MS approach.
Keywords: Anserine; Carnosinase; Carnosine; Diabetes; LC-MS; MS; Multiple reaction monitoring (MRM); Promiscuity

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.

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

Multipurpose cellulases of Promicromonospora sp. VP111, with broad substrate specificity and tolerance properties - Thomas, Lebin; Ram, Hari; Singh, Ved P. (Journal of Basic Microbiology, 2023)
Cellulolytic actinobacterium, Promicromonospora sp. VP111 concomitantly produced cellulases (CELs), xylanase and pectinase when grown on commercial cellulose and untreated agricultural lignocellulosic residues (wheat straw and sugarcane bagasse). Secreted CELs hydrolyzed (enhanced with Co2+ ion) multiple cellulosic substrates, including sodium carboxymethyl cellulose (Na-CMC), Whatman filter paper no. 1, microcrystalline cellulose (avicel), p-nitrophenyl-beta-D-glucopyranoside (pNPG), laminarin, and cellulose powder. The CELs showed stabilities in the presence of various chemicals, including glucose (0.2 M), detergents (1%, w/v or v/v), denaturants (1%, w/v or v/v), and sodium chloride (NaCl, 30%, w/v). The CELs were fractionated using ammonium sulfate precipitation and dialysis. Activities (%) of fractionated CELs were retained at 60 degrees C for endoglucanase/carboxymethyl cellulase (CMCase) (88.38), filter paper cellulase (FPase) (77.55), and beta-glucosidase (90.52), which indicated of thermo-stability. Similarly, the activities (%) for CMCase (85.79), FPase (82.48), and beta-glucosidase (85.92) at pH 8.5 indicated of alkaline-stability. Kinetic factors, K-m and V-max for endoglucanase component of fractionated CELs were 0.014 g/l and 158.23 mu M glucose/min/mL, respectively. Fractionated CELs yielded activation energies (kJ/mol) of 17.933, 6.294, and 4.207 for CMCase, FPase, and beta-glucosidase activities, respectively in linear thermostable Arrhenius plots. Thus, this study reports on the multipurpose CELs from an untreated agricultural residue utilizing Promicromonospora in relation to broad substrate specificity, halo-tolerance, alkaline-tolerance, detergent-tolerance, thermo-tolerance, organic solvent-tolerance, and end product-tolerance.
Keywords: cellulases; cellulose; Endoglucanase; Lignocellulose; Promicromonospora sp; VP111

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

Nitric acid free cyclohexane to adipic acid production using nickel and vanadium incorporated AlPO-5 molecular sieve - Prabu, Marimuthu; Sharma, Shweta; Raja, Abhishekram; Archana, Ramakrishnan; Samruddhi, Mane; Raja, Thirumalaiswamy (Molecular Catalysis, 2023)
Rationally designing a stable and sustainable metal oxide supported over the molecular sieve catalysts for oxidizing cyclohexane (CYH) to adipic acid (AA) is vital in industrial applications. The in-situ hydrothermal synthesis method successfully incorporated vanadium and nickel into the aluminium phosphate-5 (AlPO-5) molecular sieves (MFI structure). The XPS and NH3 TPD analysis disclosed that the addition of Ni into V-AlPO-5 stabilizes the ratio of V4+/V5+, creating strong acidic sites and the formation of NiOOH, which are a vital role for the selective CYH oxidation to AA. An in-situ DRIFT study reveals that nickel takes part in the formation of dicarboxylate ions as an intermediate to form AA. Our catalytic studies profoundly suggested that the Ni0.1V0.2AlPO-5 catalyst used for CYH oxidation gives better selectivity towards AA (53%) in the presence of oxygen at an appropriate amount of solvent without an initiator or promoter within a short time (3h).
Keywords: Adipic Acid; Cyclohexane oxidation; In situ DRIFT; NiOOH; NiVAlPO-5; Ratios ofV4+; V5+

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

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

Novel shear thickening fluids possessing high shear rates using monodispersed silica nanoparticles and PEG - Chavan, Nayaku; Dhage, Atul; Wale, Apparav; Thorave, Asmita; Rajdeo, Kishor; Kamble, Sanjay; Ponrathnam, Surendra; Tambe, Sanjeev; Verma, Sanjeevkumar (Polymer Bulletin, 2023)
Higher shear rate possessing homogeneous shear thickening fluids were synthesized using monodispersed silica nanoparticles and polyethylene glycol (PEG). Novel homogeneous methodology was developed for the synthesis of shear thickening fluids using monodispersed silica nanoparticles and PEG. Shear rate of shear thickening fluids (STF) was determined using rheometer at room temperature. The normal shear rate was observed in the range of 100 to 1200 s(-1), whereas higher shear rate 2000 s(-1) was obtained using monodispersed silica nanoparticles, PEG and shear rate enhancer. Monodispersed silica nanoparticles were synthesized in a typical one-pot using modified Stober's method at room temperature. Precursors were used for the synthesis of monodispersed silica nanoparticles such as tetraethyl orthosilicate (TEOS), ethanol, deionized water and ammonia as catalyst. Particle size of monodispersed silica nanoparticles was in the range of 100-1200 nm, and particle size distribution was varied from 0.000 to 0.221. Synthesis of monodispersed silica nanoparticles was studied by various parameters, namely effect of TEOS concentration, grade of ethyl alcohol, ammonia concentration and water concentration. TEOS concentration effect shows particle size and particle size distribution increases with increase in concentration of TEOS. Even though concentration of TEOS was increased up to 5 times the observation was same for all particle sizes such as 100, 300 and 500 nm. Particularly in the case of 300 nm monodispersed silica nanoparticle synthesis, as TEOS concentration was increased from 1 to 5X (5 times) the particle size was increased from 331.7, 447.8, 497.0, 512.0 and 531.7 nm and particle size distribution was 0.005, 0.000, 0.006, 0.007 and 0.089, respectively. The effect of grade of ethyl alcohol illustrates that Indian rectified spirit shows almost similar results with respect to China make ethyl alcohol. Comparative study of China and Indian rectified spirit shows silica nanoparticle size was 174.6 and 174.2 nm, and particle size distribution was 0.065 and 0.071, respectively. Ammonia concentration effect explains particle size and particle size distribution increases with increase in concentration of ammonia. Water concentration effect shows particle size and particle size distribution increases with increase in concentration of ammonia. Comparative data of water concentration effect for 1316 and 1974 mL shows particle size were 321.7 and 488.0 nm, and particle size distribution was 0.083 and 0.05, respectively, under similar conditions. Morphological studies displayed the shape of the silica nanoparticles was spherical, monodispersed and isolated. A typical TEM image of monodispersed silica nanoparticles for 500 nm was observed with extremely low polydispersity, i.e., 0.000. It is very difficult to get such a type of excellent photograph of monodispersity by Stober's method particularly on large scale. Rheology study of homogeneous shear thickening fluids studied by varying the parameters such as composition of silica nanoparticles with PEG, effect of amount of solvent, effect of refluxing time, effect of additive with respect to the mol. wt. of PEG and effect of additive such as Tannin. All these parameters of STF explored with respect to the shear rate and shear viscosity. Effect of ethanol amount on STF demonstrates the shear rate increases with increase in amount of solvent. Effect of refluxing time on STF exhibits the shear rate increases with increase in refluxing time. Effect of composition based on 500 nm monodispersed silica nanoparticles and PEG 200 with respect to 60:40, 65:35 and 70:30 composition was studied and the results predict that shear rate increases with increase in silica percentage in composition, i.e., 118, 265 and 1200 s(-1) for 60:40, 65:35 and 70:30 composition, respectively, whereas maximum viscosity decreases with increase in silica content, i.e., 2.559, 1.420 and 1.200 Pa.s for 60:40, 65:35 and 70:30 composition, respectively. Effect of additive on shear rate and shear viscosity illustrates that shear rate decreases with increase in additive percentage in composition, whereas maximum viscosity increases with increase in additive content. Effect of additives on shear rate and shear viscosity was performed using 65:35 composition with respect to PEG 200 along with PEG 6000 shows shear rate was decreased from 142 to 6.42 s(-1) and maximum viscosity was increased from 56.1 to 571.0 Pa.s when the quantity of PEG 6000 was doubled. In general, additive decreases shear rate and increases shear viscosity (maximum). But effect of Tannin as an additive on 500 nm monodispersed silica nanoparticles with PEG 200 using 70:30 composition showed enormous increase in shear rate, i.e., 2000 s(-1). This is anomalous behavior of additive was observed.
Keywords: Monodispersed silica nanoparticles; Nanocomposite; Polyethylene glycol; Shear rate; Shear thickening fluid

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

Oxidation of ethylene by Cu/TiO2: reducibility of Cu2+ in TiO2 as a possible descriptor of catalytic efficiency - Rajendran, K.; Sharma, Mandeep; Jaison, Augustine; Ankitha, Menon; Tiwari, Ankit D.; Vinod, C. P.; Jagadeesan, Dinesh (Catalysis Science & Technology, 2023)
Catalytic oxidation using non-noble metal-based catalysts is a promising approach to mitigate pollution due to VOCs in the air. In this work, mesoporous Cu/TiO2 catalysts containing different concentrations of Cu2+ (0.2, 1, 3, and 4 wt% Cu w.r.t. Ti) were synthesized using the sol-gel technique. The catalysts were characterized using inductively coupled plasma-optical emission spectrometry, XRD, Raman spectroscopy, N-2 physisorption, cyclic voltammetry, H-2-TPR and electron microscopy to understand the structure and composition. The thermal catalytic gas phase oxidation of ethylene was studied by heating a mixture of ethylene (1.5 vol%) and air (5.9 vol%) in the presence of the Cu/TiO2 samples in the temperature range of 298 to 773 K. Cu/TiO2 showed a higher catalytic activity compared to TiO2 for the thermal oxidation of ethylene, indicating a strong promotion by doped copper ions. A volcanic behaviour in the catalytic activity was observed with different concentrations of Cu doping, with 1% Cu/TiO2 showing a 99.5% ethylene conversion at 673 K and 100% selectivity to CO2. The activity of 1% Cu/TiO2 remained consistent without deactivation for 24 h. At low dopant concentrations of Cu (0.2 and 1% Cu/TiO2), the reduction of Cu2+ to Cu+ was observed. An interplay of oxygen vacancies (O-V), Cu+, Cu2+ and Ti4+ may be involved in controlling the activity. DRIFT studies indicated the formation of surface bidendate carbonate as a possible intermediate.

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

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

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

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

Physiologically-based pharmacokinetic model for tuberculosis drug disposition at extrapulmonary sites - Ramachandran, Aparna; Gadgil, Chetan J. (CPT-Pharmacometrics & Systems Pharmacology, 2023)
Tuberculosis (TB) is a leading cause of mortality attributed to an infectious agent. TB primarily targets the lungs, but in about 16% cases can affect other organs as well, giving rise to extrapulmonary TB (EPTB). However, an optimal regimen for EPTB treatment is not defined. Although the recommended treatment for most forms of EPTB is the same as pulmonary TB, the pharmacokinetics of EPTB therapy are not as well studied. To address this gap, we formulate a whole-body physiologically-based pharmacokinetic (PBPK) model for EPTB that for the first time includes the ability to simulate drug concentrations in the pleura and lymph node, the most commonly affected sites of EPTB. Using this model, we estimate the time-dependent concentrations, at potential EPTB infection sites, of the following four first-line anti-TB drugs: rifampicin, ethambutol, isoniazid, and pyrazinamide. We use reported plasma concentration kinetics data to estimate model parameters for each drug and validate our model using reported concentration data not used for model formulation or parameter estimation. Model predictions match the validation data, and reported pharmacokinetic parameters (maximum plasma concentration, time to reach maximum concentration) for the drugs. The model also predicts ethambutol, isoniazid, and pyrazinamide concentrations in the pleura that match reported experimental values from an independent study. For each drug, the predicted drug concentrations at EPTB sites are compared with their critical concentration. Simulations suggest that although rifampicin and isoniazid concentrations are greater than critical concentration values at most EPTB sites, the concentrations of ethambutol and pyrazinamide are lower than their critical concentrations at most EPTB sites.

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

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

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

Potential role of lewis acid-base adducts in enhancing stereoselectivity in ziegler-natta catalysts: a DFT study - Raj, K. Vipin; Gupta, Virendra Kumar; Vanka, Kumar (Journal of Physical Chemistry C, 2023)
Ziegler-Natta (Z-N) systems have been well established as heterogeneous catalysts that produce isotactic polypropylene and polyethylene with great efficiency. Such systems benefit considerably from donors (Lewis bases), whose addition significantly improves the stereoselectivity of polymerization. There is a consensus that the primary role of the external donors is to coordinate at the vacant site created by the extraction of internal donors and thus maintain the stereoselectivity. However, the bite difference between internal donors such as phthalates or succinate derivatives and external donors such as alkoxysilanes raises the question of how external donors can effectively replace internal donors. In order to investigate this, we have chosen four external alkoxysilane donors: (1) diisopropyl dimethoxysilane, (2) dicyclopentyl dimethoxysilane, (3) disec-butyl dimethoxysilane, and (4) sec-butyl(methyl) dimethoxysilane. DFT studies reveal that the bite difference problem can be overcome by the favorable formation of adducts between the alkoxysilane external donors and AlEt2Cl in the Z-N systems. These adducts tend to coordinate in the vicinity of the active site. Furthermore, our findings demonstrate the potential of these Lewis acid-base adducts to enhance the stereoselectivity of Z-N catalysts significantly.

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

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

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

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.

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

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

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

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

Selective oxidation of 5-HMF to DFF over alkali promoted Mn nanocomposite - Solanki, Bhanupratap Singh; Roh, Hyun-Seog; V. Rode, Chandrashekhar (Applied Catalysis A-General, 2023)
Various compositions of Cs promoted Mn catalysts were synthesized and investigated for selective oxidation of 5HMF to DFF, among which Mn-Cs(80:20) was found to be most efficient giving 91 % conversion of 5-HMF and 99 % selectivity to DFF. Detail characterization like N2-sorption, BET surface area, TG-DTA, XRD, XPS, FE-SEM-EDX, TEM, HR-TEM, CO2-TPD, H2-TPR, O2-TPO, FTIR, Raman spectra and CH3OH-IR were done to establish structureactivity correlation. Enhanced surface area, porosity, thermal stability, dual morphologies were observed due to inclusion of Cs in Mn lattice domain which further enhanced the crystallinity, and oxygen diffusion on the surface. Mixed morphologies comprising nanoparticles (4-5 nm) and nanocubes (50-60 nm) were observed with enhanced redox potential and reduced work function due to weakening of Mn-O bonds. Significant increase in the basicity of catalyst, interfacial redox properties and lattice oxygen led to highly efficient oxidation of 5-HMF to DFF via Mars-van Krevelen mechanism at relatively milder conditions i.e. T = 90 degrees C and PO2= 200 psig. The catalyst was easily recyclable up to 7 times with minor loss in activity which was regenerated heat treatment protocol.
Keywords: 5-HMF; Biomass; heterogeneous catalyst; polyurethane; Selective oxidation

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

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

Squarate-tethered enantiomeric Imido-Pd(II) cages for recognition and separation of chiral organic molecules - Jose, Cavya; Sarkar, Meghamala; Rajasekar, Prabhakaran; Tewari, Tanuja; Boomishankar, Ramamoorthy (Inorganic Chemistry, 2023)
Chiral coordination cages have emerged as an efficient platform for enantioselective processes via host-guest interactions. Here, we report an enantiomeric pair of tetrahedral cages of formula [(Pd-3[PO(N(*CH(CH3)Ph)(3)])(4)(C4O4)(6)] supported by chiral tris(imido)phosphate trianions and squarate (C4O4)(2-) linkers. These cages exhibit unusual coordination isomerism for Pd(II)-linker bonds compared with the other Pd(II) cages of this family. Further, they were employed for the recognition and separation of small chiral molecules containing various functionalities. High enantioselectivities of 67 and 41 were found in the case of R-4-hydroxydihydrofuran-2(3H)-one and S-epichlorohydrin, recognized by the R-isomer of the cage. Chiral separation studies showed remarkable enantiomeric excess values of 93 and 85% for S-epichlorohydrin and R-4-benzyl-2-oxazolidinone, respectively, from their racemic mixtures. These studies showcase the potential of coordination cages for enantioselective applications.

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

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

Synthesis of Si(IV)- and Ge(II)-substituted amines, hydrazone, and hydrazine from hypersilyl germylene - Ajithkumar, V. S.; Ghanwat, Pratiksha B.; Raj, K. Vipin; Vanka, Kumar; Gonnade, Rajesh G.; Sen, Sakya S. (Organometallics, 2023)
This study investigates the reactivity of a hypersilyl germylene [PhC-(NtBu)(2)GeSi-(SiMe3)(3)] (1) with various organic compounds including azides, diazoalkanes, 1,2-diphenylhydrazine, and trifluoroacetophenone. The reactivity observed in these reactions is driven by the insertion of the organic fragment between a silicon and germanium bond. This leads to the formation of novel compounds, including an amine featuring three different substituents from three different elements of group 14. When reacting with Me3SiCHN2, we observed the insertion of the diazoalkane fragment in an end-on fashion into the Ge-Si bond. An analogous trend was observed in reactions with 1,2-diphenylhydrazine and trifluoroacetophenone, where the N-N and C-O fragments were inserted into the Ge-Si bond. Multinuclear NMR and single-crystal X-ray diffraction analyses were conducted to characterize the newly synthesized compounds.

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

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

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

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

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.

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

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

Total and diverted total synthesis of pyrrolo-quinazolinone alkaloids and their analogues - Rasapalli, Sivappa; Huang, Yanchang; Sammeta, Vamshikrishna Reddy; Alshehry, Reem; Anver, Fazmina; Shivasankar, Krishnamoorthy; Chavan, Subash P. (ChemistrySelect, 2023)
A short and expeditious total and diverted total synthesis of luotonin, vasicinone, and their analogues has been achieved from the key tricyclic quinazolinone intermediate which was accessed from simple substituted anthranilamide obtained from the coupling of & beta;-alanate with isatoic anhydride followed by Dieckmann condensation chemistry of the resulting diester. The tricyclic ketone exhibited interesting chemical properties, e. g. keto-enol tautomerism. Friedlander condensation and Fischer-Indolization were employed for further annulations to access polycyclic alkaloids and their analogues. A short and expeditious total and diverted total synthesis of Luotonin, Vasicinone, and their analogues has been achieved from the key tricyclic quinazolinone ketone that was accessed via Dieckmann condensation chemistry of the diester which was in turn obtained from the isatoic anhydride followed by cyclodehydration. The keto-enol tautomerism of the tricyclic ketone has been studied through 1H NMR. Friedlander condensation and Fischer-Indolization were employed for further annulations on to the tricyclic ketone to yield luotonins and nor-rutaecarpines in good yields.image
Keywords: Luotonin; Quinazolinone; Rutaecarpine; Total synthesis; Vasicinone

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

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

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

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

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

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

Wurtzite CuGaS2 with an in-situ-formed CuO layer photocatalyzes CO2 conversion to ethylene with high selectivity - Chakraborty, Subhajit; Das, Risov; Riyaz, Mohd; Das, Kousik; Singh, Ashutosh Kumar; Bagchi, Debabrata; Vinod, Chathakudath P.; Peter, Sebastian C. (Angewandte chemie-international edition, 2023)
We present surface reconstruction-induced C-C coupling whereby CO2 is converted into ethylene. The wurtzite phase of CuGaS2. undergoes in situ surface reconstruction, leading to the formation of a thin CuO layer over the pristine catalyst, which facilitates selective conversion of CO2 to ethylene (C2H4). Upon illumination, the catalyst efficiently converts CO2 to C2H4 with 75.1 % selectivity (92.7 % selectivity in terms of R-electron) and a 20.6 mu mol g(-1) h(-1) evolution rate. Subsequent spectroscopic and microscopic studies supported by theoretical analysis revealed operando-generated Cu2+, with the assistance of existing Cu+, functioning as an anchor for the generated *CO and thereby facilitating C-C coupling. This study demonstrates strain-induced in situ surface reconstruction leading to heterojunction formation, which finetunes the oxidation state of Cu and modulates the CO2 reduction reaction pathway to selective formation of ethylene.
Keywords: C-C coupling; charge polarization; CO2 reduction; Photocatalysis

Zwitterionic disilanylium from an unsymmetrical disilene - Bisai, Milan Kumar; Ajithkumar, V. S.; Raj, K. Vipin; Vanka, Kumar; Gonnade, Rajesh G.; Sen, Sakya S. (Chemical Communications, 2023)
The reaction of PhC(NtBu)2SiSi(SiMe3)(3) (1) with Me3SiCH(2)Cl afforded an unsymmetrical sp(2)-sp(3) disilene, 2, with concomitant elimination of Me3SiCl. The analogous reaction with PhC(NtBu)2SiCl resulted in the oxidative addition of the C-Cl bond at the Si(II) atom (3). The reactions of 2 with sulfur and selenium led to compounds with Si=E (E=S (4) and Se (5)) double bonds. Tellurium reacted differently with 2 and furnished a zwitterionic compound, 6.

Accessing meta -enone-substituted anisoles using ArN 2 BF 4 as precatalyst via rearrangement of alkyne-tethered cyclohexadienones - Rai, Archana; Das, Utpal (Synthesis-Stuttgart, 2024)
Keywords: alkyne-tethered cyclohexadienone; diazonium salt; rearrangement; substituted anisoles

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

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

Attempted synthesis of the central 2,2-disubstituted pseudoindoxyl core of Austamide via a [Au]-catalyzed nitroalkyne cycloisomerization and intramolecular [3+2]-cycloaddition - Halnor, Swapnil V.; Ramana, Chepuri V. (Tetrahedron, 2024)
Herein, we describe an Au-catalyzed cycloisomerization process of a nitroalkyne that was projected to construct the central 2,2-disubstituted pseudoindoxyl core of the natural product Austamide. Our intended strategy for forging the pseudoindoxyl core is based on the nitroalkyne cycloisomerization followed by a subsequent intramolecular [3 + 2] cycloaddition. However, the [3 + 2] cycloaddition occurred in an undesired manner, ultimately leading to a complex hexacyclic scaffold.
Keywords: Austamide; Gold catalysis; Intramolecular [3+2] cycloaddition; Nitroalkyne cycloisomerization

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.

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

Calcination temperature impacting the structure and activity of CuAl catalyst in aqueous glycerol hydrogenolysis to 1,2-propanediol - Mane, Rasika; Potdar, Aparna; Jeon, Yukwon; Rode, Chandrashekhar (Topics in Catalysis, 2024)
This study investigated the impact of calcination temperature on the structural properties of CuAl catalyst which was found to be a robust nano-structured catalyst calcined directly without ramping at 400 °C and performed exceedingly well for aqueous phase hydrogenolysis of glycerol. Various samples of CuAl catalysts were prepared by co-precipitation at Cu: Al molar ratio 1:1 and were calcined at different temperatures (300–1000 °C). The obtained catalysts were reduced at 200 °C before their activity testing for glycerol hydrogenolysis reaction. To correlate the structure-activity, the catalysts were thoroughly characterized by XRD, XPS, BET, TEM, H2-TPR, NH3-TPD, and pyridine FTIR. It was observed that with an increase in calcination temperature from 300 to 700 °C, the glycerol conversion also increased from 47 to 55% with 93% selectivity to 1,2-PDO. The better performance of these catalysts was mainly related to the predominant presence of Brønsted acid sites, an appropriate ratio of the Cu0 to CuAl2O4 + CuO (0.33) and CuAl2O4 to CuO phases (0.35), the existence of Cu2O phase and the smaller Cu0 particle size. It was shown that altering the ramping rate for the calcination temperature of 400 °C impacted the catalytic activity. The CuAl-400 (DC) (direct calcined) catalyst exhibited a maximum glycerol conversion of 60%.

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

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

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.

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

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

Dehydrogenative coupling of alcohols with internal alkynes under nickel catalysis: an access to β-deuterated branched ketones - Subaramanian, Murugan; Gouda, Chandrakant; Roy, Triptesh Kumar; Ganesan, Sivakumar; Banerjee, Subhrashis; Vanka, Kumar; Balaraman, Ekambaram (ACS Catalysis, 2024)
In synthetic organic chemistry, unconventional strategies for advanced chemical synthesis pose interesting and challenging problems. Alcohols act as alkylating agents in the C-C and C-N bond-forming reactions via the dehydrogenative borrowing hydrogen strategy in traditional transition metal catalysis; however, as an acylating agent in the C-C bond-forming reactions is challenging and rarely reported. Here, we report the dehydrogenative coupling of benzylic alcohols with internal alkynes under nickel(II) catalysis, wherein alcohol is used as an acylating agent. This reaction system affords a wide range of alpha-branched aryl ketone derivatives with zero waste generation through the umpolung borrowing hydrogen strategy. Moreover, we have demonstrated the chemodivergent applications of the alpha-disubstituted ketones to other valuable building blocks, including large-scale synthesis of beta-deuterated branched ketones. Several spectroscopic studies, intermediate identification, and density functional theory calculations were performed to elucidate the reaction mechanism.
Keywords: Alcohols; alpha-branched aryl ketones; dehydrogenative coupling; internal alkynes; nickel catalysis; pseudoumpolung

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

Design of 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.

Designing of imine thiophene-ligated metal-complexes and implication in ethylene polymerization - Shaikh, Maulali H.; Ramekar, V. Rohan; Jawoor, Shailaja; Dash, Soumya R.; Birajadar, Rajkumar S.; Pawal, Sandip B.; Thenmani, Nandakumar; Vanka, Kumar; Chikkali, Samir H. (Journal of Macromolecular Science Part A-Pure and Applied Chemistry, 2024)
Polyethylene is the single largest volume polymer produced globally using Ziegler-type catalysts. Numerous modifications have been reported in search of a better catalyst that can control molecular weight, polydispersity, and branching. In our attempts to identify a suitable imine thiophene-ligated chromium complex, we examined 9 different titanium complexes computationally. The DFT investigations considered barriers for insertion, propagation, and termination by beta-H elimination or chain transfer, and identified N-(4-methoxyphenyl)-2-phenyl-1-(thiophen-2-yl)ethan-1-imine(L9) as the most suitable ligand. Subsequently, L9 was prepared in good yield (70%) by condensing 2-phenyl-1-(thiophen-2-yl)ethan-1-one with 4-methoxyaniline. Ligand L9 was treated with early transition metal precursors (Ti, Cr, Zr) to generate a homogenous catalyst. The identity of these catalysts was unambiguously ascertained using a combination of NMR, ICP, FT-IR, UV-Vis spectroscopy, and ESI-MS. The performance of L9-ligated titanium complex [Cat.1] was examined in ethylene polymerization using MMAO as a co-catalyst. Insertion of ethylene was tracked using high-pressure NMR experiments and Cat.1 was found to be active in the polymerization. Ethylene polymerization conditions were optimized to obtain high activity and molecular weight polyethylene. The chromium complex [Cat.2] outperformed the Ti and Zr-derived catalysts with the highest TOF of 6294 mol of PE/mol of Cr/h. Cat.2 produced high molecular weight, high-density polyethylene.
Keywords: Cr-complexes; DFT; high-density polyethylene; Imine thiophene ligand; Polyethylene

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.

Divergent synthesis of unsymmetrical Bis-heteroaryl ketones via base-promoted cascade reactions of 1,2-alkynedione-derived N-propargylic β-enaminones - Bag, Debojyoti; Saini, Sheetal; Rathod, Mahesh S.; Sawant, Sanghapal D. (JOURNAL OF ORGANIC CHEMISTRY, 2024)
Keywords: ASYMMETRIC-SYNTHESIS; heterocycles; intramolecular cyclization; pyrroles

Durable and stable bifunctional Co3O4-based nanocatalyst for oxygen reduction/evolution reactions - Chutia, Bhugendra; Chetry, Rashmi; Rao, Komateedi N.; Singh, Nittan; Sudarsanam, Putla; Bharali, Pankaj (ACS Applied Nano Materials, 2024)
The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are recognized as the core reaction processes in regenerative energy storage and conversion systems. The design of cost-effective and high-performance bifunctional ORR/OER electrocatalysts (ECs) is very important for their substantial commercialization. Herein, sponge-like Co3O4 nanoparticles anchored on carbon (Sp-Co3O4/C) are successfully fabricated by a facile two-step solvothermal strategy for ORR/OER in an alkaline electrolyte. The Sp-Co3O4/C EC exhibits promising bifunctional ORR/OER activity with ORR onset potential (E onset = 0.88 V vs RHE), half-wave potential (E (1/2) = 0.75 V), limiting current density (j = -6.60 mA cm(-2)), OER onset potential (E-onset = 1.26 V), and OER overpotential for 10% energy conversion (eta(10) = 0.38 V) in 0.1 M KOH. It demonstrates a significantly lower reversibility index (Delta E = E- j10 - E 1/2 = 0.86 V), comparable to standard Pt/C and RuO2 ECs. The superior ORR/OER performances of Sp-Co3O4/C EC can be ascribed to the synergistic contribution of a high electrochemically active surface area (48.33 m(2) g(-1)), BET surface area (131 m(2) g(-1)), the rich interfacial structure of the crystal facets (111), (220), and (311), and the abundant oxygen vacancies in the sponge-like morphology. Besides the methanol tolerance, accelerated durability and chronoamperometric test established excellent durability and stability in the electrocatalytic operation. This work offers insight into the development of high-performance ORR/OER ECs. [GRAPHICS]
Keywords: bifunctional; fuel cell; interface; oxygen evolution; oxygen reduction; Oxygen vacancy; Sp-Co3O4/C; sponge-like morphology

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

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

Editorial: microbial biodiversity and bioprospecting in polar ecosystems in the genomics era - Rizzo, Carmen; Dastager, Syed Gulam; Ay, Hilal (FRONTIERS IN MICROBIOLOGY, 2024)
Keywords: diversity; FJORD

Effect of covalently functionalized Indian bentonite clay on thermal, mechanical strength and morphology structure of extrusion/injection-molded nylon 6 composites - Shanmugam, Kumaresan; Rokade, Dhammaraj S.; Ingole, Pravin G.; Pol, Harshawardhan V.; Arunachalam, Saravanakumar; Bajaj, Hari C. (Polymers for Advanced Technologies, 2024)
The research and development of functional polymer composites and their production have posed significant challenges, particularly in creating high mechanical strength and thermal stability composites. In this study, we utilized a micro corotation extruder and injection molding to produce covalently functionalized Indian bentonite clay-nylon 6 high-strength nanocomposites. For comparison, two different amines, 3-aminopropyl trimethoxysilane and N-[3-(trimethoxysilyl) propyl] ethylene di-amine, were used to functionalize bentonite clay. Additionally, 3% and 5% less amino clay filler was added in the nanocomposite to manufacture the polymer composite. Analytical techniques such as Powder X-Ray Diffraction, Fourier transform infrared, thermal gravimetric analysis, and Brunauer-Emmett-Teller surface area were used to characterize the molecular orientation of amine functionalization on clay minerals. Wide-angle X-ray diffraction, atomic force microscopy, and transmission electron microscope were used to characterize the nylon 6 intercalated in amino clay nanocomposite and the polymer structure morphology. Thermogravimetric analysis and differential scanning calorimetry were used to investigate the crystalline thermal behavior of clay-nylon 6 composites. From the results, it was observed that the composition containing 5 wt.% amino clay demonstrated a significant improvement in tensile strength when compared with the composition containing 3 wt.% amino clay. The mechanical strength and the thermal behavior showed a significant improvement of similar to 200% for 5% amino clay-nylon 6 nanocomposite.
Keywords: amine-functionalized clay; bentonite clay; melt intercalation; Nanocomposite; nylon 6; thermal and mechanical properties

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

Effects of gamma irradiation on non-polar GaN films deposited on sapphire using pulsed laser deposition - Rajgoli, Tahir; Sant, Tushar; Jejurikar, Suhas M.; Hinge, Sandip; Banpurkar, Arun; Dahiwale, S. S.; Late, Datta (Applied Surface Science, 2024)
The GaN films/layers exposed to gamma-radiations is known to harvest defects and vacancies in the crystals producing donor, acceptor and recombination centers within the bandgap. Therefore it is important to investigate and study the gamma- ray irradiation effects on various physical and chemical properties of a material before any optoelectronic and/or electronic devices are being fabricated. To avoid Stark effect which is observed in most of the optoelectronic devices fabricated using GaN films grew along polar face, use of non-polar GaN films is suggested by researchers. To address such issues the article reports the investigations of physical and chemical properties of non-polar GaN films grown on polar substrate using pulsed laser deposition, which were exposed to the 60Co gamma rays varying dose values. Resistive nature against the impairment of the films caused by gamma-rays observed herewith is highly encouraging, suggesting the use of non-polar GaN films as radiations harden material suitable for fabricating new generation gamma-ray detectors. To our knowledge very limited information is available that report such investigations.
Keywords: Gallium nitride; Gamma rays; PL emission; pulsed laser deposition

Electrocatalytic and selective oxidation of glycerol to formate on 2D 3d-metal phosphate nanosheets and carbon-negative hydrogen generation - Chauhan, Inderjeet; Vijay, Pothoppurathu M.; Ranjan, Ravi; Patra, Kshirodra Kumar; Gopinath, Chinnakonda S. (ACS Materials Au, 2024)
In the landscape of green hydrogen production, alkaline water electrolysis is a well-established, yet not-so-cost-effective, technique due to the high overpotential requirement for the oxygen evolution reaction (OER). A low-voltage approach is proposed to overcome not only the OER challenge by favorably oxidizing abundant feedstock molecules with an earth-abundant catalyst but also to reduce the energy input required for hydrogen production. This alternative process not only generates carbon-negative green H2 but also yields concurrent value-added products (VAPs), thereby maximizing economic advantages and transforming waste into valuable resources. The essence of this study lies in a novel electrocatalyst material. In the present study, unique and two-dimensional (2D) ultrathin nanosheet phosphates featuring first-row transition metals are synthesized by a one-step solvothermal method, and evaluated for the electrocatalytic glycerol oxidation reaction (GLYOR) in an alkaline medium and simultaneous H2 production. Co3(PO4)2 (CoP), Cu3(PO4)2 (CuP), and Ni3(PO4)2 (NiP) exhibit 2D sheet morphologies, while FePO4 (FeP) displays an entirely different snowflake-like morphology. The 2D nanosheet morphology provides a large surface area and a high density of active sites. As a GLYOR catalyst, CoP ultrathin (∼5 nm) nanosheets exhibit remarkably low onset potential at 1.12 V (vs RHE), outperforming that of NiP, FeP, and CuP around 1.25 V (vs RHE). CoP displays 82% selective formate production, indicating a superior capacity for C–C cleavage and concurrent oxidation; this property could be utilized to valorize larger molecules. CoP also exhibits highly sustainable electrochemical stability for a continuous 200 h GLYOR operation, yielding 6.5 L of H2 production with a 4 cm2 electrode and 98 ± 0.5% Faradaic efficiency. The present study advances our understanding of efficient GLYOR catalysts and underscores the potential of sustainable and economically viable green hydrogen production methodologies.

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

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

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

Establishing a new efficiency descriptor for methanol oxidation reaction and its validation with commercially available Pt-based catalysts - Deshpande, Pooja S.; Radhakrishnan, Thulasi; Prasad, Bhagavatula L. V. (Fuel Cells, 2024)
Direct methanol fuel cells (DMFCs) have received a lot of attention in recent years as promising technology for generating clean and efficient energy. In DMFC, the anode catalyst is a vital component because it is involved in the oxidation of methanol, which produces electrons that can be used as an energy source. Cyclic voltammetry (CV) is commonly used to test the characteristics of the electrode materials before they are employed in the actual fuel cell. Interestingly in the case of DMFCs CV also is a useful technique to obtain vital information about the performance and expected efficiency of the electrodes. In general, the CV of methanol electrooxidation for Pt-based catalysts has two peaks, If in the forward scan (anodic scan) and Ib in the backward scan (cathodic scan). The ratio of these two peaks (If/Ib) is the most commonly used criterion for investigating CO poisoning in catalysts. However, there is a great deal of ambiguity surrounding this criterion, owing to the genesis of Ib. Addressing this we present here a new criterion to evaluate the efficiency of the catalyst using the same CV technique. We validate this newly proposed criterion with commercial Pt/C (comm. Pt/C) and other commercially available alloy catalysts.
Keywords: catalyst poisoning; CO tolerance; direct methanol fuel cells; electrocatalysis; Methanol oxidation reaction

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

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

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

Feedback driven autonomous cycles of assembly and disassembly from minimal building blocks - Reja, Antara; Jha, Sangam; Sreejan, Ashley; Pal, Sumit; Bal, Subhajit; Gadgil, Chetan; Das, Dibyendu (Nature Communications, 2024)
The construction of complex systems by simple chemicals that can display emergent network dynamics might contribute to our understanding of complex behavior from simple organic reactions. Here we design single amino acid/dipeptide-based systems that exhibit multiple periodic changes of (dis)assembly under non-equilibrium conditions in closed system, importantly in the absence of evolved biocatalysts. The two-component based building block exploits pH driven non-covalent assembly and time-delayed accelerated catalysis from self-assembled state to install orthogonal feedback loops with a single batch of reactants. Mathematical modelling of the reaction network establishes that the oscillations are transient for this network structure and helps to predict the relative contribution of the feedback loop to the ability of the system to exhibit such transient oscillation. Such autonomous systems with purely synthetic molecules are the starting point that can enable the design of active materials with emergent properties. The study of the network dynamics of complex systems formed by simple chemicals can contribute to our understanding of complex behavior from simple organic reactions. Here, built on the minimal building blocks, the authors describe a system with periodic (dis)assembly utilizing feedback loops controlled by time-delayed catalysis and pH-driven assembly.

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

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

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

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

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

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

Insights into the structure of sucralfate by advanced solid- and liquid-state NMR - Hareendran, Chaithanya; Ravindranathan, Sapna; Ajithkumar, T. G. (Molecualr Pharmaceutics, 2024)
Sucralfate, which is a sucrose octasulfate aluminum complex, is an active pharmaceutical ingredient (API) falling in the category of cytoprotective agents which are very effective for gastric and duodenal ulcers. On interaction with stomach acid, it ionizes into aluminum and sucrose octasulfate ions to form a protective layer over the ulcerated region inhibiting further attack from acid. The mechanism of action of sucralfate in the context of its structure is not well understood. Considering that at least two forms of this API are available in the market, there are no reports on the various forms of sucralfate and differences in their pharmacological action. We characterized the two forms of sucralfate using multinuclear, multidimensional solid-state NMR, and the results show significant structural differences between them arising from variation in the aluminum environment and the level of hydration. The impact of structural differences on pharmacological action was examined by studying acid-induced Al release by Al-27 liquid-state NMR. The sucralfate, European pharmaceutical standard, Form I, undergoes faster disruption in acid compared to Form II. The difference is explained on the basis of structural differences in the two forms which gives significant insights into the action of sucralfate in relation to its structure.
Keywords: (27)AlMQMAS; H-1-H-1 DQSQ; pharmacological action; solid-stateNMR; sucralfate

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

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

Intramolecular nitrone interrupted click reaction - Pothi, Tejas A.; Ramana, Chepuri V. (Organic Letters, 2024)
We document the intramolecular interception of a Cu-catalyzed azidoalkyne cycloaddition employing a suitably placed nitrone group, providing a simple route to the unprecedented spiro-polyheterocyclic scaffold. The reaction is comprised of a Cu-catalyzed [3 + 2]-cycloaddition of (2-azidoaryl)isatogen with a terminal alkyne and the intramolecular trapping of the transient Cu-triazolide intermediate with the isatogen, with a net formation of one C-C and two C-N bonds and the new heterocyclic ring being spiro-annulated.

Kinetic H2S/CO2 selectivity in an exceptionally sterically hindered amine membrane - Rao, Shraavya; Deng, Xuepeng; Zou, Changlong; Prasad, Babul; Han, Yang; Lin, Li-Chiang; Ho, W. S. Winston (JOURNAL OF MATERIALS CHEMISTRY A, 2024)
Keywords: Absorption; COMPOSITE MEMBRANES; GAS STREAMS; H2S; Thin-Film

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

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

Lead-free 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.

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)

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.

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

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.

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

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

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

Novel sulfonic acid functionalized silica supported isonicotinic acid catalyst for conversion of 2-methylfuran to diesel fuel precursors - Tarade, Komal P.; Kamble, Sanjay P.; Rode, Chandrashekhar V. (Catalysis Letters, 2024)
Polyfuranic compounds produced after carbon up-gradation of 2-methylfuran by acid catalyzed C-C bond forming reactions when undergo hydro-deoxygenation produce diesel fuel. Herein, we prepared a simple and novel silica supported sulfonic acid functionalized isonicotinic acid SO3H-INA@SiO2 catalyst by treating isonicotinic acid with chlorosulphonic acid followed by heterogenization on silica. This heterogeneous solid acid catalyst was explored for the solvent free conversion of 2-methylfuran to diesel fuel precursors of C-15 and C-20 units via tandem ring opening followed by condensation sequence. Under optimized reaction conditions, SO3H-INA@SiO2 was able to convert, 2-methylfuran completely into condensation products such as 5,5-bis(5-methylfuran-2-yl)pentan-2-one (1) and 2,4,4-tris(5-methylfuran-2-yl)pentan-1-ol (2) with 19% and 67% yields, respectively. The heterogeneous SO3H-INA@SiO2 catalyst was successfully recycled up to six consecutive runs without loss of its activity. The SO3H-INA@SiO2 catalyst offered superior activity as compared to the commercially available -SO3H functionalized resins. Superior activity of the prepared catalyst could be attributed for its higher acidity, smaller particle size and high surface area. Structure of the prepared catalyst was confirmed by FTIR and solid state NMR. Total acidity of the prepared catalyst was determined by acid-base titration.
Keywords: 2-Methylfuran; Diesel fuel; heterogeneous catalyst; Ionic solid; solid acid

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

PANI-grafted boron, nitrogen co-doped carbon fiber: An outstanding, high-performance supercapacitor electrode - Nayan, Rajiv; Sinha, Shubhra; Dixit, Vaibhav; Satnami, Manmohan L.; Ghosh, Kallol K.; Pervez, Shamsh; Deb, Manas Kanti; Shrivas, Kamlesh; Rai, Manish K.; Yenchalwar, Sandeep G.; Wasnik, Kundan; Jadkar, Sandesh R.; et al. (JOURNAL OF ENERGY STORAGE, 2024)
Keywords: Composite; polyaniline; Solid-state supercapacitor

Perturbation of fermi resonance on hydrogen-bonded > C=O: 2D IR studies of small ester probes - Sakpal, Sushil; Chakrabarty, Suranjana; Reddy, Kambham Devendra; Deshmukh, Samadhan H.; Biswas, Rajib; Bagchi, Sayan; Ghosh, Anup (Journal of Physical Chemistry B, 2024)
We utilized linear and 2D infrared spectroscopy to analyze the carbonyl stretching modes of small esters in different solvents. Particularly noteworthy were the distinct carbonyl spectral line shapes in aqueous solutions, prompting our investigation of the underlying factors responsible for these differences. Through our experimental and theoretical calculations, we identified the presence of the hydrogen-bond-induced Fermi resonance as the primary contributor to the varied line shapes of small esters in aqueous solutions. Furthermore, our findings revealed that the skeletal deformation mode plays a crucial role in the Fermi resonance for all small esters. Specifically, the first overtone band of the skeletal deformation mode intensifies when hydrogen bonds form with the carbonyl group of esters, whereas such coupling is rare in aprotic organic solvents. These spectral insights carry significant implications for the utilization of esters as infrared probes in both biological and chemical systems.

photoarchitectonic hydrogel for synergistic in vitro chemo–phototherapy of breast cancer - Paul, Shatabdi; Yadav, Binduma; Patil, Mahesh D.; Pujari, Anil Kumar; Singh, Umesh; Rishi, Vikas; Bhaumik, Jayeeta (Materials Advances, 2024)
Currently, combinatorial therapy has evoked interest in cancer treatment, and may promote achieving a synergistic effect using cancer medicines. Laser-assisted and pH-responsive therapies have attracted significant attention, and their combination leads to high efficiency cancer treatment. Herein, we developed a chemo–phototherapeutic hydrogel comprised of doxorubicin (DOX, a chemotherapeutic drug) and zinc phthalocyanine (ZnPc, a phototherapeutic drug) for combinatorial and synergistic treatment of breast cancer. Firstly, we have developed carbon dots (CDs, size of ∼5 nm) utilizing lignin and folic acid as biocompatible sources. Then doxorubicin was loaded on the surface of the carbon dots via conjugation (DOX@CDs). Later on, zinc phthalocyanine and acrylic acid derivatives were utilized to develop a laser-responsive hydrogel (ZnPc-PP H). Afterward, doxorubicin-conjugated carbon dots were incorporated into the photoarchitectonic hydrogel to develop a chemo–phototherapeutic drug-loaded hydrogel (DOX@CDs–ZnPc-PP H). Subsequently, the in vitro pH-triggering experiments demonstrated that the hydrogel loaded with both DOX and ZnPc could release the drugs in an acidic environment. Interestingly, in vitro assays confirmed that DOX@CDs–ZnPc-PP H could effectively target breast cancer cells (MCF-7). Furthermore, the developed chemo–phototherapeutic hydrogel exhibited non-cytotoxic behavior. Owing to laser assisted reactive oxygen species generation from ZnPc present in the hydrogel, the growth of MCF-7 cells was significantly lowered. In conclusion, all experimental outcomes indicate that the photoarchitectonic hydrogel has the potential to be applied in synergistic chemo- and photodynamic therapy of cancer.

Photocatalytic CO2 reduction to syngas using nickel phosphide-loaded CdS under visible light irradiation - Yadav, Poonam; Kumar, Santosh; Velankanni, Nandhakumar; Kuehne, Thomas D.; Gosavi, Suresh; Raghupathy, Ramya Kormath Madam; Bhosale, Reshma; Held, Georg; Shelke, Manjusha; Ogale, Satishchandra (Journal of Physics-Energy, 2024)
Photocatalytic CO2 reduction is a sustainable pathway to produce syngas (H-2 + CO), which is a key feedstock for the production of several important liquid fuels on the industrial scale. However, achieving an appropriate tunable ratio of H-2:CO in syngas for commercial purposes is a challenging task. In this work, we present a low-cost and non-noble metal, phosphide-based co-catalyst-Ni2P-loaded cadmium sulfide (CdS) photocatalyst system, for photocatalytic CO2 reduction. As a co-catalyst, Ni2P fosters an efficient charge separation of photoexcited charges generated in the CdS production of syngas. In total, 3 wt.% Ni2P/CdS exhibited exceptional performance of 50.6 mu mol g(-1) h(-1) in the CO evolution rate and 115 mu mol g(-1) h(-1) in the H-2 evolution rate, with a syngas composition varying from 2 to 4 in the H-2:CO ratio. Furthermore, first-principles density functional theory calculations were performed to study the surface energetics of the catalyst system and the results are found to be consistent with our experimental findings. Indeed, they establish that the composite favors CO2 photoreduction into syngas more efficiently than pure surfaces.
Keywords: CdS; CO2 reduction; Photocatalysis; Syngas; transition metal phosphides

Photocatalytic regeneration of reactive cofactors with inP quantum dots for the continuous chemical synthesis - Chakraborty, Indra Narayan; Jain, Vanshika; Roy, Pradyut; Kumar, Pawan; Vinod, Chathakudath P.; Pillai, Pramod P. (ACS Catalysis, 2024)
The shuttling of redox-active nicotinamide cofactors between the light and dark cycles is the key to the continuous production of biomass in photosynthesis. The replication of such processes in artificial photosynthetic systems demands fast photoregeneration as well as simultaneous integration of these nicotinamide cofactors into the dark cycle. Here, we report the design of an artificial photosynthetic system for the continuous production of butanol via the constant photoregeneration and consumption of nicotinamide cofactors, powered by an indium phosphide quantum dot (InP QD) photocatalyst and alcohol dehydrogenase (ADH) enzyme, respectively. A strong electrostatic attraction between the oppositely charged InP QDs and electron mediators significantly enhanced the charge extraction and utilization processes, enabling a fast (similar to 30 min, with a turn over frequency of similar to 1333 h(-1)), quantitative (>99%), and selective photoregeneration of enzymatically active nicotinamide cofactors in the light cycle. These photoregenerated nicotinamide cofactors were further coupled in the dark cycle to trigger the ADH oxidoreductase enzyme for the production of butanol, via sequential as well as simultaneous light-dark cycles. The amount of butanol produced under simultaneous light-dark cycles was higher than the stoichiometric limit, proving the constant regeneration and consumption of nicotinamide cofactors in light and dark cycles, respectively. Thus, a proper design and integration of the InP QD-based photocatalytic cycle with the enzymatic cycle led to the effective electron shuttling between light and dark cycles, as seen in photosynthesis.
Keywords: artificial photosynthesis; biologicalcofactors; charge transfer; indiumphosphide; Photocatalysis; quantum dots

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

Poly(d,l-lactide-co-glycolide) surface-anchored biotin-loaded irinotecan nanoparticles for active targeting of colon cancer - Giram, Prabhanjan S.; Nimma, Ramakrishna; Bulbule, Anuradha; Yadav, Amit Singh; Gorain, Mahadeo; Radharani, Nalukurthi Naga Venkata; Kundu, Gopal C.; Garnaik, Baijayantimala (ACS Omega, 2024)
A poly-(d,l-lactide-co-glycolide) (PLGA) copolymer was synthesized using the ring-opening polymerization of d,l-lactide and glycolide monomers in the presence of zinc proline complex in bulk through the green route and was well characterized using attenuated total reflectance-Fourier transform infrared, H-1 and C-13 nuclear magnetic resonance, gel permeation chromatography, differential scanning calorimetry, X-ray diffraction, matrix-assisted laser desorption/ionization time-of-flight, etc. Furthermore, PLGA-conjugated biotin (PLGA-B) was synthesized using the synthesized PLGA and was employed to fabricate nanoparticles for irinotecan (Ir) delivery. These nanoparticles (PLGA-NP-Ir and PLGA-B-NP-Ir) were tested for physicochemical and biological characteristics. PLGA-B-NP-Ir exhibited a stronger cellular uptake and anticancer activity as compared to PLGA-NP-Ir in CT-26 cancer cells (log p < 0.05). The accumulation and retention of fluorescence-labeled nanoparticles were observed to be better in CT-26-inoculated solid tumors in Balb/c mice. The PLGA-B-NP-Ir-treated group inhibited tumor growth significantly more (log p < 0.001) than the untreated control, PLGA-NP-Ir, and Ir-treated groups. Furthermore, no body weight loss, hematological, and blood biochemical tests demonstrated the nanocarriers' nontoxic nature. This work presents the use of safe PLGA and the demonstration of a proof-of-concept of biotin surface attached PLGA nanoparticle-mediated active targeted Ir administration to combat colon cancer. To treat colon cancer, PLGA-B-NP-Ir performed better due to specific active tumor targeting and greater cellular uptake due to biotin.

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

Reaction of 4 (Alkynyloxy)cyclohexa-2,5-dienones with Dimethyl Sulfoxide: a catalyst-free formation of 6/5/3-fused tricyclic enones - Rai, Archana; Das, Utpal (Journal of Organic Chemistry, 2024)
<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;">6/5/3-Fused tricyclic enones were obtained when 4-(alkynyloxy)cyclohexa-2,5-dienones were treated with DMSO at 150 °C. The reaction proceeded via a four-membered oxathietene intermediate. The protocol developed is atom economical, has a broad substrate scope, and is amenable to gram-scale synthesis. The products obtained are susceptible to further synthetic transformations.

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.

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

Scalable approach using a gC3N4 -covalent organic framework hybrid catalyst towards sustainable hydrogen production from seawater and wastewater - Asokan, Kiran; Bhagyasree, T. M.; Devasia, George; Krishnamurty, Sailaja; Solim, Sabah; Rueda, Lina; Al-Mohannadi, Dhabia M.; Al-Hashimi, Mohammed; Kakosimos, Konstantinos; Santhosh Babu, Sukumaran (CHEMICAL SCIENCE, 2024)

Scanning tunneling microscopy investigation of synaptic behavior in AgInS2 quantum dots: effect of ion transport in neuromorphic applications - Betal, Atanu; Chetia, Anupam; Bera, Jayanta; Saikia, Dibyajyoti; Sharma, Ashish; Rath, Arup K.; Sahu, Satyajit (ACS Applied Nano Materials, 2024)
Scanning tunneling microscopy (STM) is a powerful technique for investigating the nanoscale properties of functional materials. Additionally, scanning tunneling spectroscopy (STS) facilitates the determination of the local density of states (LDOS) within the material. In this study, we present an exploration of the resistive switching (RS) properties and neuromorphic computing capabilities of individual AgInS2 quantum dots, utilizing STM and STS techniques. By examining the material's bandgap and its temperature dependence, we uncover a nonlinear variation below the Debye temperature and a linear trend at higher temperatures. Moreover, STS measurements demonstrate changes in the conducting states induced by localized pulses, further confirming the unique characteristics of the quantum dots. The experimental devices constructed by using these quantum dots effectively replicate the RS properties observed at the nanoscale. To assess the neuromorphic application of the devices, pulse transient measurements simulating the learning and forgetting processes were conducted. The gradual set and reset processes successfully mimic the information retention and erasure capabilities essential for neuromorphic computing. Notably, the resistive switching mechanism in these devices is attributed to localized ionic transport, which highlights the significant involvement of ionic species in the observed RS behavior. The outcomes of this study contribute to the fundamental understanding of RS properties in single AgInS2 quantum dots and offer valuable insights into their potential applications in neuromorphic computing.
Keywords: corona poling; Ion transport; neuromorphic computing; quantum dots; resistive switching; Scanning tunneling microscopy; STS

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

Strain improvement for enhanced erythritol production by Moniliella pollinis Mutant-58 using jaggery as a cost-effective substrate - Khatape, Anil B.; Rangaswamy, Vidhya; Dastager, Syed G. (International Microbiology, 2024)
Erythritol has been produced by various microorganisms including Yarrowia, Moniliella, Aureobasidium, and Candida strains. Due to its relatively high price, erythritol sweetener is used lesser than other polyols despite having many advantages. Therefore, in this study, Moniliella pollinis strain was improved for erythritol production by chemical mutagenesis and subsequently screening for cost-effective carbon sources for the enhanced erythritol yield. M. pollinis was subjected to N-methyl N-nitro N-nitroso guanidine (NTG), ethyl methyl sulfonate (EMS), and UV mutagenesis for improved erythritol production. The fmutant strains were evaluated for enhanced erythritol production medium optimization by using different carbon substrates at the shake flask level. To enhance the production of erythritol and statistical media, optimization was carried out using a central composite design (CCD). Among 198 isolated mutants, Mutant-58 strain generated by EMS mutagenesis was selected for further assessment. The Mutant-58 strain showed significant morphological changes as compared to the parent strain. Furthermore, statistically optimized media composition resulted in the higher production of erythritol (91.2 & PLUSMN; 3.4 g/L) with a yield of 40.7 & PLUSMN; 3.4 % in shake flask experiments. The optimized medium composition for erythritol production constitutes (g/L) 225 jaggery, 4.4 yeast extract (YE), 4.4 KH2PO4, 0.31 MgSO4, and pH 5.5. The present study demonstrated strain improvement, media, and process optimization resulting in a 30% increase in the erythritol production in the Mutant-58 as compared to the parent strain. This is also the first instance where jaggery has been used as a cost-effective carbon source alternative to glucose for industrial-scale erythritol production.
Keywords: Erythritol; Fermentation; Moniliella pollinis; Mutation; Optimization; renewable resource

Structural insights into ketanserin salts with aliphatic acids and their physiochemical properties - Kenguva, Gowtham; Rout, Smruti Rekha; Shaikh, Tabrez R.; Baidya, Debjani; Shelke, Nikita; Sanphui, Palash; Dandela, Rambabu (CRYSTENGCOMM, 2024)
Keywords: PHARMACEUTICAL COCRYSTAL; SEROTONIN; SHYDROCHLOROTHIAZIDE; solubility

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

Sustainable bioprocess technology for producing food-flavour (+)-γ-decalactone from castor oil-derived ricinoleic acid using enzymatic activity of Candida parapsilosis: Scale-up optimization and purification using novel composite - Syed, Naziya; Singh, Suman; Chaturvedi, Shivani; Kumar, Prashant; Kumar, Deepak; Jain, Abhinav; Sharma, Praveen Kumar; Nannaware, Ashween Deepak; Chanotiya, Chandan Singh; Bhambure, Rahul; Kumar, Pankaj; Kalra, Alok; et al. (Journal of Biotechnology, 2024)
Ricinoleic acid (RA) from castor oil was employed in biotransformation of peach-flavoured gamma-decalactone (GDL), using a Candida parapsilosis strain (MTCC13027) which was isolated from waste of pineapple crown base. Using four variables-pH, cell density, amount of RA, and temperature-the biotransformation parameters were optimized using RSM and BBD. Under optimized conditions (pH 6, 10 % of microbial cells, 10 g/L RA at 28 degrees C), the conversion was maximum and resulted to 80 % (+)-GDL (4.4 g/L/120 h) yield in shake flask (500 mL). Furthermore, optimization was achieved by adjusting the aeration and agitation parameters in a 3 L bioreactor, which were then replicated in a 10 L bioreactor to accurately determine the amount of (+)-GDL. In bioreactor condition, 4.7 g/L (>85 %) of (+)-GDL is produced with 20 % and 40 % dissolved oxygen (1.0 vvm) at 150 rpm in 72 h and 66 h, respectively. Further, a new Al-Mg-Ca-Si composite column-chromatography method is developed to purify enantiospecific (+)-GDL (99.9 %). This (+)-GDL is 100 % nature-identical as validated through 14C-radio-carbon dating. Thorough chemical investigation of enantiospecific (+)-GDL is authenticated for its use as flavour. This bioflavour has been developed through a cost-effective biotechnological process in response to the demand from the food industry on commercial scale.
Keywords: (+)-gamma-Decalactone; Al-Mg-Ca-Si composite; Bioflavour; Candida parapsilosis; castor oil; Food-waste

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, characterization, and crystal structure of 2-(2-azidophenyl)-3-oxo-3H-indole 1-oxide - Dhote, Pawan; Tothadi, Srinu; Ramana, Chepuri V.; Chopra, D. (Acta Crystallographica Section E Crystallographic Communications, 2024)
<div class="abstract author" id="aep-abstract-id5" 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;"> An attempt to explore the reactivity of the nitro group in the presence of gold catalysis in comparison to the azide group yielded intriguing results. Surprisingly, only the nitro group exhibited reactivity, ultimately giving rise to the formation of the title isatogen. <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;"> An attempt to explore the reactivity of the nitro group in the presence of gold catalysis in comparison to the azide group yielded intriguing results. Surprisingly, only the nitro group exhibited reactivity, ultimately giving rise to the formation of the title isatogen, C14H8N4O2. In the crystal structure, weak C—H⋯O hydrogen bonds and π–π stacking interactions link the molecules. The structure exhibits disorder of the molecule.

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 tetracyclic benzoxazolo-indol-3-ones from isatogens and arynes through a [3+2]-cycloaddition and skeletal reorganization - Halnor, Swapnil V.; Singh, Maneesha; Dhote, Pawan S.; Ramana, Chepuri V. (Journal of Organic Chemistry, 2024)
The construction of an unprecedented tetracyclic benzoxazolo-indol-3-one scaffold has been executed through the [3 + 2]-cycloaddition of isatogens with arynes. The initially formed benzisoxazolo-indol-3-one intermediate undergoes a skeletal reorganization through a 1,3-sigmatropic shift/retro-Mannich reaction with the net formation of one C-N and two C-O bonds. The Lewis acid-catalyzed allylation of some of the resulting benzoxazolo-indol-3-ones resulted in oxazepino-indolones with promising photophysical properties.

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

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

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

TiO2 spaghetti for sustainable future - Rathod, Yugal; Natu, Varun (Matter, 2024)
TiO2 is widely utilized in applications ranging from paints to solar cells. Recent advancements in synthesizing nano-TiO2 by Badr, Barsoum, et al. have enabled its production at low cost and large scale. These nanostructures, comprising 1D lepidocrocite nanofilaments, show promise in enhancing solar water splitting and several other applications.

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.

Total synthesis of (-) and (+)-zingibergingerols A - Shet, Manoj N.; Ramana, Chepuri V. (Journal of Organic Chemistry, 2024)
The first total synthesis of both of the enantiomers of Zingibergingerol A has been accomplished. The distinctive 3,7,9-trioxabicyclo[4.2.1]nonane skeleton is crafted through gold-catalyzed alkynol cycloisomerization. The synthesis comprises sequential C-C bond formations at both ends of epichlorohydrin: first opening the epoxide with eugenol-derived alkyne, followed by subsequent epoxide installation, and again opening with a Grignard reagent. The resulting alkynol with a fixed C5 stereochemistry was subjected to O-allylation, followed by dihydroxylation and alkynol cycloisomerization.

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

Tridentate NacNac tames T-shaped nickel(I) radical - Pahar, Sanjukta; Sharma, Vishal; Raj, K. Vipin; Sangole, Mayur P.; George, Christy P.; Singh, Kirandeep; Vanka, Kumar; Gonnade, Rajesh G.; Sen, Sakya S. (Chemistry- a european journal, 2024)
The reaction of a nickel(II) chloride complex containing a tridentate beta-diketiminato ligand with a picolyl group [2,6-iPr2-C6H3NC(Me)CHC(Me)NH(CH2py)]Ni(II)Cl (1)] with KSi(SiMe3)3 conveniently afforded a nickel(I) radical with a T-shaped geometry (2). The compound's metalloradical nature was confirmed through electron paramagnetic resonance (EPR) studies and its reaction with TEMPO, resulting in the formation of a highly unusual three-membered nickeloxaziridine complex (3). When reacted with disulfide and diselenide, the S-S and Se-Se bonds were cleaved, and a coupled product was formed through carbon atom of the pyridine-imine group. The nickel(I) radical activates dihydrogen at room temperature and atmospheric pressure to give the monomeric nickel hydride. A thermally stable, T-shaped, nickel(I) radical was straightforward obtained by reduction of a tridentate nacnac nickel(II) chloride with KSi(TMS)3. The metalloradical character of the compound was demonstrated by the formation of a highly unusual nickeloxaziridine complex upon addition of TEMPO. The Ni(I) species displays a rich chemistry towards activation S-S, and Se-Se bond leading to unusual C-C coupled product as well as dihydrogen activation at room temperature and atmospheric pressure to generate monomeric nickel hydride.+image
Keywords: C-C Bond formation; Hydrogen Activation; Metalloradical; Nickel; Tridentate nacnac

Unraveling the cooperative mechanisms in ultralow copper-loaded WC@NGC for enhanced CO2 electroreduction to acetic acid - Bagchi, Debabrata; Riyaz, Mohd; Raj, Jithu; Roy, Soumyabrata; Singh, Ashutosh Kumar; Cherevotan, Arjun; Vinod, Chathakudath P.; Peter, Sebastian C. (Chemistry of Materials, 2024)
Electrochemical CO2 reduction reaction (eCO(2)RR) has been explored on tungsten carbide (WC) nanoparticles embedded on N-doped graphitic carbon (NGC), demonstrating excellent activity toward the formation of acetic acid at an extremely lower potential. The activity has been further enhanced by loading ultralow copper sites into the catalyst system, exhibiting 80.02% Faradaic efficiency (FE) toward acetic acid at an applied potential of -0.3 V (vs RHE). Potential-dependent in situ infrared (IR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, ex situ extended X-ray absorption fine structure (EXAFS) studies, and computational analysis confirm that synergy between uniformly dispersed Cu atoms and WC lattice plays a crucial role in the formation of acetic acid with high FE at a lower potential. It has been observed that the W atom of WC strongly chemisorbs CO2 with a significant change in the C-O bond length and the O-C-O bond angle, in contrast to weaker adsorption on Cu-based catalyst surfaces. The presence of a Cu site enhances the adsorption of CO2, thereby increasing the possibility of C-C coupling kinetically. Most importantly, hydrogen evolution predominates on the catalyst's surface at higher applied potentials (-0.5 to -1.1 V vs RHE), elucidating the mechanism underlying enhanced charge transfer between copper and WC, a phenomenon ascertained through in situ IR spectroscopy and ex situ XPS analysis

Unravelling polymorphism-driven luminescence in GFP chromophore analogues: insights into the phase transition and morphology-dependent optical waveguide properties - Dabke, Niteen B.; Raut, Yash; Mali, Bhupendra P.; Pandya, Rinu; Vanka, Kumar; Manoj, Kochunnoonny; Gonnade, Rajesh G. (Journal of Materials Chemistry C, 2024)
The advent of multi-emission organic solid-state materials in response to external stimuli has sparked the scientific community due to their potential application in developing sophisticated optoelectronic sensors and bioanalytical tools. This article presents green fluorescent protein chromophore (GFPc) analogue-based polymorphs exhibiting significantly different emissions due to various noncovalent interactions in the supramolecular environment and conformational alterations in the crystalline state. In both compounds (A and B), the polymorphs undergo monotropic thermal phase transitions that are characterized by DSC, HSM, and VT-PXRD techniques. The distinct fluorescent emission characteristics of these polymorphs demonstrated morphology-related optical waveguiding features. Specifically, the plate-type Form A1 emitted light with a 2D blue hue, while the needle-type Form A2 emitted light with a yellowish-green colour. Additionally, the impressive waveguiding capabilities of Form B1 were explored in both straight and singly/doubly bending configurations to facilitate fluorescence propagation. Consequently, there is significant interest in developing organic materials based on GFP chromophores, which exhibit low emission in solution but display multi-fluorescent emission in the solid state. These materials are promising for applications such as optoelectronic devices, security tags, live cell imaging, and fluorescent inks. Polymorphs of GFPc analogs A and B display differences in their optical waveguiding properties in 1D and 2D depending on the crystal shapes. Furthermore, Form B1 demonstrates efficient optical waveguiding capabilities even when the crystal is bent.

Unveiling different structural orderings in Fe5-xGeTe2 - Walve, Vaibhav; Parakh, Piyush; Rajput, Umashankar; Mhase, Akash S.; Singh, Kirandeep; Deshpande, Aparna (Physical Review B, 2024)
We investigate the metallic van der Waals itinerant ferromagnet Fe5-xGeTe2 5 - x GeTe 2 with atomic scale, spatially resolved low-temperature scanning tunneling microscopy (STM), and spectroscopy (STS). STM images unveil / / a new structural order 2a a x 1a a along with the known order 3a a x 3a a manifesting as nonuniform domains. STS shows spatial and energy resolved local density of states that reveal the crucial influence of Fe(1) site occupancy on the system's electronic interactions. Our magnetization measurements show magnetic anomalies at lower temperatures and identify a Curie temperature (Tc) c ) surpassing room temperature. Collectively, our results elucidate the intricate nature of Fe5-xGeTe2 5 - x GeTe 2 and underscore its potential for tunability of spintronics and high-temperature magnetic applications.

Visible-light-induced radical sulfonylative-cyclization cascade of 1,6-Enynol derivatives with sulfinic acids: a sustainable approach for the synthesis of 2,3-disubstituted benzoheteroles - Haritha Kumari, Arram; Jagadesh Kumar, Jangam; Sharadha, Nunavath; Rama Krishna, Gamidi; Jannapu Reddy, Raju (CHEMSUSCHEM, 2024)
Keywords: 1; 6-Enynols; Benzofurans; Benzothiophenes; indoles; Sulfones

Water-chain mediated proton conductivity in mechanically flexible redox-active organic single crystals - Hossain, Munshi Sahid; Ghosh, Meena; Mondal, Amit; Ajmal, P.; Saha, Monochura; Reddy, C. Malla; Kurungot, Sreekumar; Bandyopadhyay, Subhajit (Journal of Materials Chemistry A, 2024)
Investigating electrochemical features of proton-conducting organic crystalline materials is relevant in developing efficient energy storage and conversion devices. However, the poor structural flexibility of the crystalline materials at the molecular level often impedes hydrogen bond reorganization of the proton carriers during proton migration, ultimately leading to low ionic conductivity. Here, we report crystals of azobenzene, functionalized with dipicolylamine at both ends (Azo-DPA), which contain an extended hydrogen-bonding network with water molecules in its structure. Interestingly, the crystals display remarkable mechanical flexibility explicitly probed by the nanoindentation technique. The mechanically flexible neutral organic crystals devoid of any acidic moieties (-COOH, -PO3H2, etc.) within the system, exhibit promising proton conductivity (1.63 x 10-4 S cm-1 at 30 degrees C under 95% relative humidity) which is almost 100 times better compared to the neutral organic systems reported to date. Mechanically flexible redox-active crystalline organic material (Azo-DPA) capable of impressive proton conduction was employed as an electrode material for the first time in an aqueous battery containing Zn2+ ions. The experimental and theoretical studies on the charge storage mechanism revealed the redox activity of the azo (-N 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 N-) centers involving reversible insertion/extraction of protons and Zn2+ ions. Ultimately, the electrode displayed a specific capacity similar to 49 mA h g-1 with almost 100% retention after 1400 cycles, encouraging the scope of redox-active organic crystalline materials for energy storage applications. Investigating the electrochemical features of proton-conducting flexible organic crystalline materials is crucial for the development of efficient energy storage and conversion devices.

Yoga therapy attenuates the progression of diabetes - insights from proteomics and metabolomics analysis - Sonwane, Babasaheb P.; Raut, Pooja; Chitalkar, Jyotsna; Godbole, Smita; Sabnis, Shanta; Gupta, Jyoti; Santhakumari, B.; Deshpande, Mukund V.; Kulkarni, Mahesh J. (International Journal of Yoga, 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;"> Objective: Diabetes management remains challenging despite advancements in therapeutics, with many subjects developing complications. Yoga has been shown to aid diabetes management. This study investigates the impact of yoga therapy on diabetes progression, utilizing proteomics and metabolomics analyses to explore underlying molecular mechanisms. <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;"> Methodology: A 3-month longitudinal study involving healthy subjects with prediabetes and diabetes was conducted. Blood glucose, glycated hemoglobin (HbA1c), lipid profile, and malondialdehyde (MDA) levels were measured before and after the yoga intervention. <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;"> Results and conclusion: Healthy subjects showed no significant changes in blood glucose, lipid profile, HbA1c, or MDA levels. However, subjects with prediabetes and diabetes experienced positive changes, with decreases in HbA1c and MDA levels. Proteomics and metabolomics analyses provided insights into the molecular mechanisms by which yoga attenuates diabetes progression in subjects with prediabetes and diabetes. This study is a pioneering effort to understand the molecular basis of yoga's beneficial effects on diabetes management.

ZrO2 supported Cu nanoparticles for sonogashira and ullmann coupling reactions under palladium-free conditions - Patil, Seema P.; Rajmane, Archana S.; Jadhav, Sanjay N.; Rajmane, Vijaya S.; Rode, Chandrashekhar V.; Kumbhar, Arjun S. (Catalysis Letters, 2024)
Cu nanoparticles supported on ZrO2 (CuNPs@ZrO2) were synthesized using a one-step co-precipitation process, and their application in C-C coupling reactions was investigated. The catalyst was characterized using XRD, XPS, SEM, TEM, and TGA techniques. The prepared catalyst was used for the Sonogashira cross-coupling reactions of aryl bromides with phenyl-acetylene in the presence of K2CO3 in DMF at 110 degrees C, which resulted in substituted alkynes with good to excellent yields. The protocol was also extended for the Ullmann coupling reactions of aryl iodides under similar reaction conditions, yielding the desired products with good to excellent yields without homo-coupling. Interestingly, unlike other copper catalysts, the present catalyst worked under air and did not require an inert atmosphere to prevent alkyne. This catalytic system is versatile, tolerant, and significantly cheaper than the ``traditional'' Pd-catalyzed Sonogashira cross-coupling of terminal alkynes with aryl halides. The catalyst could be reused for five catalytic cycles with no significant change in the product yield. All of these characteristics make our prepared CuNPs@ZrO2 catalyst quite suitable for the gram-scale synthesis of biaryls and alkynes, with a simple workup.{GRAPHIACAL ABSTRACT
Keywords: CuNPs; Recyclability; Sonogashira coupling; Ullmann coupling; ZrO2

Advanced zinc-polymer composites for marine corrosion protection and self-healing - Sharma, Sanjay; Girish, Santhosh; Nayaka, G. P.; Shiva Samhitha, S.; Pilliadugula, Rekha; Shivamurthy, B. P.; Gurumurthy, S. C.; Ruiz-Robles, Mitchel A.; Rojas, D.; Surabhi, Srivathsava (NPJ Materials Degradation, 2025)
Steel corrosion in saltwater costs over \$2.5 trillion annually. This review highlights advancements in zinc and polymer-based coatings for marine protection. It covers traditional methods and emerging technologies like nanoparticle-enhanced alloys, conducting polymers, metal organic frameworks (MOFs), and 2D materials. These offer improved resistance, self-healing, and intelligent protection with a future focus on sustainability and extended service life for marine infrastructure.

Advances in metabolic engineering and fermentation for 3-hydroxypropionic acid biosynthesis: a comprehensive review - Joshi, Harshvardhan; Isar, Jasmine; Rangaswamy, Vidhya; Raghunathan, Anu (World Journal of Microbiology & Biotechnology, 2025)
The grand challenge in biobased Manufacturing Lies in achieving the sustainable, economically competitive conversion of renewable biomass into high-value Chemicals capable of replacing fossil-derived products. Among these, 3-hydroxypropionic acid (3-HP) has emerged as a top-tier target-an exceptionally versatile platform molecule. It finds applications in the synthesis of acrylic acid, 1,3-propanediol, and other derivatives, positioning it as a potential cornerstone for bio-based plastics. This review consolidates the latest breakthroughs in microbial 3-HP production, encompassing advanced strain engineering, pathway rewiring, cofactor optimization, metabolic modeling, and flux balance analysis. We critically examine strategies to overcome inherent metabolic and physiological constraints, including byproduct suppression, redox balancing, and tolerance engineering. Emerging approaches-such as dynamic regulation of metabolic flux, control of cell morphology and density, and integration of co-production pathways-are highlighted for their capacity to boost yields and process robustness. Additionally, we address the fermentation process innovations targeting enhanced productivity, substrate efficiency, minimal nutrient input, and industrially relevant titres. Collectively, these insights Chart a clear path toward the scalable, sustainable biomanufacturer of 3-HP.
Keywords: 1; 3-hydroxypropionaldehyde; 3-hydroxypropionic acid; 3-Propanediol; Fermentation; flux balance analysis; Metabolic engineering

Air-stable double halide perovskite Cs2CuBiBr6: synthesis and memristor application - Betal, Atanu; Chetia, Anupam; Saikia, Dibyajyoti; Karmakar, Krishnendu; Bera, Ganesh; Dambhare, Neha V.; Rath, Arup K.; Sahu, Satyajit (Physical Chemistry Chemical Physics, 2025)
The excellent optical and electronic properties of halide perovskite materials have attracted researchers to investigate this particular field. However, the instability in ambient conditions and toxicity of materials like lead have given some setbacks to commercial use. To overcome these issues, perovskite-inspired materials with less toxic and excellent air-stable materials are being studied. Double perovskite materials are one of the perovskite materials. In this study, we have synthesized air-stable double perovskite Cs2CuBiBr6 using a solution process approach. The characterization of the material revealed that it has excellent crystallinity and high stability. The material shows excellent optical and electronic properties. It can be used in resistive memory devices. It shows stable current-voltage characteristics and analog switching. The ion migration through the active layer and accumulation of charge near the electrode region are the reasons behind the resistive switching.

Aldol Condensation of Furfural with Acetone by Using Mg-Al-O-t-Bu HT Catalyst and Kinetic Studies - Patil, Sneha; Kamble, Paresh; Vinod, Chathakudath Prabhakaran; Rathod, Virendra; Kantam, Mannepalli Lakshmi (Industrial & Engineering Chemistry Research, 2025)
An environment-friendly method for producing jet fuel precursors involves the aldol condensation of biomass-derived chemicals. In this study, the condensation reaction between furfural and acetone was performed using a Mg-Al-O-t-Bu hydrotalcite (HT) catalyst, achieving a furfural conversion of 99% and a selectivity of 82% toward 4-(2-furyl)-3-buten-2-one (FAc). The kinetics of the process were evaluated using a Langmuir-Hinshelwood-Hougen-Watson (LHHW) model across a range of temperatures, and the model showed an excellent fit to the experimental data. The effect of different catalysts, reaction temperatures, catalyst loadings, molar ratios, and reaction times was systematically investigated. The Mg-Al-O-t-Bu HT catalyst was extensively analyzed through techniques such as XRD, XPS, FTIR, nitrogen adsorption-desorption measurements, and CO2-TPD. The catalyst exhibited excellent stability, maintaining its performance consistently across five successive reaction cycles with no notable decline in activity. These findings highlight the industrial relevance of Mg-Al-O-t-Bu HT as a robust and recyclable solid base catalyst for biomass upgrading, with strong potential for process scale-up in renewable fuel production.

Aspergillus terreus variant TB21 wet biomass optimized by in-situ transesterification for biodiesel production - Bed, Rashmi K.; Kumar, V. Ravi; RaviKumar, Ameeta (AMB Express, 2025)
The oleaginous fungus, Aspergillus terreus when subjected to random chemical mutagenesis led to isolation of TB21 variant with improved lipid content (78.1%) as compared to wild type (49.8%). The fungal wet biomass grown on sugarcane bagasse hydrolysate (SCBH) was subjected to one-step in-situ (direct) acid transesterification to optimize its conversion to biodiesel using a 2-level factorial statistical design of experiments. The process optimization revealed that wet biomass and methanol were the most significant factors and in a short reaction time period of 5 min with low methanol: wet biomass ratio (10:1) influenced FAME production Statistical optimization studies showed that TB21 exhibited a higher FAME content of 76.5 and 38.1% (w/w) from wet and dry biomass, respectively when compared to wild type (48.1 and 24.5%). FAME productivity (0.55-1 h-1) and a yield (66 gL-1) were achieved when TB21 was grown on SCBH for 120 h at 30 degrees C. The FAME profile from the wet biomass of TB21 grown on SCBH had desirable amounts of saturated (77.7%), monounsaturated (7.2%), and polyunsaturated (2.4%) methyl esters. Physico-chemical properties of TB21-derived biodiesel were determined, namely, density(0.88 g cm-3), kinematic viscosity (4.1 mm s-2), iodine value (96.82), cetane number (55.31), free fatty acid content (0.15%), total acid number (0.3 NaOH mg g-1), meeting international (ASTM D6751, EN 14214) and Indian (IS 15607) standards. Thus, the direct one-pot in situ transesterification reaction using wet biomass of variant TB21 strain showed improved production and quality of biodiesel with potential large scale application using the low-cost substrate (SCBH).
Keywords: Aspergillus Terreus; Biodiesel; In situ transesterification; Mutant; Statistical optimization; Wet biomass

Atomically dispersed Co-Cu dual active sites in carbon networks as an efficient oxygen electrocatalyst - Sinha, Nibedita; Das, Chandni; Pal, Santanu; Urkude, Rajashri R.; Ahmed, Tanbir; Ghosh, Biplab; Roy, Poulomi (Dalton Transactions, 2025)
Single-atom metal-based electrocatalysts offer extended advantages by maximizing the utilization of active sites but often suffer from complex synthesis processes and low-density metal loading. The present work showcases a strategic design for integrating highly dense cobalt-copper dual atoms dispersed on a nitrogen-rich porous carbon network (CoCu-NGC). The atomically dispersed CoCu-NGC outperforms the ORR and OER activities of their single metallic counterparts (Co-NGC or Cu-NGC) and conventional noble-metal based electrocatalysts (Pt/C and RuO2). Benefitting from the electronic modulation in the dual SAC system, the CoCu-NGC displayed outstanding bifunctional performance with low Delta E values of 0.69 V in freshwater and 0.78 V in seawater, highlighting it as a potential alternative to the costly state-of-art electrocatalysts.

Brønsted basic TMMM-hydrotrope combined catalytic system for the synthesis of diverse dihydropyranochromenes in water at ambient temperature - Rajmane, Archana; Jadhav, Aishwarya; Patil, Nita; Kumbhar, Arjun (New Journal of Chemistry, 2025)
This work describes the synthesis of a range of bioactive chromenes using a solid Br & oslash;nsted organic base called `tris(morpholinomethyl)mesitylene' (TMMM). TMMM was obtained in high yields by treating tris(bromomethyl)mesitylene (TBMM) with morpholine in the presence of K2CO3 in acetonitrile at RT. It was characterized using 1H NMR and 13C NMR spectroscopy. We developed a Br & oslash;nsted base hydrotrope combined catalytic system (BBHC) by combining TMMM and a hydrotrope (sodium p-toluene sulphonate: NaPTS) for the cascade-type Knoevenagel-Michael addition reactions of various aldehydes and malononitrile with kojic acid, 4-hydroxy coumarin, dimedone, and lawsone in water. The methodology offers diversity-oriented synthesis (DOS) of dihydropyranochromenes in high yields. The BBHC catalytic system showed at least four times recyclability without appreciable loss of its activity. TMMM is an odorless, solid organic base that can be easily handled and is resistant to air and moisture. As TMMM is a solid base, it can reduce evaporation losses, improve safety and allow its easy recovery and reuse. TMMM acts as a powerful Br & oslash;nsted base that activates reactants, while an aqueous solution of NaPTS acts as a hydrotrope that increases the solubility of organic compounds in water.

Chlorophobic iron hydrogen phosphite as OER-active electrocatalyst in anion exchange membrane (sea)water electrolysis - Das, Chandni; Sinha, Nibedita; Nair, Aathira; Pal, Santanu; Joshi, Kavita; Roy, Poulomi (Small, 2025)
Seawater electrolysis is recognized as a promising technology to cater to the worldwide drive for sustainable hydrogen production; however, its practical viability is often hindered by the inevitable anode corrosion arising from the electrode side reactions owing to the presence of high chloride content which eventually degrade the electrode performance eventually. Herein, the design of unprecedented ammonium iron hydrogen phosphite (FeHPhi) along with a trace amount of Cu, is reported as the unique and much desired electrode material for seawater electrolysis due to its special chloride repellant nature along with great electrocatalytic activity toward water oxidation. The [HPO3](2-) oxoanion as Lewis base in the structure effectively restricts chloride ions, while the Fe center acts as Lewis acid offering an active site for water oxidation, also well-supported theoretically. Leveraging this frustrated Lewis pair combination, the electrocatalyst achieves a high current density of 500 mA cm(-2) at 344 mV overpotential in alkaline real seawater with impressive robustness to sustain for 200 h when operated under chlorine evolution reaction dominating region (>2 V). The electrocatalyst also demonstrates superior performance in anion exchange membrane freshwater and seawater electrolysis, demonstrating its potential applicability.
Keywords: AEM electrolyzer; chloride repellant; electrocatalyst; hydrogen production; seawater oxidation

Concurrent utilization of e- and h+ for water splitting to H2 and biomass components into value-added products: sustainable solar-driven photocatalysis towards meeting SDG7, 12 and 13 - Rajendran, Sivaraj; Saju, Simi; Mathew, Thomas; Gopinath, Chinnakonda S. (Chemical Communications, 2025)
Photocatalytic water splitting is considered one of the efficient methods for producing green hydrogen. However, the sluggish oxygen evolution reaction (OER) kinetics with four electrons limits the overall efficiency of water splitting. Biomass components/biomass derivatives are renewable carbon feedstocks that are abundantly available in nature. It is prudent to make use of electrons and holes concurrently in photocatalysis for H2 production and oxidation of biomass components, respectively, due to the latter's occurrence at a lower potential (<= 1 V) than that of the OER (>1.23 V), to value-added products (VAPs); this approach makes the entire process energy-efficient and kinetically superior. This potential approach could effectively utilize the charge carriers and abundant renewable resources of water and biomass simultaneously, meeting the sustainability, energy conversion and economic goals together. Parallel utilization of the charge carriers for redox reactions also enhances the sustainability of the catalyst system employed. Interestingly, biomass component oxidation to VAPs occurs in several steps, which not only enhances hole utilization but also provides an opportunity to design better catalysts to enhance the selectivity of the target products. Carrying out such reactions under aerobic or anaerobic conditions and different pH conditions allows fine-tuning of the product selectivity. The current review provides a detailed overview of the recent developments in this emerging area with three different types of photocatalyst systems, namely, oxide-, chalcogenide-, and carbon-based materials. Among these, the oxide-based systems generally demonstrate the highest activity with sustainability, maintaining performance for several hours. While many of these systems exhibited high selectivity towards a single product, 100% selectivity to lactic acid from glycerol was observed with a BiVO4-integrated TiO2 catalyst. Finally, the challenges, opportunities and future perspectives in this thriving field are listed, and they underscore the role of a carbon-neutral economy towards achieving a potentially sustainable future.

Concurrent utilization of e− and h+ for water splitting to H2 and biomass components into value-added products: sustainable solar-driven photocatalysis towards meeting SDG7, 12 and 13 - Rajendran, Sivaraj; Saju, Simi; Mathew, Thomas; Gopinath, Chinnakonda S. (Chemical Communications, 2025)
Photocatalytic water splitting is considered one of the efficient methods for producing green hydrogen. However, the sluggish oxygen evolution reaction (OER) kinetics with four electrons limits the overall efficiency of water splitting. Biomass components/biomass derivatives are renewable carbon feedstocks that are abundantly available in nature. It is prudent to make use of electrons and holes concurrently in photocatalysis for H2 production and oxidation of biomass components, respectively, due to the latter's occurrence at a lower potential (≤1 V) than that of the OER (>1.23 V), to value-added products (VAPs); this approach makes the entire process energy-efficient and kinetically superior. This potential approach could effectively utilize the charge carriers and abundant renewable resources of water and biomass simultaneously, meeting the sustainability, energy conversion and economic goals together. Parallel utilization of the charge carriers for redox reactions also enhances the sustainability of the catalyst system employed. Interestingly, biomass component oxidation to VAPs occurs in several steps, which not only enhances hole utilization but also provides an opportunity to design better catalysts to enhance the selectivity of the target products. Carrying out such reactions under aerobic or anaerobic conditions and different pH conditions allows fine-tuning of the product selectivity. The current review provides a detailed overview of the recent developments in this emerging area with three different types of photocatalyst systems, namely, oxide-, chalcogenide-, and carbon-based materials. Among these, the oxide-based systems generally demonstrate the highest activity with sustainability, maintaining performance for several hours. While many of these systems exhibited high selectivity towards a single product, 100% selectivity to lactic acid from glycerol was observed with a BiVO4-integrated TiO2 catalyst. Finally, the challenges, opportunities and future perspectives in this thriving field are listed, and they underscore the role of a carbon-neutral economy towards achieving a potentially sustainable future.

DABCO dicationic ionic solid supported polymer (DDIS@PS) mediated synthesis of diverse 2-amino-4H-chromenes and xanthenes: a cascade Knoevenagel-Michael approach - Rajmane, Archana; Patil, Nita; Patil, Anuradha; Kamble, Sumit; Kumbhar, Arjun (New Journal of Chemistry, 2025)
This work documented the synthesis of diverse bioactive polysubstituted 2-amino-4H-chromenes using a DABCO dicationic ionic solid (DDIS) supported on Merrifield resin (DDIS@PS) as a catalyst. The catalyst is characterized by FT-IR, SEM-EDX, and TGA analysis. The resulting PS contains supported DABCO units with free tertiary nitrogen functionality on their external surface. The catalyst effectively catalyzed cascade Knoevenagel-Michael addition reactions of various aldehydes and active methylene compounds (malononitrile and phenyl sulfonyl acetonitrile) with dimedone, yielding good to excellent results in water or ethanol at room temperature or 78 degrees C. The time required for the reaction of phenyl sulfonyl malononitrile is comparatively very high compared to malononitrile. The synthesis of bis-dimedone derivatives and 1,8-dioxo-octahydro-xanthenes was also achieved in both solvents at RT and 78 degrees C, with high yields. The catalyst demonstrated greater efficiency and maintained its activity over at least five cycles.

Deciphering the intricate mechanisms behind the selective oxidation of methane to C1 and C2 oxygenates over FeAu/γ-Al2O3 catalysts - Prabu, Marimuthu; Manikandan, Marimuthu; Rengam, B. Sathya Sai; Ramakrishnan, Archana; Raja, Abhishekram; Urkude, Rajashri R.; Ghosh, Biplab; Varghese, Jithin John; Raja, Thirumalaiswamy (Chemical Engineering Journal, 2025)
In this work, we demonstrate an eco-benign synthesis protocol for preparing gold nanoparticles and the role of the strong interaction between gold nanoparticles and iron oxide in FeAu/gamma-Al2O3 catalysts that render it an anionic (Au delta-) character while tailoring them in a smaller size. The multifunctional FeAu/gamma-Al2O3 catalyst selectively produces ethanol (95 % selectivity, similar to 240 mu mol(-1) cat) at a mild temperature of 75 degrees C without the addition of co-reactants during liquid phase methane oxidation with molecular oxygen. Conversely, Au/gamma-Al2O3 and Fe/gamma-Al2O3 catalysts exhibited high selectivity for CH3OH and HCHO. A high dispersion accompanied by strong electronic interaction between the Au delta–FeOx, as corroborated by diverse techniques, enables methane activation across the interface and coupling on the gold nanoparticles, which are responsible for the markedly improved formation of ethanol. Furthermore, in situ DRIFTS studies and DFT investigations point to a reaction mechanism of coupling of CH2OH and CH3 intermediates as the most likely route for ethanol formation.
Keywords: Anionic gold catalysts; Au-FeOx synergism; C-H bond activation; Ethanol; Methane oxidation; Methanol

Design and synthesis of C-α-D-mannopyranoside linked mesoporous silica nanoparticles - Nechooli, Hemanth K.; Ramtenki, Vilas; Kumar, Chepuri V. Suneel; Prasad, V. B. L.; Ramana, V. Chepuri (Journal of Chemical Sciences, 2025)
Mannose functionalized mesoporous silica nanoparticles (MSNs) offer a promising approach for developing more targeted, effective, and safer cancer therapies. For many of the applications, immobilization of carbohydrates like mannose onto MSNs is a crucial aspect, and in most cases, mannose moieties are connected through O-glycosidic linkages that are susceptible to acidic/enzymatic hydrolysis. To generate a stable mannose-functionalized MSN, we designed a novel C(14)-alpha-mannosylated tetradeca-1-yne. The key steps involved in the synthesis of C-mannosylated alkyne are C1-alkynylation of tri-O-acetyl-D-glucal with 1-trimethylsilyl-tetradec-1-yne, followed by stereoselective dihydroxylation and the isomerization of the internal triple bond to a terminal position. This mannose ligand was then immobilized onto azidopropyl-functionalized SBA-15 through the Cu(I)-catalyzed azide-alkyne click (CuAAC) reaction. Various physical techniques such as low-angle powder XRD, N-2 adsorption isotherms (BET), Fourier transform infrared (FTIR), high-resolution transmission electron microscopy (HRTEM), field emission scanning electron microscopy (FE-SEM), and thermogravimetric analysis (TGA) have been employed to characterize this C-mannosyl SBA-15 silica matrix. We evaluated the binding ability of C-mannosyl SBA-15 nanoparticles by using fluorescein-labelled Con-A as a target protein.
Keywords: C-mannoside; Click reaction; mannose specific proteins; Mesoporous silica nanoparticles; Zipper reaction

Development and assessment of implant material sustainability in synthesized AV fistula assisting device - Raut, Abhijeet; Uddanwadikar, V. R.; Padole, P. M.; Ookalkar, D.; Kanekar, Jugal (Materials Research Express, 2025)
Arteriovenous fistula (AVF) failure remains a significant challenge in the treatment of end-stage renal disease, leading to increased morbidity and economic burden to the patients. The availability of effective devices to address AVF is still very limited globally. In view of the high failure rate of AVF during hemodialysis, development and selection of most appropriate material for AVF device is a test for the researcher. In the present research work, the mechanical and biocompatibility tests have been conducted on the implant grade silicon materials selected to develop the device before it is subjected to animal trials. The AVF assisting device is fabricated and a custom-designed in-vitro model is developed to replicate the human anatomical surroundings. The tensile strength and the elongation of the selected implant-grade silicon in the fabricated device are tested using a universal testing machine; also, the surface structure and the chemical composition are tested using scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) respectively. The hydrophilicity and long-term performance are analyzed using a water absorption test. The biocompatibility and cytotoxicity of the material and fabricated device are determined using cell viability assay. It is observed that the silicone material used in the AVF assisting device shows strong mechanical integrity, optimum structural stability, biocompatibility and is non-cytotoxic to mammalian cell line. Thus, it can be concluded that the implant-grade silicone material is a potential candidate for the design and development of AVF assisting device due to its observed sustainability and biocompatibility.
Keywords: arteriovenous fistula (AVF) failure; AV fistula assisting device; hemodialysis; material characterization

Development of new N -4-[(7-Chloro-5-methylpyrrolo[2,1-f ] [1,2,4]triazin-4-yl)oxy]-3-fluorophenylbenzenesulfonamide analogues: exploring anticancer potential through MerTK inhibition - Sathe, Balaji Dashrath; Meenakshi, Meenakshi; Murti, Yogesh; Mane, Madhav Shivaji; Pandey, Sarvesh Kumar; Mahajan, Shriya; Rawat, Pramod; Kandhari, Harsimrat; Goel, Kapil Kumar; Dwivedi, Ashish Ranjan; Rathod, S. V. (Synlett, 2025)
Mer proto-oncogene tyrosine-protein kinase (MerTK), a part of the TAM (TYRO3, AXL, and MerTK) family, is directly correlated with metastasis and various types of cancers. The inhibition of this receptor is a promising strategy for more-effective chemotherapy. Considering the pharmacophoric features of the active domain of MerTK and the structural characteristics of the investigational drug BMS794833, we designed five new N -{4-[(7-chloro-5-methylpyrrolo[2,1- f ][1,2,4]triazin-4-yl)oxy]-3-fluorophenyl}benzenesulfonamide analogues. In cytotoxicity studies, one of the analogues displayed a significantly higher cytotoxicity than cisplatin. It showed IC50 values of 2.09, 1.96, and 3.08 mu M against A549, MCF-7, and MDA-MB-231 cancer cell lines, respectively. In drug metabolism and pharmacokinetic studies, it was the most stable analogue and displayed a moderate MerTK inhibitory potential. Molecular-docking studies were performed to corroborate the MerTK inhibition, and the same analogue achieved the most significant docking score (-12.33 kcal/mol). Docking interactions demonstrated that the imine and amine group of the 3-chloropyridine moiety of BMS794833 formed hydrogen bonds with the main chain of the ATP pocket residue Met674, while the oxygen atoms of the 4-oxo-1,4-dihydropyridine-3-carboxamide moiety established hydrogen bonds with the Lys619 and Asp741 amino acid residues of the allosteric pocket of MerTK protein. These promising results provide evidence that the N -{4-[(7-chloro-5-methylpyrrolo[2,1- f ][1,2,4]triazin-4-yl)oxy]-3-fluorophenyl}benzenesulfonamide pharmacophore can give potential insights into the development of new MerTK inhibitors.
Keywords: cancer chemotherapeutics; kinase inhibitors; metabolic studies; pyrrolotriazines; sulfonamides

Development of novel ssDNA aptamers for detection of receptor-binding domain of SARS-COV-2 - Auti, Amogh; Yadav, Pranay; Bodkhe, Rahul; Bhandari, Yogesh; Varma, Sanjana; Chaudhari, Bhushan; Rahi, Shraddha; Ghormade, Vandana; Vamkudoth, Koteswara Rao (ACS Omega, 2025)
The highly virulent and transmissible SARS-CoV-2 causes COVID-19 and poses a global public health threat. Herein cloned, expressed, and the molecular weight of the receptor-binding domain (RBD) of the SARS-CoV-2 gene encoding protein was confirmed by SDS-PAGE electrophoresis and Western blot analysis. The pivotal aim is to develop single-stranded DNA (ssDNA) aptamers for the rapid detection of SARS-COV-2 infections in humans. In this investigation, a library of nine novel ssDNA aptamers was developed by several rounds of systematic evolution of ligands by an exponential enrichment approach and assessed by an enzyme-linked aptamer assay for binding affinity against RBD antigen (Ag). An in vitro assay resulted in a varied colorimetric signal that depends on the nature of aptamer. Quantitative determination of AptRBD3, AptRBD6, and AptRBD8 aptamers exhibited excellent binding affinity against Ag in the range of 5-10 ng/mL. The putative AptRBD3, AptRBD6, and AptRBD8 aptamers were converted into peptide sequences and docked against RBD, exhibiting good binding energy of -6.8, -6.3, and -7.1 kcal/mol respectively, which were recorded. Furthermore, docking studies of ssDNA aptamers were performed using HDOCK web server to ascertain the binding mechanism and docking score perceived as -389.74, -404.28, and -390.37. Despite this, we engineered a high-affinity AptRBD3.3 aptamer that formed a single and bulged loop, which improved binding affinity, resulted in a docking score of -361.56, and exhibited sensitivity at 4 ng of Ag of SARS-CoV-2. Moreover, computational modeling of AptRBD3.3 revealed an intriguing significant binding affinity with the RBD mutant SARS-CoV-2 S-UK variant (PDB ID: 7EDG) with a docking score of -350.21. In conclusion, the AptRBD3.3 aptamer can be used for the development of lateral flow device and electrochemical sensors for rapid, low-cost, and accurate detection of COVID-19 infection in humans for point of care diagnostics.

Diastereoselective synthesis of cyclic and spirocyclic quaternary carbons via iron-catalyzed ring contraction of cyclic ketones: a formal synthesis of perhydrohistrionicotoxin - Survase, Vijayanand U.; Rokade, Avinash D.; Handore, Kishor L. (Organic Letters, 2025)
The iron-catalyzed hydrogen atom transfer (HAT)-initiated Dowd-Beckwith rearrangement presents a new approach for synthesizing cyclic and spirocyclic quaternary carbons from readily available beta-keto esters and cyclic diketones with high yields. This reaction proceeds in a stereocontrolled manner, enabling the formation of synthetically valuable cyclic ketones with two contiguous stereocenters, including quaternary centers. This transformation introduces an innovative bond disconnection strategy for ring-contraction reactions. Additionally, a short formal synthesis of perhydrohistrionicotoxin was efficiently achieved using this methodology.

Discovery and biological evaluation of nitrofuranyl-pyrazolopyrimidine hybrid conjugates as potent antimicrobial agents targeting Staphylococcus aureus and methicillin-resistant S. aureus - Saini, Sapna; Reddy, G. Lakshma; Gangwar, Anjali; Kour, Harpreet; Nadre, Gajanan G.; Pandian, Ramajayan; Pal, Sunny; Nandi, Utpal; Sharma, Rashmi; Sawant, Sanghapal D. (RSC Medicinal Chemistry, 2025)
Nitrofuran and pyrazolopyrimidine-based compounds possess a broad antimicrobial spectrum including Gram-positive and Gram-negative bacteria. In the present work, a series of conjugates of these scaffolds was synthesized and evaluated for antimicrobial activity against Staphylococcus aureus and methicillin-resistant S. aureus (MRSA). Many compounds showed MIC values of <= 2 mu g ml-1, with compound 35 demonstrating excellent activity (MICs: 0.7 and 0.15 mu g ml-1 against S. aureus and MRSA, respectively) and safety up to 50 mu g ml-1 in HepG2 cells. Compound 35 also exhibited no hemolytic activity, biofilm eradication, and effectiveness against efflux-pump-overexpressing strains (NorA, TetK, MsrA) without resistance development. It showed synergistic effects with vancomycin (S. aureus) and rifampicin (MRSA). Mechanistic studies revealed that compound 35 exhibits good membrane-targeting abilities, as evidenced by DAPI/PI staining and scanning electron microscopy (SEM). In an intracellular model, it reduced bacterial load efficiently in both S. aureus and MRSA strains. With a strong in vitro profile, compound 35 demonstrated favorable oral pharmacokinetics at 30 mg kg-1 and potent in vivo anti-MRSA activity, highlighting its potential against antibiotic-resistant infections.

Dopant and exfoliation induced simultaneous modification of charge density and C―C coupling sites for efficient CO2 photoreduction to ethylene - Das, Kousik; Chakraborty, Subhajit; Kediya, Siddhi; Singh, Ashutosh Kumar; Das, Risov; Mondal, Soumi; Riyaz, Mohd; Goud, Devender; Dutta, Nilutpal; Vinod, Chathakudath P.; Peter, Sebastian C. (Angewandte Chemie-International Edition, 2025)
The photochemical conversion of CO2 into C2+ products has emerged as an attractive method for synthesizing valuable chemicals and fuels using abundant solar energy. However, the challenge lies in enhancing the efficiency and selectivity of C2+ product formation. In this study, we employed a heteroatom doping strategy to optimize the photocatalytic parameters and achieve excellent efficiency and selectivity in the photocatalytic CO2 reduction to C2+ product formation. Our experimental analysis revealed that the local electronic structure of the catalyst, modified by In-doping, enables enhanced efficiency. Additionally, the incorporation of Cu facilitates the coupling of C1 intermediates, resulting in excellent selectivity towards C2+ products. The CO2 reduction performance is further enhanced through exfoliation, which increases the exposure of active sites and extends the charge carrier lifetime by reducing the charge diffusion length. We report that the rate of formation of C2H4 reached 54.3 mu molh(-1)g(-1) with an outstanding selectivity of 91% over the exfoliated CuIn-doped AgBiP2S6 catalyst. By elucidating the role of heteroatom doping and exfoliation in enhancing both the efficiency and selectivity of C2+ product formation, our study contributes to advancing the development of sustainable and efficient photocatalytic CO2 conversion technologies.
Keywords: C & horbar; C coupling; CO2 reduction; Doping; Exfoliation; Photocatalysis

Dual agonist/antagonist modulation of α9-containing nicotinic acetylcholine receptors by 2-ammoniumethyl ethers of stilbenol and stilbenol analogues - Giraudo, Alessandro; Tae, Han-Shen; Hung, Andrew; Richter, Katrin; Shivankar, Bhavana; Armano, Edoardo; Grau, Veronika; Pallavicini, Marco; Adams, David J.; Bolchi, Cristiano (Journal of Medicinal Chemistry, 2025)
2-(Cyclohexyldimethylammoniumethyl)ether of 4-stilbenol (2), and its styryl-modified analogues 21 and 22, were identified as lead compounds from a series targeting human alpha 9 alpha 10, alpha 9, and alpha 7 nicotinic acetylcholine receptors (nAChRs). Compounds 2 and 21 exhibited potent, and subtype-selective modulation of alpha 9-containing receptors, with low nanomolar IC50 values and dual agonist/antagonist activity in a concentration-dependent manner. In contrast, compound 22 acted as a selective, pure antagonist. Molecular dynamics (MD) simulations of compound 21 supported a concentration-dependent allosteric mechanism, with orthosteric binding at low concentrations and vestibular site interaction at higher levels. In a human monocytic cell line, all three compounds inhibited ATP-induced IL-1 beta release at nanomolar concentrations. These findings identify alpha 9 alpha 10-selective ligands as promising scaffolds for the development of nonopioid analgesics and immunomodulators, with favorable selectivity over alpha 7 nAChRs to minimize CNS-related side effects.

Effectiveness of 3-amino-2-thiocyanato-α, β-unsaturated carbonyl compounds against chikungunya virus - Alagarasu, Kalichamy; Dhote, Radhika; Bagad, Pooja K.; Kharikar, Dwidhesh; Patil, Poonam; Roy, Diya; Shukla, Shridhar; Cherian, Sarah; Senthilkumar, Beeran; Parashar, Deepti (Future Medicinal Chemistry, 2025)
Aim Chikungunya fever (CHIKF) caused by the chikungunya virus (CHIKV) is characterized by the presence of long-term polyarthralgia in a minor proportion of the infected patients. Currently, there are no FDA-approved antivirals available. This study evaluated the anti-CHIKV potential of 16 synthetic 3-amino-2-thiocyanato-alpha, beta-unsaturated carbonyl compounds and elucidated their probable mechanisms of action. Methods Anti-CHIKV activity of 16 compounds were investigated in Vero CCL-81 cells using focus forming unit assay (FFU). Dose-dependent and time-dependent antiviral assays were performed for the effective compounds. Molecular docking was performed to find out their interactions with viral proteins. Results Five compounds showed promising anti-CHIKV activity by reducing viral titer with >1 log10 FFU/ml. Dose-dependent studies revealed that the compound 3 g was more effective in reducing the virus titer with a half-maximal inhibitory concentration (IC50) of 0.4315 mu M and a selectivity index of 35.99. Docking analyses revealed that all the compounds mainly interact with the non-structural proteins of CHIKV. Conclusions These findings demonstrate the in vitro anti-CHIKV activity of these compounds, and their possible mode of action via interference with early stages of infection and replication processes. This study warrants further preclinical and clinical evaluation to establish their safety and efficacy as novel anti-CHIKV therapeutics.
Keywords: 3-amino-2-thiocyanato-alpha; antivirals; beta-unsaturated carbonyl compounds; Chikungunya virus (CHIKV); nsP2 helicase; therapeutics

Electrochemical deconstruction of waste polyvinylidene chloride (PVDC) to value-added products in batch and flow - Mishra, Subhadip; Kar, Sourav; Rangappa, Raghavendrakumar; Patil, Prashant; Kadam, Vijay; Chikkali, Samir H.; Samanta, Ramesh C. (Chemistry-A European Journal, 2025)
Chlorinated polymers have made enormous contributions to materials science and are commercially produced on a large scale. These chlorinated polymers could be recycled as chlorine sources to efficiently produce valuable chlorinated compounds owing to their facile release of HCl. Although the thermal stability of PVDC is low compared to PVC, this can be advantageous in terms of easy and fast dehydrochlorination. Herein, we report an efficient electrochemical chlorination using poly(vinylidene chloride) (PVDC) as a chlorine source that works in an undivided cell and applies to a good number of examples. This method works on commodity polymers such as waste PVDC-PVC pharma blister film, PVDC-PO multilayer food packaging, and compression molded sheets of Ixan PVDC (with heat stabilizer) with similar efficiency. Furthermore, this method also provides the dechlorination of PVDC up to 98 %, leading to unsaturated dechlorinated material. Converting PVDC into more stable unsaturated compounds, the release of harmful chlorine-containing gases during incineration can be minimized. Additionally, this method is not only restricted to batch processes but an electroflow process for PVDC dechlorination and electrosynthesis has also been demonstrated.
Keywords: chlorination; Electrochemical recycling; Electroflow-synthesis; Graphitic material; Polyvinylidene chloride

Electronic, magnetic, and mechanical properties of co-doped GaSb: A promising diluted magnetic semiconductor - Samant, Ramnath; Saraf, Deepashri; Adhikari, Rajendra P.; Shilkar, Omkar; Raikar, Sakshit; Silveira, Allan; Sawant, Manthan; Sappati, Subrahmanyam; Joshi, Niharika; Desai, Ashish M. (Journal of Magnetism and Magnetic Materials, 2025)
{Understanding the interplay between magnetism and the electronic structure is crucial for the development of novel spintronic materials. This study employs density functional theory (DFT) calculations to investigate these properties in cubic Gallium Antimonide (GaSb) doped with Cobalt (Co) (Ga1-xCoxSb
Keywords: Density functional theory; Dilute magnetic semiconductors; Electronic properties; GaSb; mechanical properties; Spintronic materials

Energy-saving H2 production through H2S electrolysis accompanying solid sulfur recovery using a Ni3S2/Ni3N heterostructure as the electrocatalyst - Sinha, Nibedita; Das, Chandni; Pal, Santanu; Roy, Poulomi (ACS Applied Energy Materials, 2025)
The thermodynamically feasible electrochemical sulfion oxidation reaction (SOR) is advantageous for degrading the toxic H2S pollutant into the value-added chemical sulfur but often suffers from catalyst passivation due to blockage of electroactive sites by accumulation of solid sulfur. The strategic design of electrocatalysts with enhanced electrochemical activity and improved sulfur tolerance is thereby crucial to fully harness the benefits of the SOR. In this work, we developed nickel sulfide nanorods decorated with nickel nitride nanoparticles directly grown on conductive nickel foam as an efficient trifunctional electrocatalyst for the SOR, oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). Optimized Ni3S2/Ni3N showed lower electrode potentials of 0.25, 1.487, and 0.89 V to achieve a benchmark current density of 10 mA cm(-2) for the SOR, OER, and HER, respectively. The hybrid H2S electrolysis setup employing a Ni3S2/Ni3N electrocatalyst drastically reduced the cell potential by 1.24 V compared to that of conventional water electrolysis at a current density of 200 mA cm(-2). Having said that, heterostructure formation not only enhances the activity for the SOR but also helps to avoid sulfur poisoning, enabling the electrocatalyst to sustain for 100 long hours at a high current density of 100 mA cm(-2). Consequently, the approach with the developed electrocatalyst has the ability to reduce the energy consumption by 59.22%, which can make rigorous, economically viable H-2 production driven by solar energy.
Keywords: energy-economic; H-2 production; H2S electrolysis; heterostructure; solidsulfur

Enhanced electrocatalytic performances of NiCr layered double hydroxides by oxalate intercalation in anion exchange membrane water electrolysis - Pal, Santanu; Sinha, Nibedita; Das, Chandni; Chauhan, Inderjeet; Ahmed, Tanbir; Roy, Poulomi (ACS Applied Materials & Interfaces, 2025)
Layered double hydroxides (LDHs) have attracted much attention these days in the field of water electrolysis due to easy modulation in their layered structure and properties. Herein, NiCr-LDH has been developed, and its interlayer spacing has been considerably increased by oxalate intercalation. Such increased interlayer spacing allows easy access of hydroxides to a large number of electroactive sites and thereby boosts the electrocatalytic performances both for oxygen and hydrogen evolution reactions. Being very active toward both the electrocatalytic reactions, the oxalate-intercalated NiCr-LDH was further explored in an alkaline anion exchange membrane water electrolyzer (AEMWE), achieving 800 mA cm-2 at 1.88 V cell voltage at an operating temperature of 60 degrees C. In fact, the electrolyzer efficiency has been determined to be as high as 69.66%, and the calculated H2 production cost was found to be \$0.97 per gasoline-gallon equivalent, which is well below the targeted cost by the Department of Energy, USA. The electrocatalyst was also examined in harsh alkaline media, like highly saline or seawater, which also indicated its ability to carry out sustainable seawater electrolysis, restricting chlorides to a great extent. Interestingly, post-electrolysis characterization reveals the fact that oxalate decomposition aided carbonate formation within interlayers of NiCr-LDH, and high affinity toward hydroxides is responsible for restricting chlorides during the electrolysis process, apart from the great electrocatalytic activity.
Keywords: Anion exchange; hydrogen production; interlayerspacing; Layered double hydroxide; Sustainable; water electrolyzer

Enhanced Production and Techno-Economic Analysis of Sustainable Biofuel Production via Continuous Hydrogenation of Furfural Using the Cu-ZnO-Al2O3 Catalyst - Saha, Biswajit; Racha, Arundhathi; Chaudhary, Puneet Kumar; Singh, Brijesh Kumar; Samanta, Chanchal; Newalkar, Bharat L. (ACS Sustainable Chemistry & Engineering, 2025)
2-Methylfuran is a perfect green solution on the pathway of finding alternative fuels. We report here for the first time the continuous production of 2-methylfuran (2-MF), a sustainable biofuel from biomass-derived furfural (FFA), over an industrial Cu-ZnO-Al2O3 (CZA) catalyst. The modified coprecipitation method provides a uniformly dispersed crystalline structure to the synthesized catalysts, along with intended copper (Cu) loading achievement. Different Cu loadings affect the catalytic behavior and activity. Hence, CZA catalysts with two Cu loadings of 9.8 and 4.7% were studied in detail, denoted as C1 and C2, respectively. The catalysts were characterized via XRD, N-2 adsorption, H-2-TPR, NH3-TPD, XPS, ICP-MS, and TEM. Remarkably, the prepared catalysts demonstrate balanced acid sites with mesopores, a high surface area and pore volume, and better controlled nanoparticle size promoting catalytic activity. TEM and H-2-TPR studies reveal a better Cu dispersion. Existence of Cu2+ and Cu (+) even after reduction by XPS study proves the efficiency of the synthesized catalysts. Furthermore, TGA indicates the stability of CZA catalysts. To understand catalytic activity and selectivity, the investigation was carried out in a packed-bed fixed-bed stainless steel reactor. Better physiochemical properties result in high FFA conversion of 33.8% and selectivity of 99.6% for 2-MF. No side products were formed during reaction otherwise improbable via the continuous method. Compared with available literature, the CZA catalyst was found to exhibit superior catalytic performance. The reaction kinetics of furfural hydrogenation to 2-methylfuran was investigated, and it was found that the reaction order is high, and the activation energy was 61.2 kJ/mol. The rate constant k clearly obeyed the Arrhenius law from 180 to 220 degrees C. In addition, evaluation of reaction kinetics also indicated the absence of ring hydrogenation and decarbonylation products, which is difficult to achieve. Finally, the process shows significant economic viability, which resulted in the minimum levelized production cost for 2-methylfuran of 173,068.16 \$/ton with 78.32% overall energy efficiency.
Keywords: 2-methylfuran (2-MF); continuous production; Cu-ZnO-Al2O3; economic viability; furfural; green synthesis

Enzymatic pathway for kupyaphore degradation in mycobacterium tuberculosis: mechanism of metal homeostasis and turnover - Bhosale, Rashmi S.; Chakraborty, Arnab; Wong, Tsung-Yun; Masal, Dattatraya P.; Choudhury, Rahul; Srivastava, Sonali; Reddy, D. Srinivasa; Aldrich, Courtney C.; Kamat, Siddhesh S.; Mohanty, Debasisa; Gokhale, Rajesh S. (ACS Chemical Biology, 2025)
Metallophores are essential for metal homeostasis, regulating availability, and mediating host-pathogen interactions. Kupyaphores are specialized metallophores produced by Mycobacterium tuberculosis (Mtb) that primarily chelate zinc to support bacterial survival. Elevated kupyaphore levels early in infection highlight their importance, while their rapid decline, despite increasing bacterial loads, indicates tightly regulated mechanisms of production, consumption, and degradation. However, the processes driving kupyaphore catabolism and their role in preventing zinc toxicity in Mtb remain unclear. Here, we show that covalent modification of the isonitrile moiety in kupyaphores releases zinc, triggering degradation through a sequential three-step enzymatic pathway encoded by Mtb. Isonitrile hydratase converts isonitrile groups into formamides, which are subsequently processed into amines by N-substituted formamide deformylase and ultimately oxidized to beta-ketoesters by amine oxidases. The biological significance of this pathway is underscored by the upregulation of these genes under metal-depleted and biofilm-forming conditions. Mutant Mtb strains lacking these genes exhibit impaired growth in metal-limiting environments and reduced levels of biofilm formation. Catalytic intermediates detected in Mtb cultures and infected mouse lung tissues confirm the pathway's in vivo activity. Further, genome mining reveals that similar enzymes are conserved across organisms producing isonitrile-containing metabolites, emphasizing the broader importance of this pathway. Understanding these processes could pave the way for novel therapeutic strategies targeting kupyaphore catabolism.

Exploring the structural and photophysical properties of tri-cation mixed halide double perovskites (Cs2AgIn0.85-XCeXBi0.15Cl6) for high-performance phosphor-based WLEDs - Ravi, Nalini; Kanapathi, Prakash; Mohan, Subramaniam; Appadurai, Tamilselvan (Dalton Transactions, 2025)
Owing to their superior optoelectronic properties, lead-free halide double perovskites (HDPs) have been extensively studied for a wide range of optoelectronic applications, especially for fabricating white light-emitting diodes (WLEDs). Considering white light emission, the HDP structure's dual octahedral configuration facilitates greater lattice distortion, thereby fostering strong electron-phonon coupling-derived self-trapped exciton (STE) emission upon photoexcitation. Herein, we propose facile fabrication of a highly feasible phosphor-converted white light LED and an intensive analysis of the structural, compositional and photophysical properties of a tri-cation mixed halide double perovskite. We chose Cs2AgIn0.85Bi0.15Cl6 as a potential candidate for electroluminescent-based white light LED devices as its composition exhibits high stability, direct-allowed transition, and a notable photoluminescence quantum yield. However, we incorporated a lanthanide ion (Ce3+) into this cubic HDP structure via tri-cation mixing at the B `' site (Cs2AgIn0.85-XCeXBi0.15Cl6) to internally disturb structural periodicity and further enhance STE emission. Initially, powder XRD revealed the lattice expansion induced by Ce3+ incorporation, while XPS and TEM verified the substitution of Ce3+ at the In3+ site. Meanwhile, compositional and optical studies established the role of Ce3+ in retaining the direct allowed transition by effectively replacing the In3+ site. Urbach energy (EU), a measure of energetic disorderness at band edges, was found to be significantly reduced, showing a value of 135 meV for the Ce-5% sample. Most significantly, PL emission studies revealed an appreciable enhancement in the PL intensity with a prolonged STE lifetime of 670 ns for Cs2AgIn0.80Ce0.05Bi0.15Cl6, indicating improved radiative recombination. Besides, excitation-dependent Pl and PLE studies revealed that the emission solely came from the STE states. Elaboratively, vibrational studies elucidated that the Ce-5% sample exhibited a restabilized elpasolite structure and enhanced lattice phonons, which ultimately helped in boosting STE emission, as proven by the Huang-Rhys factor (S = 13). Finally, an efficient and durable phosphor-converted WLED was fabricated, and its performance was assessed, revealing CIE coordinates of (0.35,0.32), a CCT of 4368 K, and an extremely high CRI (Ra) of 92. Thus, our work provides an exclusive strategy to enhance the STE emission for potential application in electroluminescent-based WLED devices.

Facile and eco-friendly synthesis of Mn2O3 nanoparticles via microwave-assisted glycerol-thermal method - Yadav, Akash; Jha, Ratnesh; Bhatkar, Akash; Gehlot, Bhavika; Kamble, Aditi; Manikandan, Marimuthu; Bhosale, Hritvik; Vaishnav, Vishal; Rathod, Rutik; Umbarkar, Shubhangi; Raja, Thirumalaiswamy; Bhatte, Kushal D. (Journal of Chemical Sciences, 2025)
Microwave-assisted efficient synthesis of nanosized manganese oxide (Mn2O3) is reported using glycerol and manganese acetate. Glycerol in this reported methodology acts as an efficient solvent for this nanomaterial synthesis under microwave radiation. This reported method enables the synthesis of nanosized Mn2O3 without further use of additives, stabilizers, and bases other than glycerol and manganese precursor. Glycerol is a renewable biomaterial derived nonvolatile and nontoxic, safe solvent. It has a high boiling point and dielectric constant, which makes it an ideal solvent for microwave synthesis. The synthesized nanosized Mn2O3 was analyzed by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. We examined the catalytic properties of as-synthesized Mn2O3 for cinnamyl alcohol oxidation to cinnamaldehyde. In this oxidation activity experiment, nanosized Mn2O3 exhibits good conversion and selectivity towards the desired product. We also made an attempt to understand the probable mechanism of nanomaterial formation and found some conclusive evidence to support it. This research methodology is facile, energy efficient, and involves minimum chemicals for synthesis. It makes this reported methodology not only economically attractive but also environmentally friendly, which aligns well with green chemistry principles.
Keywords: Glycerol; green chemistry; Nanosized Mn2O3; nanostructured catalysis

Fermi-level equilibrium-driven trap filling in multibandgap PbS quantum dot solids enabling record voltage generation and improved carrier transport in high-performance solar cells - Dambhare, Neha V.; Biswas, Arindam; Sharma, Anjali; Shinde, Dipak Dattatray; Mitra, Anurag; Girade, Vrushali S.; Rath, Arup Kumar (ACS Energy Letters, 2025)
To leverage the unique optical properties of quantum dots (QDs) in solar cells, it is crucial to address electronic traps from unsaturated surface states of high surface area QDs. Despite advancements in surface passivation, even the best-coupled QD solids exhibit significant sub-bandgap trap states. This study introduces engineered multibandgap PbS QD solids that achieve passivation of deep traps below the conduction band through electron migration from dopant QDs. Our findings indicate that electron flow, driven by Fermi energy balancing in blend films, fills deep trap states, reducing trap density by half and shifting trap energy positions closer to the conduction band. During electrical transport, trap filling minimizes trapping and detrapping events, enhancing overall carrier mobility, despite higher-bandgap dopant QDs not contributing to carrier transport due to their unfavorable energy positions. Improved trap passivation in coupled QD solids leads to a record V oc of 725 +/- 10 meV for the 1.33 eV excitonic peak of QDs and a power conversion efficiency exceeding 14% in solar cells.

Genomic insights and biotechnological potential of “Mesobacillus aurantius” strain S13: a canthaxanthin pigment-producing bacterium - Karthik, Shankar; Raman, Gurusamy; Srinivasan, Arumugam; Dastager, Syed Gulam; Wagh, Vasudev; Ayyadurai, Niraikulam (Gene Reports, 2025)
<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;">This study explores the discovery and characterization of pigments, from a microorganism thriving under environmentally challenging conditions. Utilizing a polyphasic taxonomic approach, we successfully isolated and identified a bacterial strain S13 within the <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;">Mesobacillus<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;"> genus and Bacillaceae family, designated as “<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;">Mesobacillus aurantius<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;">” S13. We confirmed the species based on comprehensive phenotypic, physiological, and biochemical analyses, molecular phylogenetics, DNA–DNA hybridization, average nucleotide identity, and whole-genome sequencing. The strain S13 (MTCC13141 = VKM B-3583 = NBIMCC 9084) possesses a 4.81 Mbp genome that encodes genes for pigment production. Notably, this study uses various spectroscopic methods to characterize canthaxanthin, an orange pigment and delineates its biosynthetic pathway from the genome of S13. The methylerythritol phosphate (MEP) pathway and canthaxanthin biosynthesis genes highlight the capacity of the bacterium to synthesize crucial isoprenoids and terpenoids, including canthaxanthin. This research provides a detailed account of the isolation, characterization, and taxonomic classification 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;">Mesobacillus aurantius<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;">” S13 and underscores the potential biotechnological applications of the bacterium in producing pharmaceuticals, biofuels, and cosmetics. Therefore, “<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;">Mesobacillus aurantius<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;">” S13 is a potentially valuable microbial resource for the industrial production of isoprenoids and pigments.

Germylene mediated reductive C-C and C-N coupling of an isocyanide and its device application - Gour, Kritika; Pramanik, Debjit; Dash, Soumya Ranjan; Shinde, Dipak Dattatray; Venugopal, Geethu; Vanka, Kumar; Rath, Arup K.; Sen, Sakya S. (Angewandte Chemie-International Edition, 2025)
We have demonstrated a unique reductive coupling of 4-iodophenyl isocyanide, facilitated by a perimidine-based N-heterocyclic germylene (NHGe), which yields a bis-spirogerma compound featuring simultaneous C-C and C-N bond formation. This reaction, which leads to the oxidation of germanium from +2 to +4, represents a significant departure from previously documented isocyanide-germylene interactions. The product exhibits extensive conjugation across its bicyclic C4Ge2N2 framework, conferring distinct photophysical properties, including prominent orange luminescence in both solution and solid states. The photophysical properties are supported by the TD-DFT calculations confirming an n ->pi* transition. The potential application of this compound in optoelectronic devices, particularly as a hole transport layer in PbS quantum dot solar cells, is also explored, with promising preliminary results.
Keywords: Germylene; hole transport layer; Isocyanide; reductive coupling

Gram-scale synthesis of (±)-tylophorine - Masal, Dattatraya P.; Reddy, D. Srinivasa (Synlett, 2025)
We report a practical scalable synthesis of the natural product (+/-)-tylophorine by using an operationally simple protecting-group-free route from readily accessible starting materials. Synthesis of a cyclic N-acetyl diester compound through cyclization, followed by two key steps (decarboxylation and a Clemmensen reduction), provides access to the target molecule.
Keywords: alkaloids; Clemmensen reduction; decarboxylation; gram-scale synthesis; tylophorine

Green one-pot three component synthesis of thiazolidine-2,4-dione based bisspirooxindolo-pyrrolidines with [Bmim]BF4: their in vitro and in silico anti-TB studies - Rukyanaik, V.; Gamidi, Rama Krishna; Kumari, Jyothi; Sriram, Dharmarajan; Basavoju, Srinivas (Molecular Diversity, 2025)
A simple and effective three-component one-pot green methodology was employed for the synthesis of a new thiazolidine-2,4-dione based bisspirooxindolo-pyrrolidine derivatives using [Bmim]BF4 ionic liquid via [3 + 2] cycloaddition reaction. It is an environmentally benign, column chromatography-free, shorter reaction time, good yield and easy product isolation method. The synthesized compounds 10a-x, were thoroughly characterized by using various spectroscopic methods like FT-IR, H-1 NMR, C-13 NMR, Mass spectrometry and finally by single crystal X-ray diffraction method. In vitro anti-tubercular (anti-TB) activity studies were carried out on these synthesized compounds, and they showed good to moderate anti-TB activity against Mycobacterium tuberculosis H37Rv strain. The compound 10a exhibited good anti-TB activity, with an MIC (Minimum Inhibitory Concentration) value of 12.5 mu g/mL, and the compounds 10m, 10o and 10r showed moderate activity with an MIC value of 25.0 mu g/mL. Remaining compounds exhibited poor activity against Mycobacterium tuberculosis. Ethambutol, rifampicin and isoniazid were used as standard drugs. Furthermore, in silico molecular docking experiments on the TB protein (PDB ID: 1DF7) were carried out to understand the binding interactions, and they showed least binding energy values ranging from -8.9 to -7.2 kcal/mol.
Keywords: 4-dione based bisspirooxindolo-pyrrolidines; Anti-TB activity; green synthesis; Molecular docking; Thiazolidine-2; [3+2] cycloaddition reaction; [Bmim]BF4

Harnessing DABCO ionic salts for synthesis of heterocycles via multi-component reactions - Rajmane, Archana; Narande, Poonam; Patil, Nita; Kumbhar, Arjun (Chemical Papers, 2025)
The review article discusses the advancements in synthesis and applications of acidic, basic, and neutral 1,4-diazabicyclo[2.2.2]octane (DABCO) ionic salts in multi-component reactions. Compared to imidazolium-based ionic salts, the number of DABCO-based ionic salts is significantly lower. Recently, there has been increasing focus on these salts due to their selective salt formation capabilities. A significant challenge lies in the limited availability of physical data regarding DABCO-based ionic salts; hence, most of them are not ionic liquids. While many of these salts could be reused several times with only a minimal reduction in their catalytic effectiveness, there is a significant limitation in the availability of DABCO-based salts.
Keywords: 1; 4-Diazabicyclo[2.2.2]octane; Ionic salts; Multi-component reactions; Recyclability

Harnessing microRNAs and their targets for salt stress tolerance in Pandanus odorifer - Rashmi, Deo; Barvkar, Vitthal T.; Nadaf, Altafhusain B.; Kadoo, Narendra Y. (Journal of Plant Biochemistry and Biotechnology, 2025)
Salinity poses a formidable challenge to agriculture, detrimentally impacting plant growth and the yield of several crops globally. Pandanus odorifer (Forssk.) Kuntze is a highly salt-stress resilient plant that grows naturally along the coastal regions of Asia, Southeast Asia, and Polynesia. It is frequently found as a frontier species along the sandy shores receiving constant salt sprays. MicroRNAs (miRNAs) play essential regulatory roles in growth, development, and combating various biotic and abiotic stresses. Thus, characterizing miRNAs and their targets is critical to understanding their roles in salt stress tolerance. Through a rigorous analysis based on homology, secondary structure and signatures of other miRNA genes, we identified 52 conserved nonredundant miRNAs from the P. odorifer transcriptome data. These miRNAs were diverse and belonged to 23 miRNA phylogenetic families. Several miRNAs, including pod-MIR156a, pod-MIR164d, and pod-MIR535d, demonstrated distinct expression patterns in response to salt stress. Their target genes exhibited opposing expression trends, corroborating the intricate miRNA-target relationship. Delving deeper into their influence, we discovered that these miRNAs mainly targeted transcription factors that are known for their pivotal roles in stress responses. We also detected four miRNA-star (miRNA*) sequences (the complementary strands of functional mature miRNAs), which supports the authenticity of the identified miRNAs. This study unveils the intricate regulatory mechanism through which miRNAs may reinforce salt stress tolerance in P. odorifer, providing a promising avenue for enhancing crop resilience to various stresses through miRNA-based strategies.
Keywords: Abiotic stress; microRNA; miRNA targets; Salinity tolerance; salt stress; Transcription factors

Heteroatom-synergistic effect on anchoring polysulfides in chalcone-linked nanographene covalent organic frameworks for high-performance Li―S batteries - Ranjeesh, Kayaramkodath Chandran; Javaregowda, Bharathkumar H.; Gaber, Safa; Bhauriyal, Preeti; Kumar, Sushil; Skorjanc, Tina; Finsgar, Matjaz; Heine, Thomas; Krishnamoorthy, Kothandam; Shetty, Dinesh (Advanced Science, 2025)
Lithium-sulfur (Li & horbar;S) batteries are an attractive option for future energy storage devices because they offer higher theoretical specific capacity, energy density, and cost-effectiveness than commercial lithium-ion batteries. However, the practical applications of Li & horbar;S batteries are significantly limited by the shuttle effect caused by intermediate lithium polysulfides (LiPSs) and slow redox kinetics. In this study, the molecular engineering of chalcone-linked, sp(2)-bonded nanographene-type covalent organic frameworks (COFs) as sulfur hosts is reported to enhance interactions with LiPSs, thereby effectively suppressing the shuttle effect. The developed sulfur-hosting cathode material demonstrated outstanding battery performance, surpassing most reported materials by achieving a specific capacity of 1228 mA h g(-1) at 0.5C, with 80% retention after 500 cycles and an average Coulombic Efficiency (C.E.) of 99%. Additionally, the mechanisms of sulfur immobilization, the subsequent conversion into lithium polysulfides (LiPSs), and their binding energies with COFs are investigated using density functional theory (DFT) calculations. These findings offer valuable insights into the structure-property relationships essential for developing more efficient sulfur-hosting cathodes.
Keywords: anion-pi interaction; covalent organic frameworks; lithium-sulfur battery; nanographene; polysulfide shuttle

High performance and enhanced stability of Mn-Co3V2O8 coral-like structure for supercapacitor applications - Venkatesan, Sethuraman; Rajkumar, Palanisamy; Radhika, Govindaraju; Iyer, Maalavika S.; Manigandan, Ramadoss; Rajaiah, Dhilip Kumar; Radhakrishnan, S.; Raman, Sasikumar; Marimuthu, Senthilkumaran; Kim, Jinho (ACS Applied Energy Materials, 2025)
This study explores Mn-doped Co3V2O8 as a promising electrode material for high-performance supercapacitors. Mn doping significantly enhances the electrochemical properties of Co3V2O8, resulting in improved specific capacitance and cycling stability. Structural characterization reveals a coral-like morphology that increases the active sites and facilitates efficient charge transport and ion diffusion. Electrochemical tests show an impressive specific capacitance of 2352 F g(-1) in 2 M KOH at 1 A g(-1). For the assembled MCV5//AC asymmetric supercapacitor device, it has a high capacitance retention of 87.6% and a high Coulombic efficiency of 96% over 5000 cycles. The developed asymmetric MCV5/AC supercapacitor device achieved an energy density of 45 Wh kg(-1) and a power density of 750 W kg(-1). These findings establish Mn-doped Co3V2O8 as a durable and efficient electrode material, offering valuable insights into the relationship between the morphology and electrochemical performance. This work provides a foundation for the development of advanced materials for sustainable energy storage applications
Keywords: Co3V2O8; Electrode material; Energy storage; stability; supercapacitor

Highly efficient, co-solvent assisted glycolytic depolymerization of waste polyethylene terephthalate (PET) into Bis(2-hydroxyethyl) terephthalate (BHET) monomer - Markandeya, Nishant; Solanki, Bhanupratap Singh; Ramalingam, Karthick; Kamble, Sanjay (Industrial & Engineering Chemistry Research, 2025)
Recently, growing use of plastics has led to the accumulation of waste that must be dealt with paramount priority. Among all plastic wastes, polyethylene terephthalate (PET) is the most widely used thermoplastic polyester globally because of its extensive applications in packaging, automotive manufacturing, and textile markets. Thus, there is a need to develop a sustainable and viable PET recycling process. This study presents an efficient solvothermal process for the depolymerization of PET into bis(2-hydroxyethyl) terephthalate (BHET) using co-solvent assisted glycolysis. The process uses N-methylimidazole (NMI) as a cosolvent with ethylene glycol (EG), achieving complete PET conversion and 92% BHET yield under optimized reaction conditions (180 degrees C, 45 min, PET:EG:NMI ratio of 1:7:8) without using a catalyst. The effectiveness of the cosolvent system was attributed to its polarity and H-bonding capabilities, which enhanced polymer swelling and facilitated the depolymerization. SEM analysis revealed pore formation in the NMI-treated PET, whereas FTIR studies confirmed the progressive formation of ester groups during depolymerization of PET. Kinetics studies based on different models indicated that, at higher temperatures, the surface reaction and homogeneous model proved to be rate-controlling due to the elimination of mass transfer limitations. A preliminary technoeconomic analysis and recyclability experiments further supported the scalability potential of the present study.

Hydrodeoxygenation of guaiacol to cyclohexanol using noble metal-supported Ni-based perovskite-derived catalysts - Marimuthu, Prabu; Raja, Thirumalaiswamy; Vinu, Ravikrishnan (ChemCatChem, 2025)
This study focuses on the role of noble metal-doped Ni-based perovskites, specifically LaNiO3 and NiTiO3 catalysts in the hydrodeoxygenation (HDO) of guaiacol. The findings demonstrate that reduced Ru-LaNiO3 catalyst achieved superior performance with 100% guaiacol conversion and a 75% selectivity toward cyclohexanol, compared to reduced Ru-NiTiO3, which achieved only 43% conversion and 25% cyclohexanol selectivity under identical conditions (240 degrees C, 30 bar H2, and 4 h). High-resolution transmission electron microscopic (HR-TEM) analysis reveals that LaNiO3-supported catalysts exhibit better metal dispersion and smaller nickel nanoparticle sizes compared to NiTiO3-supported counterparts. X-ray photoelectron spectroscopy (XPS) analysis shows that the reduction of nickel and noble metals is more facile on LaNiO3. Additionally, the O 1s XPS profile for reduced Ru-LaNiO3 indicates a higher proportion of lattice oxygen (OLat similar to 79%) and a lower proportion of oxygen vacancies (OVac similar to 21%) compared to other catalyst systems. The optimized OLat/OVac ratio is shown to be critical for the effective HDO of guaiacol. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) demonstrates a high HDO reaction rate using reduced Ru-LaNiO3 than reduced Ru-NiTiO3, with cyclohexanol formation attributed to the keto-enol tautomerization pathway. Overall, this study underscores the critical roles of oxygen vacancies, metal dispersion, and metal-metal oxide interactions in the HDO of guaiacol.
Keywords: Cyclohexanol; Guaiacol; Hydrodeoxygenation; In-situ DRIFT; Ni-based perovskites

Hypersilylsilylene-supported Ni(0) toluene and Ni(II) complexes with catalytic application - Ajithkumar, V. S.; Bisai, Milan Kumar; Ghanwat, Pratiksha B.; Raj, K. Vipin; Singh, Geetika; Vanka, Kumar; Sen, Sakya S. (Organometallics, 2025)
The reaction of Ni(COD)2 with [PhC(NtBu)2SiSi(SiMe3)3] (1) in toluene results in the formation of an 18-electron silylene-Ni(0) toluene complex (2). The analogous reaction with 1,3-DFB instead of toluene affords the C-H activation followed by ring walking leading to the allylic cyclooctene adduct, the (eta 3-C8H13)Ni(II) complex (3). DFT calculations were carried out to elucidate the mechanism as well as to gain insight into why 1,3-DFB undergoes C-H bond activation instead of C-F bond activation. The use of NiCl2DME permits access to 16-electron (tetrylene)2NiCl2 (Si(4) and Ge(5)) species, and 4 was later used as a catalyst for the C-N coupling reaction.

Hypervalent-iodine-mediated base-free oxidative olefination of benzylic amines to access α,β-unsaturated ketones - Rupanawar, Bapurao D.; Bansode, Ajay H.; Suryavanshi, Gurunath (Synlett, 2025)
We report a one-pot base-free protocol for the oxidative olefination of benzylic amines promoted by a hypervalent iodine reagent for the synthesis of alpha,beta-unsaturated ketones. Mechanistically, (diacetoxyiodo)benzene oxidizes the benzylic amine to the corresponding imine, which, on reaction with a phenacyl(triphenyl)phosphonium bromide salt and an in situ generated acetoxy anion leads to an alpha,beta-unsaturated ketone. A wide range of alpha,beta-unsaturated ketones were easily accessed through direct oxidative olefination of substituted benzylic amines in good to excellent yields and with high E -selectivity.
Keywords: benzylic amines; enones; hypervalent iodine; olefination; Oxidation