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

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

Detection of a target protein (GroEl2) in Mycobacterium tuberculosis using a derivative of 1,2,4-triazolethiols - Sarkar, Sampa; Swami, Sagar; Soni, Sarvesh Kumar; Holien, Jessica K.; Khan, Arshad; Korwar, Arvind M.; Likhite, Anjali P.; Joshi, Ramesh A.; Joshi, Rohini R.; Sarkar, Dhiman (Molecular Diversity, 2022)
Herein, we identified a potent lead compound RRA2, within a series of 54 derivatives of 1,2,4-triazolethiols (exhibit good potency as an anti-mycobacterial agents) against intracellular Mycobacterium tuberculosis (Mtb). Compound RRA2 showed significant mycobactericidal activity against active stage Mycobacterium bovis BCG and Mtb with minimum inhibitory concentration (MIC) values of 2.3 and 2.0 mu g/mL, respectively. At MIC value, RRA2 compound yielded 0.82 log reduction of colony-forming unit (cfu) against non-replicating Mtb. Furthermore, RRA2 compound was selected for further target identification due to the presence of alkyne group, showing higher selectivity index (> 66.66 +/- 0.22, in non-replicating stage). Using ``click'' chemistry, we synthesized the biotin linker-RRA2 conjugate, purified with HPLC method and confirmed the conjugation of biotin linker-RRA2 complex by HR-MS analysis. Furthermore, we successfully pulled down and identified a specific target protein GroEl2, from Mtb whole-cell extract. Furthermore, computational molecular modeling indicated RRA2 could interact with GroEl2, which explains the structure-activity relationship observed in this study.
Keywords: 1; 2; 4-triazolethiols; GroEl2; Mycobactericidal activity; Mycobacterium bovis BCG; Mycobacterium tuberculosis

Dietary influence on modulation of Helicoverpa armigera oral secretion composition leading to differential regulation of tomato plant defense - Gopal S. Kallure; Balkrishna A. Shinde; Vitthal T. Barvkar; Archana Kumari; Ashok P. Giri (Plant Science, 2022)
Little is known about how different plant-based diets influence the insect herbivores’ oral secretion (OS) composition and eventually the plant defense responses. We analyzed the OS composition of the generalist Lepidopteran insect, Helicoverpa armigera feeding on the host plant tomato (OSH), non-host plant capsicum (OSNH), and artificial diet (OSAD) using Liquid Chromatography-Quadrupole Time of Flight Mass Spectrometry. Higher numbers and levels of alkaloids and terpenoids were observed in OSH and OSNH, respectively while OSAD was rich in phospholipids. Interestingly, treatment of H. armigera OSAD, OSH and OSNH on wounded tomato leaves showed differential expression of (i) genes involved in JA and SA biosynthesis and their responsive genes, and (ii) biosynthetic pathway genes of chlorogenic acid (CGA) and trehalose, which exhibited increased accumulation along with several other plant defensive metabolites. Specifically, high levels of CGA were detected after OSH and OSNH treatments in tomato leaves. There was higher expression of the genes involved in phenylpropanoid biosynthesis, which may lead to the increased accumulation of CGA and related metabolites. In the insect bioassay, CGA significantly inhibited H. armigera larval growth. Our results underline the differential accumulation of plant and insect OS metabolites and identified potential plant metabolite(s) affecting insect growth and development.
Keywords: Chlorogenic acid; defense; Metabolites; Non-host; Oral secretion; trehalose

Dietary influence on modulation of Helicoverpa armigera oral secretion composition leading to differential regulation of tomato plant defense. - Kallure, Gopal S.; Shinde, Balkrishna A.; Barvkar, Vitthal T.; Kumari, Archana; Giri, Ashok P. (Plant Science, 2022)
Little is known about how different plant-based diets influence the insect herbivores' oral secretion (OS) composition and eventually the plant defense responses. We analyzed the OS composition of the generalist Lepidopteran insect, Helicoverpa armigera feeding on the host plant tomato (OSH), non-host plant capsicum (OSNH), and artificial diet (OSAD) using Liquid Chromatography-Quadrupole Time of Flight Mass Spectrometry. Higher numbers and levels of alkaloids and terpenoids were observed in OSH and OSNH, respectively while OSAD was rich in phospholipids. Interestingly, treatment of H. armigera OSAD, OSH and OSNH on wounded tomato leaves showed differential expression of (i) genes involved in JA and SA biosynthesis and their responsive genes, and (ii) biosynthetic pathway genes of chlorogenic acid (CGA) and trehalose, which exhibited increased accumulation along with several other plant defensive metabolites. Specifically, high levels of CGA were detected after OSH and OSNH treatments in tomato leaves. There was higher expression of the genes involved in phenyl-propanoid biosynthesis, which may lead to the increased accumulation of CGA and related metabolites. In the insect bioassay, CGA significantly inhibited H. armigera larval growth. Our results underline the differential accumulation of plant and insect OS metabolites and identified potential plant metabolite(s) affecting insect growth and development.
Keywords: Chlorogenic acid; defense; Metabolites; Non-host; Oral secretion; trehalose

Diethyl phosphite-mediated switchable synthesis of bis(imidazoheterocycles) derived disulfanes and sulfanes using imidazoheterocycles and octasulfur - Reddy, Raju Jannapu; Shankar, Angothu; Kumar, Jangam Jagadesh; Sharadha, Nunavath; Krishna, Gamidi Rama (New Journal of Chemistry, 2022)
A practical and highly efficient oxidative dual C-H sulfenylation of imidazoheterocycles using odorless, inexpensive elemental sulfur in DMSO to synthesize sulfur-bridged imidazoheterocycles under metal-free conditions is reported. The amount of diethyl phosphite and sulfur powder most attractively permits a tunable synthesis of bis(imidazoheterocycle)disulfanes and bis(imidazoheterocycle)sulfanes in good to high yields. A comprehensive substrate scope with a broad range of functional group tolerance was realized, and the efficacy of the process was proved at gram-scale reactions. Next, the bis(imidazopyridine)disulfanes were smoothly reacted with various indoles under similar conditions to form the corresponding imidazo[1,2-a]pyridine-indole-derived thioethers in high yields. A plausible mechanism has been proposed based on the control experiments.

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

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

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

Dynamic kinetic resolution of gamma,gamma-disubstituted indole 2-carboxaldehydes via NHC-Lewis acid cooperative catalysis for the synthesis of tetracyclic epsilon-lactones - Balanna, Kuruva; Barik, Soumen; Shee, Sayan; Gonnade, Rajesh G.; Biju, Akkattu T. (2022)
The ubiquity of epsilon-lactones in various biologically active compounds inspired the development of efficient and enantioselective routes to these target compounds. Described herein is the enantioselective synthesis of indole-fused epsilon-lactones by the N-heterocyclic carbene (NHC)-Lewis acid cooperative catalyzed dynamic kinetic resolution (DKR) of in situ generated gamma,gamma-disubstituted indole 2-carboxaldehydes. The Bi(OTf)(3)-catalyzed Friedel-Crafts reaction of indole-2-carboxaldehyde with 2-hydroxy phenyl p-quinone methides generates gamma,gamma-disubstituted indole 2-carboxaldehydes, which in the presence of NHC and Bi(OTf)(3) afforded the desired tetracyclic epsilon-lactones in up to 93% yield and >99 : 1 er. Moreover, preliminary studies on the mechanism of this formal [4 + 3] annulation are also provided.

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

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

Efficient cascade C-N coupling reactions catalyzed by a recyclable MoOx/ Nb2O5 nanomaterial for valuable N-heterocycles synthesis - Singh, Nittan; Kalbande, Pavan Narayan; Umbarkar, Shubhangi; Sudarsanam, Putla (Molecular Catalysis, 2022)
The efficient cascade synthesis of pharmaceutically valuable N-heterocycles at solvent-free conditions was achieved using a robust, recyclable MoOx/Nb2O5 nanocatalyst. The results of catalyst screening revealed that the MoOx/Nb2O5 nanorods, calcined at 500 degrees C (MoNb5), exhibit excellent catalytic activity in the oxidative coupling of benzylamine with 96.5% conversion and >99.6% selectivity to the desirable imine product. The uniform dispersion of Mo-oxide nanoparticles (average particle size: 5.2 +/- 0.5 nm) on shape-controlled Nb2O5 nanorods (width: 5.3 +/- 0.5 nm and length: 23-38 nm) in MoNb5 catalyst led to improved structural and acid properties, beneficial for the cascade C-N bond construction. The shape-controlled MoNb5 catalyst showed versatile activity in various cascade C-N coupling reactions to obtain 2-phenylbenzimidazole, 2-phenyl-quinaxoline, and 2-phenyl-2,3-dihydroquinazolin-4(1H)-one with good to excellent yields at solvent-free con-ditions. The optimum ratio of Lewis/Bronsted acid sites, the unique structure of Nb2O5 nanorods, and the strong MoO3-Nb2O5 interaction are the key reasons for the higher activity of MoNb5 catalyst. The efficient reusability of MoNb5 catalyst, its remarkable activity in diverse N-heterocycles synthesis, and efficient gram-scale synthesis emphasize its practical application for the cascade C-N coupling reactions under benign conditions.
Keywords: Acid sites optimization; Cascade C-N bond formation; Diverse nitrogenous chemicals; Heterogeneous nanosized catalyst; MoO3-Nb2O5 interaction; Nb2O5 nanorods

Efficient synthesis of 5-(hydroxymethyl)furfural esters from polymeric carbohydrates using 5-(chloromethyl)furfural as a reactive intermediate - Bhat, Navya Subray; Hegde, Shobhita L.; Dutta, Saikat; Sudarsanam, Putla (ACS Sustainable Chemistry & Engineering, 2022)
This work reports an efficient, gram-scale synthesis of 5-(hydroxymethyl)furfural (HMF) esters using biomass-derived 5-(chloromethyl)furfural (CMF) as a reactive intermediate. The HMF-esters have potential applications as chemicalintermediates, fuel additives, and bioactive compounds. Initially, CMF was prepared in good yields directly from polymericcarbohydrates (starch, inulin, and cellulose) and cellulosic materials (cotton andfilter paper) using a biphasic batch reaction system,consisting of aqueous hydrochloric acid and 1,2-dichloroethane. The use of ZnCl2as an additive allowed the reaction to proceedunder milder conditions while significantly improving the isolated yield of CMF. The effects of reaction temperature, reaction time,extracting solvent, and ZnCl2loading on CMF yield were investigated. Microcrystalline cellulose was converted into CMF with a72% isolated yield under optimized reaction conditions (80 degrees C, 2 h). After that, CMF was transformed into various novel esters ofHMF in excellent isolated yields (>85%) by reacting with a slight excess amount of the triethylammonium salt of various alkyl/arylcarboxylic acids under solvent-free conditions
Keywords: catalysis; cellulose; furanics; HMF-esters; renewable synthesis

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

Electrospun zinc-manganese bimetallic oxide carbon nanofibers as freestanding supercapacitor electrodes - Joshi, Bhavana; Samuel, Edmund; Kim, Yongil; Kim, Taegun; El-Newehy, Mohamed; Aldalbahi, Ali; Yoon, Sam S. (International Journal of Energy Research, 2022)
Flexible, lightweight, and freestanding zinc-manganese oxide carbon nanofibers are promising materials for the fabrication of portable electronic devices. Composite nanofibers were synthesized using terephthalic acid and sodium dodecyl sulfate. Terephthalic acid improves the flexibility of the composite fibers and facilitates the diffusion of electrolytic ions. Meanwhile, sodium dodecyl sulfate aids to elevate the metal (zinc) oxide particles to the surface of the nanofibers during annealing. The texturing of the carbon nanofiber surface with ZnO enhances the electrochemical activity of the composite fibers. Parametric studies were conducted by varying the weight ratio of zinc and manganese acetates from zero to unity. The optimal case with a ratio of 0.75 produces specific capacitances of 1080 and 817 F center dot g(-1) at current densities of 1 and 10 A center dot g(-1), respectively, with a wide potential window of 1.6 V, indicating outstanding energy storage capabilities. The capacitance retention was 92% after 10 000 galvanostatic charge-discharge cycles. The bending angle test confirmed the mechanical durability of the freestanding carbon nanofiber electrodes, and the corresponding change in the cyclic voltammetry curve was negligible.
Keywords: electrospinning; freestanding electrode; high-energy-density; supercapacitor; ZnMn2O4

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

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

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

Enantioselective synthesis of dihydrothiopyranones via NHC- catalyzed [3+3] annulation of 2-bromoenals with beta-oxodithioesters - Barik, Shilpa; Shee, Sayan; Gonnade, Rajesh G.; Biju, Akkattu T. (Organic Letters, 2022)
The N-heterocyclic carbene (NHC)-organocata-lyzed [3 + 3] annulation of 2-bromoenals with fi-oxodithioesters resulting in the enantioselective synthesis of dihydrothiopyranones is presented. The chiral a,fi-unsaturated acylazoliums generated from 2-bromoenals and carbenes underwent smooth interception with the sulfur nucleophiles to furnish the sulfur heterocycles in satisfactory yields/selectivity. The regioselective formation of dihydrothiopyranones over the competing dihydropyranones is noteworthy.

Enceleamycins A-C, furo-naphthoquinones from amycolatopsis sp. MCC0218: isolation, structure elucidation, and antimicrobial activity - Khan, Abujunaid; Said, Madhukar S.; Borade, Balasaheb R.; Gonnade, Rajesh; Barvkar, Vitthal; Kontham, Ravindar; Dastager, Syed G. (Journal of Natural Products, 2022)
Three novel furo-naphthoquinones, enceleamycins A-C (1-3), and a new N-hydroxypyrazinone acid (4) were identified from the strain Amycolatopsis sp. MCC 0218, isolated from a soil sample collected from the Western Ghats of India. Their chemical structure and absolute and relative configurations were established by 1D and 2D NMR spectroscopy, single-crystal X-ray crystallography, and high-resolution mass spectrometry. Compounds 1 and 3 were active against methicillin-susceptible and -resistant Staphylococcus aureus with MIC values of 2-16 mu g/mL.

Engineering nucleotide sugar synthesis pathways for independent and simultaneous modulation of N-glycan galactosylation and fucosylation in CHO cells - Prabhu, Anuja; Shanmugam, Dhanasekaran; Gadgil, Mugdha (Metabolic Engineering, 2022)
Glycosylation of recombinant therapeutics like monoclonal antibodies (mAbs) is a critical quality attribute. N-glycans in mAbs are known to affect various effector functions, and thereby therapeutic use of such glycoproteins can depend on a particular glycoform profile to achieve desired efficacy. However, there are currently limited options for modulating the glycoform profile, which depend mainly on over-expression or knock-out of glyco-syltransferase enzymes that can introduce or eliminate specific glycans but do not allow predictable glycoform modulation over a range of values. In this study, we demonstrate the ability to predictably modulate the gly-coform profile of recombinant IgG. Using CRISPR/Cas9, we have engineered nucleotide sugar synthesis pathways in CHO cells expressing recombinant IgG for combinatorial modulation of galactosylation and fucosylation. Knocking out the enzymes UDP-galactose 4 `-epimerase (Gale) and GDP-L-fucose synthase (Fx) resulted in ablation of de novo synthesis of UDP-Gal and GDP-Fuc. With Gale knock-out, the array of N-glycans on recom-binantly expressed IgG is narrowed to agalactosylated glycans, mainly A2F glycan (89%). In the Gale and Fx double knock-out cell line, agalactosylated and afucosylated A2 glycan is predominant (88%). In the double knock-out cell line, galactosylation and fucosylation was entirely dependent on the salvage pathway, which allowed for modulation of UDP-Gal and GDP-Fuc synthesis and intracellular nucleotide sugar availability by controlling the availability of extracellular galactose and fucose. We demonstrate that the glycoform profile of recombinant IgG can be modulated from containing predominantly agalactosylated and afucosylated glycans to up to 42% and 96% galactosylation and fucosylation, respectively, by extracellular feeding of sugars in a dose-dependent manner. By simply varying the availability of extracellular galactose and/or fucose, galactosylation and fucosylation levels can be simultaneously and independently modulated. In addition to achieving the pro-duction of tailored glycoforms, this engineered CHO host platform can cater to the rapid synthesis of variably glycoengineered proteins for evaluation of biological activity.
Keywords: Antibody; Cell engineering; Fucosylation; Fx; Galactosylation; Gale; glycosylation; Nucleotide sugar synthesis; Recombinant therapeutics

Enhanced hydrogen fuel production using synergistic combination of solar radiation and TiO2 photocatalyst coupled with Burkholderia cepacia lipase - de Souza Brandao, Luma Mirely; Barbosa, Milson dos Santos; de Jesus, Roberta Anjos; Bharad, Pradnya Arunrao; Lima, Alvaro Silva; Faria Soares, Cleide Mara; Navarro Yerga, Rufino Manuel; Bilal, Muhammad; Romanholo Ferreira, Luiz Fernando; Iqbal, Hafiz M. N.; Gopinath, Chinnakonda S.; Figueiredo, Renan Tavares (International Journal of Hydrogen Energy, 2022)
Promising and sustainable alternatives for hydrogen production have been investigated. Among these, the use of enzymes may represent an efficient alternative. In this work, an increase in hydrogen production under simulated sunlight by combining TiO2 and TiO2/MgCl2 with Burkholderia cepacia lipase (BCL) was reported. The samples (TiO2, TiO2/MgCl2, and TiO2 /MgCl2/BCL) were characterized by X-ray diffraction (XRD), thermo-gravimetric (TGA), N-2 adsorption-desorption isotherms (BET), scanning electron microscopy (SEM), and UV-Visible absorption spectra. Hydrogen production tests were performed in aqueous methanol solutions under simulated sunlight. The results demonstrated that 130-times greater increase in hydrogen production rate was observed by the addition of BCL than individual TiO2. This better hydrogen production rate can be attributed to the increase in the amount of reduction equivalent of the system due to the oxidation of protein peptides caused by TiO2. In conclusion, the results indicate that hydrogen production efficiency can be significantly improved when integrating TiO2/MgCl2 with BCL. (C) 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Keywords: hydrogen production; Lipase; Nano-conjugated enzymes; Photocatalyst; Solar radiation; Titanium dioxide

Facile fabrication of nano silver phosphate on B-doped g-C3N4: an excellent p-n heterojunction photocatalyst towards water oxidation and Cr (VI) reduction - Sahoo, Mitarani; Babu, Pradeepta; Singh, Chandrodai Pratap; Krishnamurty, Sailaja; Parida, Kulamani (Journal of Alloys and Compounds, 2022)
A photostable Ag3PO4/BCN type-II p-n heterojunction has been demonstrated by loading nano Ag3PO4 on B-doped g-C3N4 nanosheet (BCN). The photocatalysts were successfully characterized by various physicochemical techniques and their photocatalytic activities were tested towards the water oxidation reaction to produce oxygen and Cr (VI) reduction under visible light. The HRTEM confirms Ag3PO4 with a particle size of 15 nm has been deposited on BCN to construct a p-n heterojunction. The BCNS-50 absorbs more visible light in the solar spectrum as compared to other catalyst, demonstrating the ability to generate 587 mu mol h(-1)g(-1) O-2 and reduces 98% of 20 ppm Cr (VI) solution in 1 h. The lower PL intensity as well as lower arc value in case of BCNS-50 suggests the maximum e-h separation and lower charge transfer resistance across the semiconductor/electrolyte interface. The BCN sheet provides a compact heterojunction where the oxidation peak of Ag3PO4 decreases gradually and disappear in case of BCNS-50 suggesting the enhance stability of Ag3PO4 in the heterojunction. BCNS-50 could able to produce -139 and 3087.5 mu A photocurrent both in cathodic and anodic direction which is approximately 7 and 2.4 folds higher as compared to nano Ag3PO4. The generation of photocurrent in both cathodic and anodic direction confirms the formation of p-n heterojunction which further supported by Mott-Schottky analysis. Furthermore the construction of the p-n heterojunction is verified via Mott-Schottky study. DFT calculation explains the contribution of various atomic orbital of Ag3PO4 and BCN towards the formation of hybrid orbital in the heterojunction and the path for charge delocalization between them. This work may provide a limelight and alternative pathway for enhanced photocatalytic performance on construction of the p-n heterojunction in a simple way. (C) 2021 Elsevier B.V. All rights reserved.
Keywords: Cr (VI) reduction; Density functional theory; Interfacial zone; p-n heterojunction; Photocatalyst; Water oxidation

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

Facile synthesis of the spiro-pyridoindolone scaffold via a gold-catalysed intramolecular alkynol cyclisation/hydroindolylation - Shinde, Mahesh H.; Ramana, V. Chepuri (Organic & Biomolecular Chemistry, 2022)
A simple approach for the synthesis of pyridoindolone scaffolds with a spiroannulated tetrahydrofuran ring is described. The overall process comprises intramolecular sequential gold-catalysed 5-endo-dig alkynol cycloisomerization and subsequent addition of indole C2 to the in situ generated oxocarbenium cation.

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

First-principles investigation of the electrocatalytic reduction of CO2 on zirconium-based single-, double-, and triple-atom catalysts anchored on a graphitic carbon nitride monolayer - Hassan, Afshana; Anis, Insha; Shafi, Sadaf; Assad, Assif; Rasool, Anjumun; Khanam, Romana; Bhat, Gulzar Ahmad; Krishnamurty, Sailaja; Dar, Manzoor Ahmad (ACS Applied Nano Materials, 2022)
Conversion of carbon dioxide (CO2) with the help of an appropriate electrocatalyst with high stability, low onset potential, and exceptional selectivity is still one of the great tasks in the electrocatalytic reduction of CO2 to valuable chemicals. Herein, by means of systematic first-principles simulations, we investigate the CO2 reduction reaction (CO2RR) activity of zirconium-based single-, double-, and triple-atom (Zrn@C2N; n = 1-3) catalysts anchored on a graphitic carbon-nitride monolayer. In tune with the Sabatier principle, our results reveal that a moderate CO2 binding is vital for a low onset potential for the CO2RR. Consequently, based on rigorous free energy calculations, the Zr-based single-atom catalyst (SAC) is found to be most effective to convert CO2 to valuable products such as HCOOH and CH3OH. It is worth noting that CO2 reduction to HCOOH is spontaneous via the *HCOO intermediate on Zr1@C2N and involves a low onset potential of -0.23 V with respect to the reversible hydrogen electrode from the *COOH intermediate. Among all the catalysts evaluated computationally, the Zr SAC further reveals the lowest onset potential of -0.89 V for CH3OH formation. The results show that the Zr-based catalysts especially Zr1@C2N are found to effectively suppress the competitive hydrogen evolution reaction and promote the CO2RR. Moreover, all three catalysts exhibit high kinetic and thermal stability with negligible distortion due to which their structures can be retained very well up to 600 K. Thus, the current work may provide effective catalyst-design strategies for enhancing the electrocatalytic CO2RR performance of Zr-based materials.
Keywords: C1 and C2 products; CO2 reduction; first-principles simulations; hydrogen evolution reaction; onset potential; single-atom catalysts (SACs); Zrn@C2N catalysts

First-row transition metal complexes of a phosphine-silylene- based hybrid ligand - Akhtar, Ruksana; Kaulage, Sandeep H.; Sangole, Mayur P.; Tothadi, Srinu; Parvathy, Parameswaran; Parameswaran, Pattiyil; Singh, Kirandeep; Khan, Shabana (Inorganic Chemistry, 2022)
We have prepared two new silylene-phosphine-based hybrid ligands Si{N(R)C6H4(PPh2)}{PhC((NBu)-Bu-t)(2)} [R = TMS {trimethylsilyl} (1) and TBDMS {tert-butyldimethylsilyl} (2)], which possess two donor sites. Furthermore, the treatment of the bidentate ligand 1 with base metal halides {FeBr2, CoBr2, NiCl(2)middotdme [nickel chloride(II) ethylene glycol dimethyl ether]} and 2 with NiBr(2)middotdme [nickel bromide(II) ethylene glycol dimethyl ether] afforded four-coordinate six-membered metal complexes 3-6, respectively, which feature coordination from both Si(II) and P(III) sites. Subsequently, complexes 3 [(FeBr2)Si{N(SiMe3)C6H4(PPh2)}{PhC((NBu)-Bu-t)(2)}], 4 [(CoBr2)Si{N(SiMe3)C6H4(PPh2)}{PhC((NBu)-Bu-t)(2)}], 5 [(NiCl2)Si{N(SiMe3)C6H4(PPh2)}{PhC((NBu)-Bu-t)(2)}], and 6 [(NiBr2)Si{N((SiBuMe2)-Bu-t)C6H4(PPh2)}{PhC((NBu)-Bu-t)(2)}] are studied for their redox and magnetic properties with the help of UV-vis spectroscopy, cyclic voltammetry, SQUID magnetometry, and theoretical calculations. Complexes 3-6 were found to display a paramagnetic behavior. All the compounds are well established by single-crystal X-ray diffraction studies.

Flexible ultracapacitor device fabricated with an organic electrode material- naphthalene diimide nitrile/reduced graphene oxide - Deshmukh, Ashvini B.; Biradar, Madan R.; Pawar, Meenakshi D.; Bhosale, Sidhanath V.; Shelke, Manjusha V. (Journal of Energy Storage, 2022)
In this work, we have demonstrated a high-performance flexible supercapacitor electrode based on reduced graphene oxide (rGO) and naphthalene diimide nitrile (NDI-CN) composite. The rGO/NDI-CN composite was prepared by a simple approach. This composite was well characterized using various techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) etc. Besides, the pi -pi stacking of NDI-CN on rGO surface was confirmed using UV-vis and FTIR techniques. As fabricated rGO/NDI-CN composite was examined as an electrode material for the supercapacitor applications. The rGO/NDI-CN electrode has delivered an excellent specific capacitance (C-sp) of 336 F g(-1) at 0.5 A g(-1)current density. The fabricated supercapacitor (SC) displays robustness with 80 % capacitance retention over 10,000 cycles at higher current density of 10 A g(-1). To further explore the real-world application of electrode materials, the corresponding flexible supercapacitor was designed and examined. The flexible device exhibited an energy density of 9.54 mu Wh cm(-2) at a power density of 0.3 mWcm(-2). These results confirmed that the rGO/NDI-CN electrode material has good potential as an energy storage device. Furthermore, the facile construction and fabrication of flexible device displayed operation of LED when fully charged. The assembled flexible supercapacitor device could be bent and twisted, signifying the potential to be used in practical applications in various high-performance electrochemical devices.
Keywords: flexible supercapacitor; Naphthalene diimide; Organic molecule electrodes; pi -pi interaction; rGO

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

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

Free base phthalocyanine coating as a superior corrosion inhibitor for copper surfaces: a combined experimental and theoretical study - Samal, Pragnya Paramita; Dekshinamoorthy, Amuthan; Arunachalam, Shivakami; Vijayaraghavan, Saranyan; Krishnamurty, Sailaja (Colloids and Surfaces A-Physicochemical and Engineering Aspects, 2022)
In the quest of novel, eco-benign copper corrosion inhibitors, free base and a set of six metal Phthalocyanine (Pc) coatings (where metal is Zn, Cu, Fe, Co, Ni, Mn) are systematically evaluated for their corrosion inhibition efficiency. The study demonstrates that the free base Phthalocyanine coatings are superior corrosion inhibitors for Cu surface in HCl with a corrosion inhibition efficiency of 88% as compared to its metal counterparts. A detailed and indepth study involving concerted electrochemical polarisation, impedance measurements at various concentrations of HCl assert the superior corrosion inhibition efficiency of free base Pc coatings as compared to its metal counterparts. Underlying factors/interface chemistry contributing to it is brought out using first principle based studies. First principles based computational studies establish that superior corrosion inhibition ability of free base phthalocyanine molecule is attributed to its innate binding ability with copper surface and its better inter-molecular packing. Thus, the theoretical adsorption trends of various studied phthalocyanine molecules while clearly following the experimental corrosion inhibition efficiency trends undermine the importance of contribution of chelating factors for the formation of a stable and efficient corrosion inhibition coating on a surface and that the adhesion/adsorption strength of a molecule correlates directly to its corrosion inhibition efficiency. The experimental observations are further substantiated through FE-SEM, EDAX and XPS studies. The corrosion inhibition efficiency of free base phthalocyanine is followed by its zinc based counterpart at 85%.
Keywords: Copper surface; Corrosion inhibitors; DFT studies; Impedance; Phthalocyanine coatings

From ``Cosmic Cooking'' to chemistry of the future: a collective dialogue on chemistry as a tribute to Prof. Sourav Pal. - Roy, Soumyajit; Krishnamurty, Sailaja; Schoefberger, Wolfgang (Frontiers in Chemistry, 2022)
Keywords: cosmic cooking; coupled cluster and density functional calculations; dialogue on chemistry; pincers porphyrinoids and oxometalates; small molecule activation; Theoretical chemistry

Graphical Biology Insights into the dynamic interactions at chemokine-receptor interfaces and mechanistic models of chemokine binding - Sonawani, Archana; Kharche, Shalmali; Dasgupta, Debjani; Sengupta, Durba (Journal of Structural Biology, 2022)
Chemokine receptors are the central signaling hubs of several processes such as cell migration, chemotaxis and cell positioning. In this graphical review, we provide an overview of the structural and mechanistic principles governing chemokine recognition that are currently emerging. Structural models of chemokine-receptor cocomplexes with endogenous chemokines, viral chemokines and therapeutics have been resolved that highlight multiple interaction sites, termed as CRS1, CRS1.5 etc. The first site of interaction has been shown to be the Nterminal domain of the receptors (CRS1 site). A large structural flexibility of the N-terminal domain has been reported that was supported by both experimental and simulation studies. Upon chemokine binding, the Nterminal domain appears to show constricted dynamics and opens up to interact with the chemokine via a large interface. The subsequent sites such as CRS1.5 and CRS2 sites have been structurally well resolved although differences arise such as the localization of the N-terminus of the ligand to a major or minor pocket of the orthosteric binding site. Several computational studies have highlighted the dynamic protein-protein interface at the CRS1 site that seemingly appears to resolve the differences in NMR and mutagenesis studies. Interestingly, the differential dynamics at the CRS1 site suggests a mixed model of binding with complex signatures of both conformational selection and induced fit models. Integrative experimental and computational approaches could help unravel the structural basis of promiscuity and specificity in chemokine-receptor binding and open up new avenues of therapeutic design.
Keywords: Chemokine receptors; GPCRs; Intrinsically disordered protein domains; protein-protein interactions

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

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

Highly efficient chemoselective hydrogenation of 5-HMF to BHMF over reusable bimetallic Pd-Ir/C catalyst - Ratrey, Geetanjali; Solanki, Bhanupratap S.; Kamble, Sanjay P.; Rode, V. Chandrashekhar (ChemistrySelect, 2022)
Catalytic synergism was observed for a bimetallic Pd-Ir catalyst supported on activated carbon for chemoselective hydrogenation of 5-hydroxymetahyl furfural (5-HMF) to 2, 5-(bishydroxymethyl) furan (BHMF) with complete conversion and 97 % selectivity under very mild reaction conditions. The structural characterization like XRD, N-2 sorption, FE-SEM and TEM suggested formation of fine nanoparticles (1.95-3.08 nm) having very higher surface area, uniform distribution and mesoporous nature of the material. XPS spectra and Pyridine-IR spectroscopy revealed formation of Pd-PdO and Ir/IrO2/IrO3 interface on the catalytic surface along with strong Bronsted acidic sites which were responsible for high efficiency of catalyst at 80 degrees C, 100 psig H-2 pressure at 5-HMF/Catalyst=20 and within 2.5 h of reaction time. A plausible reaction mechanism is also elucidated based on structure activity correlation.
Keywords: 5-HMF; Carbon; Catalytic synergism; Selective hydrogenation; Valorization

Hydrodechlorination of 4-chloro-2-aminophenol into a recyclable product using Ni- and Cu-based catalysts - Shetty, Rohit R.; Raut, Sandesh S.; Kulkarni, Prashant S.; Kamble, Sanjay P. (Industrial & Engineering Chemistry Research, 2022)
The 4-chloro-2-amino phenol (4C2AP) bearing wastewater is produced while manufacturing dyes and pharma-ceutical ingredients. Ni-and Cu-based cost-effective catalysts were developed, typically characterized, and subjected to hydrodechlori-nation (HDC) of 4C2AP. The role of reducing agents, concentration, pH of wastewater, presence of salt, reaction temperature, catalyst reuse, and the kinetics was investigated. A selective makeover of 2-amino phenol (2AP) was analyzed by HPLC, LCMS, and NMR. A complete HDC of 4C2AP with remarkable selectivity (98%) toward 2AP was achieved using a Ni0 catalyst and NaBH4 at room temperature. It is observed that the alkaline condition, the presence of salt, and a high reaction temperature favor the HDC process. A maximum of 1 g L-1 of the Ni0 loading is found to be sufficient to dechlorinate the pollutant. It can be concluded that the catalytic HDC is a technically viable and inexpensive process for the conversion of 4C2AP into a valuable product, 2AP.

Hypersilyl substituent in heavier low-valent group 14 chemistry - Gour, Kritika; Bisai, Milan Kumar; Sen, Sakya S. (European Journal of Inorganic Chemistry, 2022)
The isolation of unusual compounds with low-valent main-group elements would not have been possible without the development of a series of sterically demanding ligands with bulky substituents. While early literature recognizes the advent of the sterically demanding tris(trimethylsilyl)silyl (SiMe3)(3)Si- group, also known as hypersilyl group, to stabilize species with new coordination modes for the main group elements, it has largely been more recent studies that have utilized this group for isolating stable compounds with low-valent main-group elements. Such compounds are not only interesting from the structure-bonding point of view but showcase potential for small molecule activation under ambient conditions. This review will cover the recent developments in stabilizing unusual compounds with group 14 elements using the exceptionally strong sigma-donor properties and pronounced steric effects of the hypersilyl moiety, emphasizing their synthesis, structure, and reactivity.
Keywords: Germylenes; Hydroboration; Hypersilyl; silylenes; Stannylenes

Hyperthermia and doxorubicin release by Fol-LSMO nanoparticles induce apoptosis and autophagy in breast cancer cells - Kulkarni-Dwivedi, Neha; Patel, Pratikshkumar R.; Shravage, V. Bhupendra; Umrani, Rinku D.; Paknikar, Kishore M.; Jadhav, Sachin H. (Nanomedicine, 2022)
Background: Studies on the anticancer effects of lanthanum strontium manganese oxide (LSMO) nanoparticles (NPs)-mediated hyperthermia at cellular and molecular levels are scarce. Materials & methods: LSMO NPs conjugated with folic acid (Fol-LSMO NPs) were synthesized, followed by doxorubicin-loading (DoxFol-LSMO NPs), and their effects on breast cancer cells were investigated. Results: Hyperthermia (45 degrees C) and combination treatments exhibited the highest (similar to 95%) anticancer activity with increased oxidative stress. The involvement of intrinsic mitochondria-mediated apoptotic pathway and induction of autophagy was noted. Cellular and molecular evidence confirmed the crosstalk between apoptosis and autophagy, involving Beclin1, Bcl2 and Caspase-3 genes with free reactive oxygen species presence. Conclusion: The study confirmed hyperthermia and doxorubicin release by Fol-LSMO NPs induces apoptosis and autophagy in breast cancer cells.
Keywords: Apoptosis; Autophagy; Breast cancer; combination therapy; doxorubicin; Folic acid; hyperthermia; LSMO; MDA-MB231 cells; PEG

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

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

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

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

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

Incorporating conducting polypyrrole into a polyimide COF for carbon-free ultra-high energy supercapacitor - Haldar, Sattwick; Rase, Deepak; Shekhar, Pragalbh; Jain, Chitvan; Vinod, Chathakudath Prabhakaran; Zhang, En; Shupletsov, Leonid; Kaskel, Stefan; Vaidhyanathan, Ramanathan (Advanced Energy Materials, 2022)
Redox-active covalent organic frameworks (COFs) store charges but possess inadequate electronic conductivity. Their capacitive action works by storing H+ ions in an acidic electrolyte and is typically confined to a small voltage window (0-1 V). Increasing this window means higher energy and power density, but this risks COF stability. Advantageously, COF's large pores allow the storage of polarizable bulky ions under a wider voltage thus reaching higher energy density. Here, a COF-electrode-electrolyte system operating at a high voltage regime without any conducting carbon or redox active oxides is presented. Conducting polypyrrole (Ppy) chains are synthesized within a polyimide COF to gain electronic conductivity (approximate to 10 000-fold). A carbon-free quasi-solid-state capacitor assembled using this composite showcases high pseudo-capacitance (358 mF cm(-2)@1 mA cm(-2)) in an aqueous gel electrolyte. The synergy among the redox-active polyimide COF, polypyrrole and organic electrolytes allows a wide-voltage window (0-2.5 V) leading to high energy (145 mu Wh cm(-2)) and power densities (4509 mu W cm(-2)). Amalgamating the polyimide-COF and the polypyrrole as one material minimizes the charge and mass transport resistances. Computation and experiments reveal that even a partial translation of the modules/monomers intrinsic electronics to the COF imparts excellent electrochemical activity. The findings unveil COF-confined polymers as carbon-free energy storage materials.
Keywords: carbon free capacitors; cation-anion co-storage; conductivity; high energy capacitors; polypyrrole doped COFs

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

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

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

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

Investigation of the captopril-insulin interaction by mass spectrometry and computational approaches reveals that captopril induces structural changes in insulin - Ghosh, Amrita; Pawar, Aiswarya B.; Chirmade, Tejas; Jathar, Swaraj M.; Bhambure, Rahul; Sengupta, Durba; Giri, Ashok P.; Kulkarni, Mahesh J. (ACS Omega, 2022)
ABSTRACT: Post-translational modifications remarkably regulate proteins' biological function. Small molecules such as reactive thiols, metabolites, and drugs may covalently modify the proteins and cause structural changes. This study reports the covalent modification and noncovalent interaction of insulin and captopril, an FDA-approved antihypertensive drug, through mass spectrometric and computation-based approaches. Mass spectrometric analysis shows that captopril modifies intact insulin, reduces it into its ``A'' and ``B'' chains, and covalently modifies them by forming adducts. Since captopril has a reactive thiol group, it might reduce the insulin dimer or modify it by reacting with cysteine residues. This was proven with dithiothreitol treatment, which reduced the abundance of captopril adducts of insulin A and B chains and intact Insulin. Liquid chromatography tandem mass spectrometric analysis identified the modification of a total of four cysteine residues, two in each of the A and B chains of insulin. These modifications were identified to be Cys6 and Cys7 of the A chain and Cys7 and Cys19 of the B chain. Mass spectrometric analysis indicated that captopril may simultaneously modify the cysteine residues of intact insulin or its subunits A and B chains. Biophysical studies involving light scattering and thioflavin T assay suggested that the binding of captopril to the protein leads to the formation of aggregates. Docking and molecular dynamics studies provided insights into the noncovalent interactions and associated structural changes in insulin. This work is a maiden attempt to understand the detailed molecular interactions between captopril and insulin. These findings suggest that further investigations are required to understand the long-term effect of drugs like captopril.

Isoeugenol affects expression pattern of conidial hydrophobin gene RodA and transcriptional regulators MedA and SomA responsible for adherence and biofilm formation in Aspergillus fumigatus - Gupta, Lovely; Sen, Pooja; Bhattacharya, Asish K.; Vijayaraghavan, Pooja (Archives of Microbiology, 2022)
Aspergillus fumigatus is one of the major pathogenic fungal species, causing life-threatening infections. Due to a limited spectrum of available antifungals, exploration of new drug targets as well as potential antifungal molecules has become pertinent. Rodlet layer plays an important role in adherence of fungal conidia to hydrophobic cell surfaces in host, which also leads to A. fumigatus biofilm formation, contributing factor to fungal pathogenicity. From decades, natural sources have been known for the development of new active molecules. The present study investigates effect of isoeugenol on genes responsible for hydrophobins (RodA), adhesion as well as biofilm formation (MedA and SomA) of A. fumigatus. Minimum inhibitory concentrations (MIC and IC50) of isoeugenol against A. fumigatus were determined using broth microdilution assay. The IC50 results showed reduced hydrophobicity and biofilm formation as well as eradication after treatment with the compound and electron micrograph data corroborated these findings. The qRT-PCR showed a significant downregulation of genes RodA, MedA, SomA and pksP involved in hydrophobicity and biofilm formation. SwissADME studies potentiated drug-like propensity for isoeugenol which formed four hydrogen bonds with low binding energy (- 4.54 kcal/mol) at the catalytic site of RodA protein studied via AutoDock4. Hence, the findings conclude that isoeugenol inhibits conidial hydrophobicity and biofilm formation of A. fumigatus and further investigations are warranted in this direction.
Keywords: Aspergillus fumigatus; Hydrophobicity; Isoeugenol; Transcription regulators; Virulence

Isolation and structural characterization of exopolysaccharide from marine Bacillus sp. and its optimization by Microbioreactor - Wagh, Vasudev S.; Said, Madhukar S.; Bennale, Jagadish S.; Dastager, Syed G. (Carbohydrate Polymers, 2022)
In the present study, a cost-effective, robust Microbioreactor based production optimization of levan like exopolysaccharide from marine Bacillus sp. SGD-03 was analysed. FE-SEM analysis has showed the significant fibrillar structure of EPS. Size exclusion chromatography and other analytical data revealed that, produced EPS has a molecular weight of 1.0 x 10(4) Da and is composed of fructose monosaccharide with hydroxyl, carbonyl, and ether groups. The backbone structure of EPS has a branching pattern of beta-(2,6) linkages which confirms the similarity with available levan like polymers. The cost-effective media composition for levan production was demonstrated. The maximum yield of crude levan obtained was 123.9 g/L by response surface methodology using robust BioLector Pro Microbioreactor, and same has been validated with shake flask, 1 L and 10 L pilot-scale fermentation.
Keywords: EPS; marine; Microbioreactor; Optimization; structure

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

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

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

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

Lewis acid-catalyzed chemodivergent and regiospecific reaction of phenols with quaternary peroxyoxindoles - Shaikh, Moseen A.; Samal, Pragnya Paramita; Ubale, Akash S.; Krishnamurty, Sailaja; Gnanaprakasam, Boopathy (Journal of Organic Chemistry, 2022)
The indium-catalyzed regiospecific coupling of substituted phenol derivatives and quaternary peroxyoxindoles for the synthesis of C2 or C4 benzoxazin-3-one-substituted phenols via skeletal rearrangement is described. This reaction is demonstrated with 17 examples with good yields and diverse aryl substituents. In contrast to the indium-catalyzed reaction, the Cu(OTf)2- catalyzed reaction of the phenol with quaternary peroxyoxindoles afforded C2 or C4 2-oxindole-substituted phenol derivatives. This diverse catalytic reaction generated various biologically important phenol-substituted 2-oxindole derivatives directly without any skeleton rearrangement and was demonstrated with 19 examples in high yield. The regiospecificity and the reaction pathways were explained with the support of density functional theory (DFT).

Ligands as ``Matchmakers'': alloying from a physical mixture of metal nanoparticle dispersions by digestive ripening - Shimpi, Jayesh R.; Prasad, V. Bhagavatula L. (Langmuir, 2022)
Digestive ripening (DR) of a physical mixture of different metal nanoparticles (NPs) in the presence of a suitable ligand is demonstrated to be a convenient way to obtain alloy NPs. The results show that the right choice of metal-ligand combination is extremely important for efficient alloying. The results are rationalized on the basis of hard soft acid base principles, and it is concluded that better alloying ensues if DR is carried out with soft ligands when soft metals are being used and hard ligands facilitate alloying between hard metals. On the other hand, when a physical mixture of hard-soft metals is taken, ligands with intermediate character work better. The results presented here could prove to be extremely valuable and open new avenues of making interesting alloy/intermetallic systems.

Lignocellulose degradation by Penicillium janthinellum enzymes is influenced by its variable secretome and a unique set of feedstock characteristics - Christopher, Meera; Sreeja-Raju, Athiraraj; Sankar, Meena; Gokhale, Digambar Vitthal; Pandey, Ashok; Sukumaran, Rajeev K. (Bioresource Technology, 2022)
Substrate characteristics and proteins that affect lignocellulose-hydrolysis by the hypercellulolytic fungus Peni-cillium janthinellum NCIM 1366 (PJ-1366) were investigated. The hydrolysis rate of PJ-1366 enzymes was very high, with upto 75 % of the reaction being completed in initial 4 h. Comparison of the hydrolytic efficiencies on differently pretreated biomass indicated that the greatest (negative) effect was imparted by lignin, suggesting that improving ligninase activity of the PJ-1366 enzymes may help to improve hydrolysis. Larger pore sizes and higher crystallinity of substrates, which favor enzyme penetration and processive hydrolysis, positively influ-enced hydrolysis efficiency. For alkali-pretreated substrates, 16 FPU/g of PJ-1366 cellulases released the sugar -equivalent of using 10 FPU/g of a commercial biomass hydrolyzing enzyme. By correlation analysis, 41 proteins, including 20 CAZymes were identified, whose abundance in the secretome positively correlated with the cellulase activities of the culture filtrate. These proteins may be considered as the primary drivers of FPase/ CMCase/pNPGase/xylanase activity in PJ-1366.
Keywords: Biofuel; CAZyme; Cellulase; Penicillium; Secretome

Luminescence turn-off detection of metal ions and explosives using graphene quantum dots - Jyotsna, Shubhra; Sadhu, Subha; Sharma, Vinay; Gupta, Preeti; Sharma, Geeta; Poddar, Pankaj (MRS Communications, 2022)
Green luminescent graphene quantum dots (GQDs) obtained from combustion of white printing paper were used for detection of fourteen different metal ions and six different explosives in an aqueous medium. These were obtained using a microwave-assisted synthesis process. After optimizing the experimental conditions (pH 6; quantum yield (QY) similar to 38.2%), a sensitive sensing system was developed to detect explosives and free residual metal ions in the environment based on fluorescence quenching of GQDs. The as-synthesized GQDs, as a sensing system, is most sensitive for Cu2+ ion and 2,4-DNP with a detection limit of 0.62 mu M and 0.50 mu M, respectively.

Luminescent magnesium complexes with intra- and inter-ligand charge transfer - Kumar, Rohit; Pahar, Sanjukta; Chatterjee, Joy; Dash, Soumya Ranjan; Gonnade, Rajesh G.; Vanka, Kumar; Sen, Sakya S. (Chemical Communications, 2022)
Herein, we report two 2,2'-pyridylpyrrolide (PyPyrH) ligand supported magnesium complexes (1 and 2), which demonstrate bright luminescence with a quantum yield of 22% and 14% in the solid state, respectively. Theoretical calculations reveal that their emissive properties originate from the intra- and inter-ligand charge transfer.

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

Magnetostriction studies on transition metal substituted cobalt ferrite - Bhame, D. Shekhar; Bhapkar, Abhishek; Shirolkar, Mandar M.; Joy, Pattayil A. (Journal of the Indian Chemical Society, 2022)
Structural, magnetic and microstructural properties of transition metal (TM) substituted cobalt ferrite Co0.9TM0.1Fe2O4 (where TM = Ti, Cr, Mn, Ni and Cu and Zn) were investigated. The present study shows marked dependence of the magnetostriction on the concentration of the substituted transition metal ions for Cobalt in CoFe2O4. The magnetic characteristics of the prepared compositions such as coercivity, anisotropy constant and saturation magnetization changed significantly on transition metal substitution. The present study shows the way to tune the anisotropy of cobalt ferrite by effective substitution of other transition metal ions for Co which subsequently affects the stress sensing performance by changing the slope of the magnetostriction curve. Apart from the magnetic properties the microstructure can also be effectively modified by substitution of other transition metal ions. Only 10% substitution of cobalt showed drastic influence on magnetostriction and slope of magnetostriction curve. The composition with 10% nickel Co0.9Ni0.1Fe2O4 exhibited maximum slope for the magnetostriction curve of -53.7 ppm/Oe, along with reasonably high magnitude of strain of 186 ppm making it a suitable for exploring stress sensing applications.
Keywords: Ferrite; Magnetoelastic; Magnetostriction; oxide; stress sensing

Maltooligosaccharide forming amylases and their applications in food and pharma industry - Shinde, Vidhya K.; Vamkudoth, Koteswara Rao (Journal of Food Science and Technology-Mysore, 2022)
Oligosaccharides are low molecular weight carbohydrates with a wide range of health benefits due to their excellent bio-preservative and prebiotic properties. The popularity of functional oligosaccharides among modern consumers has resulted in impressive market demand. Organoleptic and prebiotic properties of starch-derived oligosaccharides are advantageous to food quality and health. The extensive health benefits of oligosaccharides offered their applications in the food, pharmaceuticals, and cosmetic industry. Maltooligosaccharides and isomaltooligosaccharides comprise 2-10 glucose units linked by alpha-1-4 and alpha-1-6 glycoside bonds, respectively. Conventional biocatalyst-based oligosaccharides processes are often multi-steps, consisting of starch gelatinization, hydrolysis and transglycosylation. With higher production costs and processing times, the current demand cannot meet on a large-scale production. As a result, innovative and efficient production technology for oligosaccharides synthesis holds paramount importance. Malto-oligosaccharide forming amylase (EC 3.2.1.133) is one of the key enzymes with a dual catalytic function used to produce oligosaccharides. Interestingly, Malto-oligosaccharide forming amylase catalyzes glycosidic bond for its transglycosylation to its inheritance hydrolysis and alternative biocatalyst to the multistep technology. Genetic engineering and reaction optimization enhances the production of oligosaccharides. The development of innovative and cost-effective technologies at competitive prices becomes a national priority.
Keywords: Glycosyl hydrolases; Isomaltooligosaccharides; Maltooligosaccharide; Maltooligosaccharide forming amylase; Transglycosylation

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

Mathematical model of the multi-amino acid multi-transporter system predicts uptake flux in CHO cells - Sreejan, Ashley; Gadgil, Mugdha; Gadgil, Chetan J. (Journal of Biotechnology, 2022)
Supply and uptake of amino acids is of great importance to mammalian cell culture processes. Mammalian cells such as Chinese hamster ovary (CHO) cells express several amino acid (AA) transporters including uniporters and exchangers. Each transporter transports multiple AAs, making prediction of the effect of changed medium composition or transporter levels on individual AA transport rate challenging. A general kinetic model for such combinatorial amino acid transport, and a simplified analytical expression for the uptake rate as a function of amino acid concentrations and transporter levels is presented. From this general model, a CHO cell-specific AA transport model, to our knowledge the first such network model for any cell type, is constructed. The model is validated by its prediction of reported uptake flux and dependencies from experiments that were not used in model construction or parameter estimation. The model defines theoretical conditions for synergistic/repressive effect on the uptake rates of other AAs upon external addition of one AA. The ability of the CHO-specific model to predict amino acid interdependencies experimentally observed in other mammalian cell types suggests its robustness. This model will help formulate testable hypotheses of the effect of process changes on AA initial uptake, and serve as the AA transport component of kinetic models for cellular metabolism.
Keywords: Amino acid transport; CHO cell; Exchanger; mathematical model; Multiple transporters

Mechanics of soft polymeric materials using a fractal viscoelastic model - Pramanik, R.; Soni, F.; Shanmuganathan, K.; Arockiarajan, A. (Mechanics of Time-Dependent Materials, 2022)
Soft materials are known for their plethora of biomedical applications, intricate structure-property correlation and nonlinear mechanical response. Multiple length-time scale phenomena and hierarchical structure results in their nonlinearity. Phenomenological and continuum mechanical models have been developed to predict their mechanics, which have mostly been very material-specific with inability to predict the mechanics of different types of soft materials simultaneously. This shortcoming has been addressed in the present work, wherein a generic nonlinear viscoelastic model has been proposed to predict the mechanical response of hydrogels, sponges, and xerogels. A fractal derivative viscoelastic model is proposed considering a fractal Maxwell model in parallel with a nonlinear spring. In particular, this model is chosen to qualitatively mimic the material nonlinearity inherent in soft materials. The fractal dashpot in combination with the nonlinear spring accounts for the power law time-dependent rheology of generic soft materials. These two different aspects in the form of nonlinear stiffness and non-Newtonian rheology account for mechanics of most soft materials. The present model is shown to fit well the existing literature results for mechanical response of a multitude of soft material classes with different test conditions and loading rates, which is one of the salient features of the model, apart from its simplistic mathematical framework. Further, a parametric study is reported on the mechanics of nanocellulose loaded poly(vinyl alcohol) xerogel. The model predictions are observed to be in conjunction with the experimental observations.
Keywords: Mechanics; Nonlinear; Polymeric composites; Soft materials; viscoelastic

Mechanistically guided one pot synthesis of phosphine-phosphite and its implication in asymmetric hydrogenation - Sen, Anirban; Kumar, Rohit; Pandey, Swechchha; Raj, K. Vipin; Kumar, Pawan; Vanka, Kumar; Chikkali, Samir H. (European Journal of Organic Chemistry, 2022)
Although hybrid bidentate ligands are known to yield highly enantioselective products in asymmetric hydrogenation (AH), synthesis of these ligands is an arduous process. Herein, a one pot, atom-economic synthesis of a hybrid phosphine-phosphite (L1) is reported. After understanding the reactivity difference between an 0-nucleophile versus C-nucleophile, one pot synthesis of Senphos (L1) was achieved (72%). When L1 was treated with [Rh], P-31 NMR revealed bidentate coordination to Rh. Senphos, in the presence of rhodium, catalyzes the AH of Methyl-2-acetamido-3-phenylacrylate and discloses an unprecedented turn over frequency of 2289, along with excellent enantio-selectivity (92%). The generality is demonstrated by hydrogenating an array of alkenes. The AH operates under mild conditions of 1-2 bar H-2 pressure, at room temperature. The practical relevance of Ll is demonstrated by scaling-up the reaction to 1 g and by synthesizing DOPA, a drug widely employed for the treatment of Parkinson's disease. Computational insights indicate that the R isomer is preferred by 3.8 kcal/mol over the S isomer.
Keywords: asymmetric hydrogenation; catalysis; DOPA synthesis; One pot synthesis; Phosphine-phosphite ligand

Metagenomic mining of Indian river confluence reveal functional microbial community with lignocelluloytic potential - Rajput, Vinay; Samson, Rachel; Yadav, Rakeshkumar; Dastager, Syed; Khairnar, Krishna; Dharne, Mahesh (3 Biotech, 2022)
Microbial carbohydrate-active enzymes (CAZyme) can be harnessed for valorization of Lignocellulosic biomass (LCB) to value-added chemicals/products. The two Indian Rivers Ganges and the Yamuna having different origins and flow, face accumulation of carbon-rich substrates due to the discharge of wastewater from adjoining paper and pulp industries, which could potentially contribute to the natural enrichment of LCB utilizing genes, especially at their confluence. We analyzed CAZyme diversity in metagenomic datasets across the sacred confluence of the Rivers Ganges and Yamuna. Functional annotation using CAZyme database identified a total of 77,815 putative genes with functional domains involved in the catalysis of carbohydrate degradation or synthesis of glycosidic bonds. The metagenomic analysis detected similar to 41% CAZymes catalyzing the hydrolysis of lignocellulosic biomass polymers- cellulose, hemicellulose, lignin, and pectin. The Beta diversity analysis suggested higher CAZyme diversity at downstream region of the river confluence, which could be useful niche for culture-based studies. Taxonomic origin for CAZymes revealed the predominance of bacteria (97%), followed by archaea (1.67%), Eukaryota (0.63%), and viruses (0.7%). Metagenome guided CAZyme diversity of the microflora spanning across the confluence of Ganges-Yamuna River, could be harnessed for biomass and bioenergy applications.
Keywords: CAZymes; Confluence (Sangam); Lignocellulosic; River Ganges; River Yamuna

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

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

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

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

Molecular phylogeny, structure modeling and in silico screening of putative inhibitors of aerolysin of Aeromonas hydrophila EUS112 - Yadav, Sunita Kumari; Panwar, Deepak; Singh, Ankita; Tellis, Meenakshi B.; Joshi, Rakesh Shamsunder; Dixit, Aparna (Journal of Biomolecular Structure & Dynamics, 2022)
Aeromonas hydrophila, a Gram-negative bacterium, causes diseases in fish, resulting in excessive loss to the aquaculture industry. Aeromonas is a highly heterogeneous group of bacteria, and the heterogeneity of the genus is attributed to variation and diversity in the virulence factors and toxins among various Aeromonas strains. One of the major toxins aerolysin, secreted by the bacterium, causes hemorrhagic-septicemia and diarrhea and can serve as a drug target. Here, we describe characterization, molecular phylogeny, and homology modeling of the aerolysin of A. hydrophila strain EUS112 (Ah(EUS112)) cloned in our lab. The encoded aerolysin is 485 amino acids long with an N-terminal signal sequence of 23 amino acids. Phylogenetic analysis of the aerolysin of Ah(EUS112) revealed that it belongs to a diverse group of toxins, showing maximum similarity with aerolysins of other Aeromonas strains followed by Vibrio toxin. The homology model of the mature aerolysin of Ah(EUS112) was generated using the crystal structure of a mutant aerolysin (PDB#3g4n) as the template, which showed that the encoded aerolysin exists as a channel protein. Validation of the generated model using bioinformatics tool confirmed it to be a good quality model that can be used for drug design. Molecular dock analysis revealed that drugs, aralia-saponin I, cyclamin, ardisiacrispin B, and aralia-saponin II bind to aerolysin with a higher affinity as compared to other drugs and at functionally important amino acids of aerolysin. Hence, these molecules can act as an effective therapeutics for inhibiting the aerolysin pore formation and curtail the severity of Aeromonas infection. Communicated by Ramaswamy H. Sarma
Keywords: Aerolysin; homology modeling; Molecular docking; Molecular dynamic simulation; phylogenetic tree

Monomeric magnesium catalyzed alkene and alkyne hydroboration - Kumar, Rohit; Dutta, Sayan; Sharma, Vishal; Singh, Praval P.; Gonnade, Rajesh G.; Koley, Debasis; Sen, Sakya S. (Chemistry-A European Journal, 2022)
In this work, two monomeric magnesium alkyl complexes (1 and 2) were prepared using bis(phosphino)carbazole framework and among them 1 has been used as a catalyst for hydroboration of alkenes and alkynes with pinacolborane (HBpin). A broad variety of aromatic and aliphatic alkenes and alkynes were efficiently reduced. Anti-Markovnikov regioselective hydroboration of alkenes and alkynes was achieved, which was confirmed by deuterium-labelling experiments. The work represents the first example of the use of magnesium in homogeneous catalytic hydroboration of alkene with broad substrate scope. Experimental mechanistic investigations and DFT calculations provided insights into the reaction mechanism. Finally, the hydroboration protocol was extended to terpenes.
Keywords: carbazole; Magnesium; monomeric complexes; phosphorous; X-ray Structure

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

Multi-purpose synthetic alpha-amino acid featuring coumarin and ureidopyrimidinone motifs on its backbone: Synthesis and peptide formation - Rashid, P. P.; Sanjayan, Gangadhar J. (Tetrahedron Letters, 2022)
Herein we report a synthetic a-amino acid featuring intensely fluorescent coumarin moiety and a strongly self-assembling ureidopyrimidinone (UPy) motif. This two-in-one synthetic amino acid, displaying both fluorescence and self-assembling property, has been synthesized in four easy steps starting from commercially available inexpensive starting materials. Suitably protected amino acid has been incorporated into various peptide sequences, following solution-phase peptide coupling protocols, to demonstrate its synthetic feasibility.(c) 2022 Elsevier Ltd. All rights reserved.
Keywords: Fluorescent amino acids; Fluorescent Peptides; Quadruple hydrogen bonding; Unnatural amino acids; Ureidopyrimidinone

MXenes: advances in the synthesis and application in supercapacitors and batteries - Wasnik, Kundan; Pawar, Meenakshi D.; Raphael, Leya Rose; Pullanchiyodan, Abhilash; Shelke, V. Manjusha; Raghavan, Prasanth (Journal of Materials Research, 2022)
MXenes, the newest family member of the two-dimensional materials have been widely investigated for different applications, particularly in the energy storage realm. With regard to this, MXene precursors have attained widespread attention for the application in electrochemical energy storage devices especially supercapacitors and batteries. This review has comprehensively studied various synthesis strategies adopted for MXenes including the top-down and bottom-up approaches. The shift to renewable energy alternatives have focused on the electrochemical choices such as supercapacitors and batteries, the most common and relevant ones. Thus the application of MXenes and its composite in supercapacitors as electrodes have been analyzed along with its detailed mechanism and electrochemical performance. Several battery chemistries including lithium-ion, sodium-ion and other battery systems utilizing MXenes have also been discussed here. Thus the existing strategies, advancements, and drawbacks regarding the inclusivity of MXenes in the electrochemical energy systems of supercapacitors and batteries are reviewed in this article.

Nanocellulose/melanin-based composites for energy, environment, and biological applications - Ram, Farsa; Yadav, Prashant; Shanmuganathan, Kadhiravan (Journal of Materials Science, 2022)
Melanins, a class of brown-black pigments present in many natural sources, exhibit unique physical and chemical properties such as photoprotection, photoconductivity, metal ion chelation, free radical quenching, proton conductivity, and significant antimicrobial properties. These properties could be leveraged in various environmental and energy applications. However, their limited solubility makes them less amenable to processing. Over the last decade, there has been tremendous interest in developing synthetic analogs of melanin that are easy to dissolve and process. Nonetheless, melanins or their synthetic analogs cannot form mechanically robust free-standing films and fibers. This drawback could be partly circumvented by creating composites of melanin with nanocellulose, a nanomaterial derived from cellulosic biomass. Composites of melanins and nanocellulose offer an opportunity to utilize the functional aspects of melanin-like polymers in a mechanically stable nanocellulose network. This review attempts to capture the recent developments on this topic with special emphasis on technologically relevant applications.

Noble-metal-free heterojunction photocatalyst for selective CO2 reduction to methane upon induced strain relaxation - Das, Risov; Sarkar, Shreya; Kumar, Ritesh; Ramarao, Seethiraju D.; Cherevotan, Arjun; Jasil, Mohammed; Vinod, Chathakudath P.; Singh, Abhishek Kumar; Peter, Sebastian C. (ACS Catalysis, 2022)
Sunlight-driven CO2 hydrogenation has drawn tremendous attention. However, selective CH4 formation via CO2 photoreduction is very challenging. Herein, we report a metal oxide semiconductor heterojunction consisting of BiVO4 and WO3 as a photocatalyst for the efficient conversion of carbon dioxide (CO2) selectively to methane (105 mu mol g(-1) h(-1)) under visible light in the absence of a sacrificial agent. Wise selection of the reaction medium and the strategically tuned heterojunction upon strain relaxation suppresses the competitive hydrogen generation reaction. The detailed photophysical, photoelectrochemical, and X-ray absorption spectroscopy studies pointed to the Z-scheme mechanism of electron transfer, which favors superior electron and hole separation compared to the individual components of the composite catalyst and other well-known photocatalysts reported for CO2 reduction. The observations are further corroborated by experimental diffuse reflectance infrared Fourier transform spectroscopy and theoretical density-functional theory calculations, which reveal that the heterojunction has a lower free-energy barrier for CO2 conversion to CH4 due to the larger stabilization of the *CH2O intermediate on the strain-relaxed heterojunction surface, in comparison to the pristine BiVO4 surface. The present work provides fundamental insights for constructing high-performance heterojunction photocatalysts for the selective conversion of CO2 to desired chemicals and fuels.
Keywords: CO2 reduction; heterostructure; methane; Photocatalysis; Z-scheme

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

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

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

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

Nucleophilic substitution at a coordinatively saturated five-membered NHC center dot haloborane centre - Kundu, Gargi; Tothadi, Srinu; Sen, Sakya S. (Inorganics, 2022)
In this paper, we have used a saturated five-membered N-Heterocyclic carbene (5SIDipp = 1,3-bis-(2,6-diisopropylphenyl)imidazolin-2-ylidine) for the synthesis of SNHC-haloboranes adducts and their further nucleophilic substitutions to put unusual functional groups at the central boron atom. The reaction of 5-SIDipp with RBCl2 yields Lewis-base adducts, 5-SIDipp center dot RBCl2 [R = H (1), Ph (2)]. The hydrolysis of 1 gives the NHC stabilized boric acid, 5-SIDipp center dot B(OH)(3) (3), selectively. Replacement of chlorine atoms from 1 and 2 with one equivalent of AgOTf led to the formation of 5-SIDipp center dot HBCl(OTf) (4) and 5-SIDipp center dot PhBCl(OTf) (5a), where all the substituents on the boron atoms are different. The addition of two equivalents of AgNO3 to 2 leads to the formation of rare di-nitro substituted 5-SIDipp center dot BPh(NO3)(2) (6). Further, the reaction of 5-SIDipp with B(C6F5)(3) in tetrahydrofuran and diethyl ether shows a frustrated Lewis pair type small molecule activated products, 7 and 8.
Keywords: NHC-haloboranes; nucleophilic substitution; saturated NHC; tetra-coordinate boron

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

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

Perception of glycerol carbonate as green chemical: synthesis and applications - Gade, Swapna M.; Saptal, Vitthal B.; Bhanage, Bhalchandra M. (Catalysis Communications, 2022)
Glycerol carbonate (GC) is a prominent component in industrial practice and has a remarkable potential for the sophisticated applications. While GC has come into prominence due to the perceived overflow of glycerol (GLY) as a coproduct of biodiesel industry, its contemporary and future downstream applications are driving tremendous interest in recent years. This review comprises strategies for glycerol carbonate synthesis, properties and its applications. The conversion of GLY to GC via transesterification has appeared in consensus to be the most promising route. A detailed explanation of the effect of the catalysts and operating conditions on the GC yield to provide an updated understanding of the process are summarized. Future directions for GC production through catalytic transesterification are also discussed.
Keywords: Biodiesel; biofuels; catalysis; Glycerol; Glycerol carbonate; green chemistry; transesterification

Pharmaceutical standardization and physicochemical characterization of traditional ayurvedic mineral drug red ochre roasted in cow's ghee (Shuddha Gairik) - Chavan, S. B.; Gupta, V. S.; Deshmukh, V. V.; Sardeshmukh, S. P. (Indian Journal of Traditional Knowledge, 2022)
Rasashastra is a pharmaceutics branch of Ayurveda describing scientific methods to convert metals and minerals into bio-compatible formulations used individually or plant admixed to enhance their bioavailability and efficacy. In the present study, red ochre (Gairik) powder was processed in cow's ghee by textual method of roasting. The steps of preparation and changes in the properties therein were documented and validated in triplicate batches to develop a monograph. Ayurvedic and basic tests were performed to determine the properties of Shuddha Gairik. The physical characterization included Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), Fourier Transform Infra-red (FT-IR), Dynamic Light Scattering (DLS) and Thermo-gravimetric Analysis (TGA). Elemental composition was estimated by titration and gravimetric analysis while heavy metal limits were assessed using Inductively Coupled Plasma Optical Emission Spectrophotometry (ICPOES). This study depicted that crude red ochre, containing Kaolinite with high iron percentage, on roasting in cow's ghee led to the formation of fatty acids adsorbed red ochre particles. The developed monograph will be a guideline to the Ayurvedic industry for precise formulation of Shuddha Gairik. This will help researchers for better understanding the importance of Ayurvedic methods of pharmaceutical preparations and carry out their mechanistic studies in various diseases.
Keywords: Ferric oxide; Gairik; Kaolinite; Monograph; Red ochre; Roasting

Poly(N-vinylcaprolactam) containing solid lipid polymer hybrid nanoparticles for controlled delivery of a hydrophilic drug gemcitabine hydrochloride - Surapaneni, Sai Geetika; Ambade, V. Ashootosh (RSC Advances, 2022)
Folic acid tagged and hydrophilic polymer containing solid lipid nanoparticles (SLNs) were formulated for the controlled and targeted delivery of gemcitabine, a hydrophilic drug. Drug loaded SLNs were prepared by double emulsion method and optimized by 3(2) level factorial design. Then, a hydrophilic polymer, namely, poly(N-vinylcaprolactam) (PVCL) was incorporated in the optimized SLN batch in the first aqueous phase (W1) to obtain solid lipid polymer hybrid nanoparticles (SLPHNs) that were further decorated with folic acid (F-SLPHNs). TEM analysis of SLNs and SLPHNs revealed the spherical shape with no aggregation while SLPHNs showed higher % EE. SLPHNs exhibited limited burst release of gemcitabine compared to SLNs as well as lower overall % release. All the formulations showed good cytocompatibility against MDA-MB-231 cell lines and folic acid-tagged hybrid particles (F-SLPHNs) showed remarkably higher cellular uptake.

Potential- and time-dependent dynamic nature of an oxide-derived pdin nanocatalyst during electrochemical CO2 reduction - Bagchi, Debabrata; Sarkar, Shreya; Singh, Ashutosh Kumar; Vinod, Chathakudath P.; Peter, Sebastian C. (ACS Nano, 2022)
Electrochemical reduction of CO2 into valuable fuels and chemicals is a promising route of replacing fossil fuels by reducing CO2 emissions and minimizing its adverse effects on the climate. Tremendous efforts have been carried out for designing efficient catalyst materials to selectively produce the desired product in high yield from CO2 by the electrochemical process. In this work, a strategy is reported to enhance the electrochemical CO2 reduction reaction (ECO2RR) by constructing an interface between a metal-based alloy (PdIn) nanoparticle and an oxide (In2O3), which was synthesized by a facile solution method. The oxide-derived PdIn surface has shown excellent eCO(2)RR activity and enhanced CO selectivity with a Faradaic efficiency (FE) of 92.13% at -0.9 V (vs RHE). On the other hand, surface PdO formation due to charge transfer on the bare PdIn alloy reduces the CO2RR activity. With the support of in situ (EXAFS and IR) and ex situ (XPS, Raman) spectroscopic techniques, the optimum presence of the Pd-In-O interface has been identified as a crucial parameter for enhancing eCO(2)RR toward CO in a reducing atmosphere. The influence of eCO(2)RR duration is reported to affect the overall performance by switching the product selectivity from H-2 (from water reduction) to CO (from eCO(2)RR) on the oxide-derived alloy surface. This work also succeeded in the multifold enhancement of the current density by employing the gas diffusion electrode (GDE) and optimizing its process parameters in a flow cell configuration.
Keywords: CO2 reduction; Electrochemistry; heterostructure interface; in situ mechanism; nanocatalyst

Preface to special issue on protein-mediated membrane remodeling - Chakraborty, Hirak; Sengupta, Durba (Journal of Membrane Biology, 2022)

Probes and techniques used in active and the hypoxia-based dormant state of an antitubercular drug screening assay - Yeware, Amar; Akhtar, Shamim; Sarkar, Dhiman (Medicine in Drug Discovery, 2022)
Current antitubercular drug therapy requires more than six months and is unable to kill latent or dormant forms of tuberculosis. Thus, it is a need of new drug therapy to fight against dormant tuberculosis. However, the major obstacle in the development of novel drugs for dormant tuberculosis is the lack of relevant screening systems and using reliable probes to measure growth inhibition. Until now, several probes used in active state assays are significantly determining the inhibitory effect against the active state of mycobacteria. The dormant condition assays are based on hypoxia-derived dormancy which include resazurin reduction assay, nitrite reductase assay, XTT reduction menadione assay and low oxygen recovery assay. Major probes used in those assays are colorimetric/fluorescent dyes, enzymatic activity, and reporter genes include luciferase and fluorescent proteins. Although these dormant assays are based on hypoxia-induced features and difficult to maintain for a longer duration. Also, they further complicated by growth detection and pursuit of high throughput screening criteria. Here we reviewed complications of probes and assay techniques used for anti-dormant drug screening programs of tuberculosis. This will provide the knowledge to design better alternative drug screening method for the anti-dormant form of tuberculosis.
Keywords: Active and dormant states; and; Drug screening assay; Probes; tuberculosis

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

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

Profiling of metabolic alterations in mice infected with malaria parasites via high-resolution metabolomics - Chhibber-Goel, Jyoti; Shukla, Anurag; Shanmugam, Dhanasekaran; Sharma, Amit (Molecular and Biochemical Parasitology, 2022)
Background: Malaria infection can result in distinct clinical outcomes from asymptomatic to severe. The association between patho-physiological changes and molecular changes in the host, and their correlation with severity of malaria progression is not fully understood. Methods: In this study, we addressed mass spectrometry-based temporal profiling of serum metabolite levels from mice infected with Plasmodium berhgei (strain ANKA). Results: We show global perturbations and identify changes in specific metabolites in correlation with disease progression. While metabolome-wide changes were apparent in late-stage malaria, a subset of metabolites exhibited highly correlated changes with disease progression. These metabolites changed early on following infection and either continued or maintained the change as mice developed severe disease. Some of these have the potential to be sentinel metabolites for severe malaria. Moreover, glycolytic metabolites, purine nucleotide precursors, tryptophan and its bioactive derivatives were many fold decreased in late-stage disease. Interestingly, uric acid, a metabolic waste reported to be elevated in severe human malaria, increased with disease progression, and subsequently appears to be detoxified into allantoin. This detoxification mechanism is absent in humans as they lack the enzyme uricase. Conclusions: We have identified candidate marker metabolites that may be of relevance in the context of human malaria.
Keywords: Host response; Infectious diseases; malaria; metabolite; Plasmodium

Progress and potential of electrospinning-derived substrate-free and binder-free lithium-ion battery electrodes - Joshi, Bhavana; Samuel, Edmund; Kim, Yong-il; Yarin, Alexander L.; Swihart, Mark T.; Yoon, Sam S. (Chemical Engineering Journal, 2022)
Carbon nanofibers derived from electrospun precursors show great promise for electronic applications owing to their flexibility, conductivity, high surface area, and open structure. The integration of metal oxides and sulfides in carbon nanofibers, rather than using them with other binders, eliminates many problems caused by poor adhesion, nanomaterial agglomeration, excess mass contributed by inactive binders, and low conductivity of embedded active materials. The engineering of electrospun fibers with novel morphologies, such as core-shell, hollow, or porous structures, and the use of decorated carbon nanofibers (e.g., by electrodeposition or co precipitation) are discussed in this review. Representative schematic illustrations of the lithium-storage mechanism for these binder-free electrodes are presented. We describe how the electrospinning technique can offer a cost-effective strategy for fabrication of lightweight lithium-ion batteries with high capacity and excellent bendability. This review presents the fascinating morphologies of these specially designed carbon nanofiber electrodes, which enhance the electrochemical performance of metal oxides and sulfides, illustrating their enormous potential for use in wearable electronic devices and hybrid electric vehicles.
Keywords: Carbon nanofibers; Co-axial; composites; core-shell; electrospinning; Flexible

Protophilic solvent-impelled quasi-catalytic CO2 valorization to formic acid and N-formamides - Wu, Hongguo; Li, Hu; Zhao, Wenfeng; Sudarsanam, Putla; Yang, Song (Fuel, 2022)
As a low-price and luxuriant C1 sustainable resource, CO2 has the privilege of synthesizing hydrogen carriers and valuable chemicals. However, expensive metallic and organic catalysts are often indispensable for going on wheels of the relevant reaction processes. In this work, a protophilic solvent-impelled quasi-catalytic system was developed for efficient synthesis of formic acid and various N-formamides with high yields of 76-94% via reductive CO2 functionalization under mild reaction conditions (50 ?). Direct activation of the liquid hydrosilane toward the reduction of CO2 enabled by DMSO with optimum basicity/protophilicity is the predominant reaction route among the examined interaction models, while carbonic acid potentially derived from excessive CO2 and residual water inhibits the reaction, as explicitly disclosed by theoretical calculations and isotope labeling experiments. In addition, the in situ formed O-formyl species is conductive to the cascade CO2 reduction steps, which remarkably facilitated the overall quasi-catalytic upgrading process.
Keywords: CO2 utilization; Formic acid; Green energy; Nitrogenous chemicals; Quasi-catalysis

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

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

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

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

Research progress and perspective on lithium/sodium metal anodes for next-generation rechargeable batteries - Patrike, Apurva; Yadav, Poonam; Shelke, Vilas; Shelke, Manjusha (ChemSusChem, 2022)
With the development of consumer electronic devices and electric vehicles, lithium-ion batteries (LIBs) are vital components for high energy storage with great impact on our modern life. However, LIBs still cannot meet all the essential demands of rapidly growing new industries. In pursuance of higher energy requirement, metal batteries (MBs) are the next-generation high-energy-density devices. Li/Na metals are considered as an ideal anode for high-energy batteries due to extremely high theoretical specific capacity (3860 and 1165 mAh g(-1) for Li and Na, respectively) and low electrochemical potential (-3.04 V for Li and -2.71 V for Na vs. standard hydrogen electrode). Unfortunately, uncontrolled dendrite growth, high reactivity, and infinite volume change induce severe safety concerns and poor cycle efficiency during their application. Consequently, MBs are far from commercialization stage. This Review represents a comprehensive overview of failure mechanism of lithium/sodium metal anode and its progress for rechargeable batteries through (i) electrolyte optimization, (ii) artificial solid-electrolyte interphase (SEI) layer formation, and (iii) nanoengineering at materials level in current collector, anode, and host. The challenges in current MBs research and potential applications of lithium/sodium metal anodes are also outlined and summarized.
Keywords: anode; Batteries; dendrite growth; Electrolytes; Energy storage

Review of recent progress in electrospinning-derived freestanding and binder-free electrodes for supercapacitors - Joshi, Bhavana; Samuel, Edmund; Kim, Yong-il; Yarin, Alexander L.; Swihart, Mark T.; Yoon, Sam S. (Coordination Chemistry Reviews, 2022)
The versatile electrospinning technique is scalable and suitable to fabricate highly conducting freestanding carbon nanofiber composite electrodes for energy storage devices. Freestanding/flexible electrodes hold enormous potential for use in wearable electronic devices. Carbon-yielding polymers and the optimal use of sacrificial polymers, metal oxides, and sulfides retain the flexibility and enhance the surface area and pseudocapacitance of electrodes. Both as-prepared electrospun fibers and carbonized nanofibers are compatible with surface decoration via various chemical and electrochemical routes. Metal oxides/sulfides with various morphologies, such as nanocones and nanosheets, can be grown on the carbon nanofibers or on the as-prepared electrospun fibers using chemical synthesis methods such as electro-deposition, hydrothermal processes, and chemical impregnation to enhance the pseudocapacitance of the electrodes. Similarly, the deposition of metal organic frameworks on as-prepared electrospun fibers embellishes these fibers with nanostructures of specific morphologies such as dodecahedral and spindle-shaped structures. Under optimal conditions, these morphologies do not hamper the flexibility of the fibers, and binders are not required to retain them or maintain the electrode integrity. The engineering of electrodes with various morphologies and process parameters is presented systematically. Electrospinning-derived electrodes that have demonstrated significant electrochemical performance are highlighted and critically analyzed, and the energy storage mechanisms of these supercapacitors are described in detail. (C) 2022 Elsevier B.V. All rights reserved.
Keywords: Carbon nanofibers; Co-axial; composites; core-shell; electrospinning; Flexible; Porous; supercapacitor

Review on computational analysis of big data in breast cancer for predicting potential biomarkers - Shaikh, Nilofer; Bapat, Sanket; Karthikeyan, Muthukumarasamy; Vyas, Renu (Current Topics in Medicinal Chemistry, 2022)
Breast cancer is the most predominantly occurring cancer in the world. Several genes and proteins have been recently studied to predict biomarkers that enable early disease identification and monitor its recurrence. In the era of high-throughput technology, studies show several applications of big data for identifying potential biomarkers. The review aims to provide a comprehensive overview of big data analysis in breast cancer towards the prediction of biomarkers with emphasis on computational methods like text mining, network analysis, next-generation sequencing technology (NGS), machine learning (ML), deep learning (DL), and precision medicine. Integrating data from various computational approaches enables the stratification of cancer patients and the identification of molecular signatures in cancer and their subtypes. The computational methods and statistical analysis help expedite cancer prognosis and develop precision cancer medicine (PCM). As a part of case study in the present work, we constructed a large gene-drug interaction network to predict new biomarkers genes. The gene-drug network helped us to identify eight genes that could serve as novel potential biomarkers.
Keywords: Big data; Biomarkers; Breast cancer; Driver genes; Network analysis; text mining

Role of 2D material families in energy harvesting: an editorial overview - Raghavan, Prasanth; Ahn, Jou-Hyeon; Shelke, Manjusha (Journal of Materials Research, 2022)
The ever increasing proportion of an energy consuming society and the boost in industrialization accelerated the depletion of fossil fuel based energy sources at an alarming rate. This emphasizes the necessity of sustainable energy generation and storage to meet the daily energy demands. But, these alternative renewable energy sources like solar and wind power are intermittent and highly depend on weather, place and individuals. This creates the inevitability of suitable energy storage devices like batteries and supercapacitors. The interfacing of energy storing devices is required to maintain the supply chain equilibrium, power efficiency, regulate power fluctuations and reduce pollution. Besides, the boom in electric mobility and consumer electronics also require uninterrupted power supply. Hence, in the upcoming years the energy storing devices play a vital role in addressing the energy crisis. Innovations in new materials and technologies will be the core area of research and development in the coming future. 2D materials like graphene,transition metal carbides and nitrides (MXenes), transition metal borides (MBenes) and so on are the new class of materials among them MXenes are getting more attention in energy storage owing to its exceptional properties.

Room temperature chemoselective hydrogenation of C=C, C=O and C=N bonds by using a well-defined mixed donor Mn(I) pincer catalyst - Shabade, Anand B.; Sharma, Dipesh M.; Bajpai, Priyam; Gonnade, Rajesh G.; Vanka, Kumar; Punji, Benudhar (Chemical Science, 2022)
Chemoselective hydrogenation of C=C, C=O and C=N bonds in alpha,beta-unsaturated ketones, aldehydes and imines is accomplished at room temperature (27 degrees C) using a well-defined Mn(I) catalyst and 5.0 bar H-2. Amongst the three mixed-donor Mn(I) complexes developed, kappa(3)-((PNNPyz)-P-R2-N-3)Mn(CO)(2)Br (R = Ph, Pr-i, Bu-t); the Bu-t -substituted complex ((PNNPyz)-P-tBu2-N-3)Mn(CO)(2)Br shows exceptional chemoselective catalytic reduction of unsaturated bonds. This hydrogenation protocol tolerates a range of highly susceptible functionalities, such as halides (-F, -Cl, -Br, and -I), alkoxy and hydroxy, including hydrogen-sensitive moieties like acetyl, nitrile, nitro, epoxide, and unconjugated alkenyl and alkynyl groups. Additionally, the disclosed method applies to indole, pyrrole, furan, thiophene, and pyridine-containing unsaturated ketones leading to the corresponding saturated ketones. The C=C bond is chemoselectively hydrogenated in alpha,beta-unsaturated ketones, while the aldehyde's C=O bond and imine's C=N bond are preferentially reduced over the C=C bond. A detailed mechanistic study highlighted the non-innocent behavior of the ligand in the ((PNNPyz)-P-tBu2-N-3) Mn(I) complex and indicated a metal-ligand cooperative catalytic pathway. The molecular hydrogen (H-2) acts as a hydride source, whereas MeOH provides a proton for hydrogenation. DFT energy calculations supported the facile progress of most catalytic steps, involving a crucial turnover-limiting H-2 activation.

Room temperature Z-selective hydrogenation of alkynes by hemilabile and non-innocent (NNN)Co(ii) catalysts - Sharma, Dipesh M.; Gouda, Chandrakant; Gonnade, Rajesh G.; Punji, Benudhar (Catalysis Science & Technology, 2022)
Hemilabile and phosphine-free quinolinyl-based NNN-type pincer and non-pincer cobalt complexes were developed for the room temperature catalytic transfer semi-hydrogenation of alkynes to Z-alkenes. Treatment of the quinolinyl-amine ligand, [C9H6N(NH)CH2CH2NEt2] ((NNN2NEt2)-N-Q-N-CH)-H with CoX2 afforded the pincer complexes kappa(3)-((NNN2NEt2)-N-Q-N-CH)CoX2 (X = Cl, Br), whereas, the quinolinyl-amide ligand, [C9H6N(NH)C(O)CH2NEt2] ((NNNNEt2)-N-Q-N-C(O))-H gave chelate anionic complexes kappa(2)-((NN)-N-Q)CoX2((NHNEt2)-H-C(O)) (X = Cl, Br). The well-defined anionic non-pincer cobalt complexes efficiently catalyzed the semi-hydrogenation of diverse alkynes to deliver highly chemoselective and stereodivergent Z-alkenes at room temperature. This hydrogenation exhibited broad substrate scope with the tolerance of sensitive functional groups, such as -Cl, -Br, -I, -OH, -NH2, -COOMe, and pyridinyl, employing a stable and user-friendly ammonia borane hydrogen source.

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

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

Scan-find-scan-model: discrete site-targeted suppressor design strategy for amyloid-beta - Bhagavatula, Hasathi; Sarkar, Archishman; Santra, Binit; Das, Atanu (ACS Chemical Neuroscience, 2022)
Alzheimer's disease is undoubtedly the most well-studied ranks at the top in terms of getting attention from the scientific community for structural property-based characterization. Even after decades of extensive research, there is existing volatility in terms of understanding and hence the effective tackling procedures against the disease that arises due to the lack of knowledge of both specific targetand site-specific drugs. Here, we develop a multidimensional approach based on the characterization of the common static-dynamic-thermodynamic trait of the monomeric protein, which efficiently identifies a small target sequence that contains an inherent tendency to misfold and consequently aggregate. The robustness of the identification of the target sequence comes with an abundance of a priori knowledge about the length and sequence of the target and hence guides toward effective designing of the target-specific drug with a very low probability of bottleneck and failure. Based on the target sequence information, we further identified a specific mutant that showed the maximum potential to act as a destabilizer of the monomeric protein as well as enormous success as an aggregation suppressor. We eventually tested the drug efficacy by estimating the extent of modulation of binding affinity existing within the fibrillar form of the A beta protein due to a single-point mutation and hence provided a proof of concept of the entire protocol.
Keywords: configurational misfoldability; drug developability; inherent frustration; potential aggregability; sequence-based mutability; target specificity

Selective production of C9 monomeric phenols via hydrogenolysis of lignin using Pd-(W/Zr/Mo oxides)-supported on biochar catalyst - Gurrala, Lakshmiprasad; Kumar, M. Midhun; Sharma, Shweta; Paek, Changyub; Vinu, R. (Fuel, 2022)
Valorizing lignin to phenolic monomers and fine chemicals is an essential component of a sustainable biorefinery that uses lignocellulosic feedstocks. In this study, Pd-metal oxides (ZrO2, WOx, MoO3) supported on activated biochar (ABC) catalysts were developed for hydrogenolysis of lignin. The metals (2% Pd, 5% Zr, 5% W, 5% Mo) were supported on activated biochar using the wetness impregnation method, and the catalysts were extensively characterized. The effect of addition of secondary metals on active surface properties such as acidity, Pd metal particle size and dispersion were also evaluated. The selectivity to C9 monomeric phenols followed the trend: 2Pd-5Mo/ABC (57.3%) > 2Pd-5Zr/ABC (49.2%) > 2Pd-5W/ABC (45%) > 2Pd/ABC (42.9%). The maximum C9 phenolic monomer yield achieved in this study was similar to 22 wt%. The fractional conversion of lignin was 67-69% with Pd-metal oxide catalysts. The presence of Mo in the catalyst inhibited the hydrogenation of aliphatic C-alpha = C-beta in lignin and led to the formation of t-isoeugenol, while the presence of W and Zr resulted in selective formation of the hydrogenated product, propyl guaiacol. Using model compounds, it is proved that the formation of propyl guaiacol is via hydrogenation of t-isoeugenol, and not through dehydroxylation of propanol guaiacol. The dehydroxylation activity of the catalysts is attributed to the higher Lewis acidity and electropositive nature of the metals. A notable carbon atom economy of 47-50% towards total phenolic monomers was achieved with 2Pd/ABC, 2Pd-5Mo/ABC and 2Pd-5Zr/ABC catalysts.
Keywords: Activated biochar; Guaiacol; Hydrogenolysis; lignin; Metal oxides; Palladium

Shape-controlled nanostructured MoO3/CeO2 catalysts for selective cyclohexene epoxidation - Sudarsanam, Putla; Singh, Nittan; Kalbande, Pavan Narayan (Catalysis Communications, 2022)
This study reported a vital role of CeO2 shape on the structure-activity properties of MoOx/CeO2 catalysts for cyclohexene epoxidation. Uniform dispersion of MoOx on the surface of shape-controlled CeO2 nanocubes (average particle size: 23.5 nm) and nanorods (average width: 6.3 nm and length: 15-95 nm) was found in MoOx/CeO2 nanomaterials. The MoOx/CeO2 nanocubes showed higher epoxide selectivity (97.3%) with 98.9% cyclohexene conversion, although it has lower BET surface area (30.2 m(2)/g) compared with MoOx/CeO2 nanorods (72.8 m(2)/g). The presence of more electropositive Mo6+ species and the strong Mo-Ce interaction led to improved catalytic efficacy of MoOx/CeO2 nanocubes in cyclohexene epoxidation.
Keywords: CeO2 nanocubes; CeO2 shapes; Nanosized MoOx/CeO2 catalyst; Selective epoxidation; Structure-activity properties

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

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

Single-step insertion of M-Nx moieties in commercial carbon for sustainable bifunctional electrocatalysis: mapping insertion capacity, mass loss, and carbon reconstruction - Garg, Reeya; Sahoo, Lipipuspa; Kaur, Komalpreet; Vinod, C. P.; Gautam, Ujjal K. (Carbon, 2022)
Atomically dispersed earth-abundant metals in N-doped carbon (M-N-Cs) have emerged as a new class of electroactive materials that can match not only the performance of the precious metals but can catalyze both the cathodic and the anodic reactions due to their bifunctional behaviour. This inspires the development of simpler strategies for scale-up production since the existing ones rely on precursors whose commercial viability is not yet ascertained. Herein, we demonstrate the insertion prospects of M-Nx (M = Fe, Co, Ni) moieties, the electrocatalytic centers in the M-N-Cs, into commercial carbon to establish that a single-step heating of the inexpensive precursors is sufficient to generate bifunctional electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) with efficiencies that bypass the majority of the known catalysts. Further importantly, we quantify both the ORR and OER trends and the metal insertion limits for each metal while maintaining an atomic dispersion, without the formation of surface migration-induced clustering, because such clustering is inevitable in the existing processes to necessitate an extra acid-leaching step to remove them. We further quantify and explain for each metal a negative mass balance originating from anomalous mass loss of both metal and carbon content, and a massive reconstruction of the carbon backbone catalyzed by the very metal, an event documented for the first time though it ought to be associated with other M-N-C syntheses too. The study establishes an incredibly simple and inexpensive strategy for the realization of M-N-Cs and outlines the parameters to be considered during mass-production.
Keywords: Bifunctional catalysis; Carbon reconstruction; Commercial carbon; Metal insertion; Oxygen electrocatalysis

Single-step synthesis of exfoliated Ti3C2Tx MXene through NaBF4/HCl etching as electrode material for asymmetric supercapacitor - Ghosh, Meena; Szunerits, Sabine; Cao, Ning; Kurungot, Sreekumar; Boukherroub, Rabah (ChemistrySelect, 2022)
Two-dimensional Ti3C2Tx MXene, derived from the parent Ti3AlC2 phase, is considered a promising electrode material for electrochemical energy storage applications. Ti3C2Tx MXene synthesis methods often employ concentrated hydrofluoric acid (HF), which is harsh, corrosive, and hazardous to the environment. Herein, we report the preparation of Ti3C2Tx MXene following a new synthetic route under a mild reaction condition comprising an aqueous solution of NaBF4 and HCl. This etching environment at a moderate temperature of 130 degrees C effectively removes the Al layer of the Ti3AlC2 precursor, assisted by the in situ formed HF in the reaction medium. Electron microscopy images of the as-prepared Ti3C2Tx (MX-130) reveal a partially exfoliated nanosheet-like morphology. The material displays a specific capacitance of 262 F g(-1) (three-electrode assembly, 1 A g(-1), -0.85 to -0.25 V vs. Hg/Hg2SO4) in 1 M H2SO4 electrolyte. The achieved specific capacitance is superior to that of Ti3C2Tx prepared via the common HF-treatment (25 F g(-1)). Additionally, the potential application of the optimized MXene as a negative electrode material is demonstrated in a quasi-solid-state RuO2|MX-130 asymmetric supercapacitor device.
Keywords: asymmetric supercapacitor; Electrochemistry; Fluoride salt etchant; Layered electrode materials; Transition metal carbides

Six-membered saturated NHC-stabilized borenium cations: isolation of a cationic analogue of borinic acid - Kundu, Gargi; Balayan, Kajal; Tothadi, Srinu; Sen, Sakya S. (Inorganic Chemistry, 2022)
The reaction of six-membered saturated NHC [1,3-di(2,6-diisopropylphenyl) tetrahydropyrimidine-2-ylidene; henceforth abbreviated as 6-SIDipp] with PhBCl2 yields a Lewis base adduct, 6-SIDipp.PhBCl2 (1), which readily undergoes nucleophilic substitution reaction with AgNO3, leading to the single (2) and double (3) substitution of both chlorides with ONO2 moieties at the boron atom. The reaction of 1 with 1 equiv of AlCl3 resulted in a borenium cation of composition [6-SIDipp.B(Ph)Cl]+ (4) with AlCl4- as the counteranion. Although borenium cations with different substituents on boron have been reported, a structurally characterized phenylchloroborenium cation remains unknown. Similarly, the reaction of 1 with triflic acid provides the first representative of a new class of borenium cations bearing one hydroxyl and one phenyl group on boron (5), a cationic analogue of borinic acid. Ph-BN H Diphenylborinic acid

Solvent-driven mono- and bis-sulfenylation of (E)-beta-iodovinyl sulfones with thiols for flexible synthesis of 1,2-thiosulfonylalkenes and 1,2-dithioalkenes - Reddy, Raju Jannapu; Kumari, Arram Haritha; Sharadha, Nunavath; Krishna, Gamidi Rama (Journal of Organic Chemistry, 2022)
The nature of solvent is a key factor for stereoselective mono-and bis-thiolation of (E)-beta-iodovinyl sulfones with thiols under basic conditions. A novel and unprecedented vicinal bisthiolation of (E)-beta-iodovinyl sulfones with thiols under the influence of K2CO3/DMSO at room temperature for quick assembly of (E)-1,2-dithio-1-alkenes is presented. Solvent-induced stereoselective monosulfenylation of (E)-beta-iodovinyl sulfones with thiols has also been established for the synthesis of both (E)- and (Z)-1,2-thiosulfonylethenes in MeCN and MeOH, respectively. Moreover, K2CO3-mediated desulfonylative-sulfenylation of (Z)-1,2-thiosulfonylethenes with thiols in DMSO furnished unsymmetrical (Z)-1,2-dithio-1-alkenes for the first time. The solvent-dependent versatile reactivity of (E)-beta-iodovinyl sulfones has been successfully explored to provide a set of (E)-/(Z)-1,2-dithio-1-alkenes and (E)-/(Z)-1,2-thiosulfonyl-1-alkenes in good to high yields with excellent stereoselectivities. Notably, this operationally simple process utilizes a broad substrate scope with good functional group tolerance and compatibility. The efficacy of the process has been proven for gram-scale reactions, and plausible mechanistic models are outlined on the basis of experimental results and control experiments.

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

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

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

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

Strain-enhanced phase transformation of iron oxide for higher alcohol production from CO2 - Goud, Devender; Churipard, Sathyapal R.; Bagchi, Debabrata; Singh, Ashutosh Kumar; Riyaz, Mohd; Vinod, C. P.; Peter, Sebastian C. (ACS Catalysis, 2022)
Conversion of CO2 to higher alcohols (HAs) and higher hydrocarbons (HCs) has a greater advantage compared to C1 products because of their high energy density and wide range of applications in daily life. Despite the immense potential of these chemicals, not much of scientific research has been focused on the conversion of CO2 to HAs. In the present work, we have introduced the concept of strain in designing the material to enhance the CO(2 )to HA performance. We introduced strain in a traditional iron-based catalyst, Fe2O3, by the introduction of indium (In), which facilitates the selective conversion of CO2 to HA. An optimum strain favored a 36.7% CO2 conversion with a 42% HA selectivity, and a record yield of 15.42%. The strain has been tuned further with the introduction of K as a promoter. The introduced strain upon In substitution and K promotion favored the conversion of CO2, which is mapped by powder X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy. Further, the change in the mechanism upon In incorporation and K promotion has been probed by in situ diffuse reflectance infrared fourier transform spectroscopy, and it is found that the OCHx intermediate, which produces HAs, is more prominent upon In substitution, which favored the enhancement of HA production compared to that of pristine Fe2O3.
Keywords: CO2 to HA; Fischer-Tropsch synthesis (FTS); Phase transformation; reverse water gas shift (RWGS) reaction; strain

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

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

Studies toward the total synthesis of (+)-neopeltolide using N-heterocyclic carbene-catalyzed oxo-acyloxylation/reductive oxa-Michael addition strategy - Reddi, Rambabu N.; Sudalai, Arumugam; Jo, Changbum (Bulletin of the Korean Chemical Society, 2022)
This article describes a concise synthesis of two important fragments (tetrahydropyran [THP] and ketone moieties) of the cytotoxic macrolide (+)-neopeltolide in 10 long linear steps in enantiomerically pure form. Asymmetric Keck allylation to install the required C11 and C13 stereocenters, N-heterocyclic carbene (NHC)-catalyzed oxoacyloxylation to functionalize alkenes, and reductive oxa-Michael addition to construct 2,6-difunctionalized THP unit intramolecularly are the important steps in synthetic efforts. Finally, Keck asymmetric allylation and Lewis acid-catalyzed diastereoselective allylation of the aldehyde were sequentially employed to establish the stereocenters at C11 and C13 positions, respectively.
Keywords: (+)-neopeltolide; Keck allylation; Macrolide; NHC-catalyzed oxoacyloxylation; reductive oxa-Michael addition

Substitution at sp(3) boron of a six-membered NHC center dot BH3: convenient access to a dihydroxyborenium cation - Kundu, Gargi; Ajithkumar, V. S.; Raj, K. Vipin; Vanka, Kumar; Tothadi, Srinu; Sen, Sakya S. (Chemical Communications, 2022)
Herein, we have undertaken the synthesis and investigated the reactivity of a 6-membered saturated NHC borane adduct (1). Direct electrophilic halogenation of 1 with a stoichiometric amount of I-2 led to NHC boryl iodides, 6-SIDipp center dot BH2I (2) and 6-SIDipp center dot BHI2 (3), which were further reacted with various nucleophiles to give novel 6-SIDipp based mono and disubstituted boranes with OTf (4 and 6) or ONO2 (5 and 7) functional groups. The addition of Br-2/H2O to 1 smoothly results in a dihydroxyborenium cation (8).

Substrate induced dynamical remodeling of the binding pocket generates GTPase specificity in DOCK family of guanine nucleotide exchange factors - Roy, Debopriya; Sengupta, Durba; Kulkarni, Kiran (Biochemical and Biophysical Research Communications, 2022)
Dedicator of cytokinesis (DOCK) family of guanine nucleotide exchange factors (GEFs) activate two members of Rho family GTPases, Rac1/Cdc42, to exert diverse cellular processes, including cell migration. As DOCK GEFs have been critically implicated in tumour cell migration, understanding their function and specificity is imperative for designing anti-metastatic drugs. Based on their GTPase specificity they have been classified as Rac, Cdc42 and dual specific GEFs. Despite extensive structural studies, the factors that determine GTPase specificity of DOCK GEFs have remained elusive. Here, we show that subtle dynamical coupling between GEF and GTPase structures modulate the binding interface to generate mutual spec-ificity. To cluster the dynamically coupled residues in GEF-GTPase complexes a novel intra-residue backbone-torsion-angles based mutual information (TMI) technique was employed. TMI was calcu-lated from 4500 trajectories obtained from a total of 4.5ms molecular dynamics simulations performed on members of all the three clades of DOCK GEFs. The obtained clusters suggest a specificity generation mechanism that involves optimization of the binding pocket for the crucial divergent residue at the 56th position of Rac/Cdc42 (FCdc42/WRac1). These clusters encompass five residues from the structural segment lobe C -a10 helix of the DOCK proteins and functional SWI region of GTPase, which induce orchestrated structural modulations to generate the specificity. Even the conserved residues from SWI region are seen to augment the specificity defining dynamical rearrangements. Furthermore, the pro-posed dynamical GTPase-DOCK GEF specificity model was verified using mutagenesis studies on Rac1 and dual GTPase specific Dock2 and Dock6, respectively. Thus the current study provides the generic substrate specificity determinants of DOCK GEFs, which are not apparent from the conventional struc-tural analysis.(c) 2022 Elsevier Inc. All rights reserved.
Keywords: Dedicator of cytokinesis; GTPase specificity; Guanine exchange factors; Molecular dynamics simulations; Mutual information; Rho GTPases

Suitability of different supported Ru, Pt and Ni catalysts for the hydrogenolysis of sorbitol - Kandasamy, Thirunavukkarasu; Banu, Marimuthu; Shanthi, R. Vijaya; Sivasanker, S. (Results in Engineering, 2022)
<ul class="issue-navigation u-margin-s-bottom u-bg-grey1" id="issue-navigation" style="box-sizing: border-box; margin-top: 0px; margin-right: 0px; margin-left: 0px; padding-right: 0px; padding-left: 0px; list-style: none; overflow: hidden; font-size: 16px; line-height: 24px; color: rgb(46, 46, 46); font-family: NexusSans, Arial, Helvetica, "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", STIXGeneral, "Cambria Math", "Arial Unicode MS", sans-serif; margin-bottom: 16px !important; background-color: rgb(245, 245, 245) !important;"> <div class="Abstracts u-font-gulliver text-s" id="abstracts" style="box-sizing: border-box; margin: 0px; padding: 0px; --sd-ui-line-height: calc(1em + 10px); font-size: 0.8rem; line-height: var(--sd-ui-line-height); color: rgb(46, 46, 46); font-family: ElsevierGulliver, Georgia, "Times New Roman", STIXGeneral, "Cambria Math", Arial, Helvetica, "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif !important;"> In this article, the results of sorbitol <a class="topic-link" href="https://www.sciencedirect.com/topics/engineering/hydrogenolysis" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: transparent; word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(46, 46, 46); color: rgb(46, 46, 46); text-underline-offset: 1px;" title="Learn more about hydrogenolysis from ScienceDirect's AI-generated Topic Pages">hydrogenolysis (15% aq. solution), done in an autoclave reactor, over Ru, Pt and Ni loaded on SBA15, carbon coated SBA15 (SBA15C), activated carbon (AcC), Na–Y, Fly Ash (FA) and hydroxyapatite (HAP) catalysts by our group, were compared to find the best metal-support combinations. The metal loading was 1 wt% for Ru and Pt, 6 wt% for Ni and the catalysts' preparations were carried out by impregnation of respective salts. The catalysts were characterized with nitrogen and hydrogen adsorption measurements and X-ray diffraction. Addition of a base (Calcium hydroxide) to the reactants' mixture increased the overall conversion and selectivities of the glycols, ethylene glycol (EG) and 1,2-propylene glycol (PG). The catalysts’ performance at 60 bar and 220 °C with the presence of base (B), evaluated by the yield of glycols (PG + EG), showed the following order: Ni/Na–Y > Ru/AcC ∼ Ru/SBA15C > Ni/HAP ∼ Ru/SBA15 > Ni/SBA15 > Ru/Na–Y > Ni/FA ∼ Ni/AcC and the yields were 57, 40, 39, 33, 31, 29, 26, 22 and 21 wt%, respectively. Na–Y appeared to be the best support, especially for Ni metal; AcC and SBA15C were good supports for Ru and Pt respectively. <a class="topic-link" href="https://www.sciencedirect.com/topics/engineering/reusability" style="box-sizing: border-box; margin: 0px; padding: 0px; background-color: transparent; word-break: break-word; text-decoration-thickness: 1px; text-decoration-color: rgb(46, 46, 46); color: rgb(46, 46, 46); text-underline-offset: 1px;" title="Learn more about Reusability from ScienceDirect's AI-generated Topic Pages">Reusability studies revealed that Ni on HAP was the best catalyst and exhibited only a small deactivation during four runs of loading it.

SUMOylation of dorsal attenuates Toll/NF-kappa B signaling - Hegde, Sushmitha; Sreejan, Ashley; Gadgil, Chetan J.; Ratnaparkhi, Girish S. (Genetics, 2022)
In Drosophila, Toll/NF-kappa B signaling plays key roles in both animal development and in host defense. The activation, intensity, and kinetics of Toll signaling are regulated by posttranslational modifications such as phosphorylation, SUMOylation, or ubiquitination that target multiple proteins in the Toll/NF-kappa B cascade. Here, we have generated a CRISPR-Cas9 edited Dorsal (DL) variant that is SUMO conjugation resistant. Intriguingly, embryos laid by dl(SCR) mothers overcome dl haploinsufficiency and complete the developmental program. This ability appears to be a result of higher transcriptional activation by DLSCR. In contrast, SUMOylation dampens DL transcriptional activation, ultimately conferring robustness to the dorso-ventral program. In the larval immune response, dl(SCR) animals show an increase in crystal cell numbers, stronger activation of humoral defense genes, and high cactus levels. A mathematical model that evaluates the contribution of the small fraction of SUMOylated DL (1-5%) suggests that it acts to block transcriptional activation, which is driven primarily by DL that is not SUMO conjugated. Our findings define SUMO conjugation as an important regulator of the Toll signaling cascade, in both development and host defense. Our results broadly suggest that SUMO attenuates DL at the level of transcriptional activation. Furthermore, we hypothesize that SUMO conjugation of DL may be part of a Ubc9-dependent mechanism that restrains Toll/NF-kappa B signaling.
Keywords: Drosophila; haploinsufficiency; innate immunity; SUMO; transcription

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

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

Sustainable fabrication of copper nanoparticles: a potent and affordable candidate for water treatment, water disinfection, antioxidant activity and theranostic agent - Sinha, Tanur; Adhikari, Partha Pradip; Bhandari, Vinay M. (ChemistrySelect, 2022)
This study reports a simple, green, and large-scale biosynthetic fabrication of spherical copper nanoparticles (Cu NPs), approximate 28 nm, using the aqueous extracts of Diaplazium esulentum (Retz.) Sw. fern. Characterization was carried out for morphology, size, elemental analysis, crystallinity and for identification of functionalities responsible for reduction and stabilization. Extraordinary remediation efficiency was obtained for the developed Cu NPs for the elimination of two industrially important pollutants; Methyl Violet 6B and Methylene Blue (greater than 92 % within 150 mins). A mechanism was postulated for the process using the data on the identification of NPs and also spent NPs apart from degraded products. Furthermore, the Cu NPs revealed excellent antibacterial activity against gram positive bacteria: Staphylococcus aureus, Streptococcus pneumonia and Bacillus subtilis, as well as gram negative bacteria: Pseudomonas aeruginosa, Escherichia coli and potential action against fungal strains; Aspergillus niger and Candida albicans. Additionally, the assay depicted that Cu NPs has fairly decent radical scavenging activity with IC50 value 2.11 mM. Moreover, the Cu NPs were found to exhibit profound anticancerous activity against two human cancer line cells. The present research work has implications for exploitation of DE fern extract for the development of Cu NPs and their numerous applications ranging from pollutants removal to antibacterial, antifungal, antioxidant and anticancerous agents.
Keywords: Anticancer; antifungal; Antimicrobial; Antioxidant; Photodegradation and Phytosynthesis

Synergetic storage of ammonia over Al quantum dots embedded graphene sheets: a first principles perspective - Singh, Chandrodai Pratap; Krishnamurty, Sailaja (International Journal of Hydrogen Energy, 2022)
In view of the increasing energy demand and global warming, it is imperative to search for a renewable and environmental friendly fuel in lieu of non-renewable energy resources. Hydrogen stands out to be the best fuel as both, renewable and clean. Concerning the use of hydrogen as a fuel, its production as well as storage are current global challenges being worked on. In this article, a density functional theory based study is performed to identify the potential of supported Al cluster cages for ammonia storage. In this context, initially, stability of pristine and doped aluminum nanoclusters anchored on graphene sheet is evaluated following which thus supported stable nanoclusters are studied for the adsorption of NH3 to identify their storage capacity. For both, complexes and NH3 adsorbed complexes, Density of States (DOS), Charge Density Difference (CDD) and Bader charge analysis is done to understand their electronic properties.(c) 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Keywords: Aluminum nanoclusters; Defective graphene; Endohedral doping; NH 3 adsorption

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

Synergistic electronic effects in AuCo nanoparticles stabilized in a triazine-based covalent organic framework: a catalyst for methyl orange and methylene blue reduction - Devulapalli, Venkata Swaroopa Datta; Kushwaha, Rinku; Ovalle, Edwin; Singh, Himan Dev; Shekhar, Pragalbh; Chakraborty, Debanjan; Vinod, Chathakudath Prabhakaran; Vaidhyanathan, Ramanathan; Borguet, Eric (ACS Applied Nano Materials, 2022)
Developing stable active catalysts for reducing water-soluble pollutants is a desirable target. In this pursuit, we have functionalized covalent organic frameworks (COFs) with gold (Au) and cobalt (Co) nanoparticles via a one-step aqueous synthesis process, and their catalytic activity in reducing methyl orange and methylene blue is examined. Operando absorbance measurements of methyl orange (anionic dye) reduction revealed AuCoCOF (1.3 Au/1.0 Co) to have superior kinetics over many other catalysts, which typically require additional external stimuli (e.g., photons) and higher catalyst loadings. After confirming the homogeneous dispersion of the nanoparticles on the COF support using three-dimensional (3D) tomography and material stability through powder X-ray diffraction (PXRD), infrared (IR), and thermal studies, we investigated their redox activity. Cyclic voltammetry (CV) confirmed the involvement of both metals in the redox process, while spectroelectrochemical measurements show that their activity and kinetics remain unaltered by an applied potential. Solid-state UV measurements reveal that the neat COF is a semiconductor with a large band gap (2.8 eV), which is substantially lowered when loaded with cobalt nanoparticles (2.2 eV for CoCOF). The electronic synergy between Au and Co nanoparticles further reduces the band gap of AuCoCOF (1.9 eV). Thus, there is a definite advantage in doping non-noble metal nanoparticles into a noble metal lattice and nanoconfining them into a porous COF support. Our study highlights the significance of bimetallic COF-supported nanocatalysts, wherein one can engage each component toward targeted applications that demand redox activity with favorable kinetics.
Keywords: AuCoCOF; band gaps; Covalent organic framework; methyl orange reduction; Nanoparticles; UV-vis spectroscopy

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

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

Synthesis of central spiro-bis-THF fragments of symbiospirols A-C - Shinde, Mahesh H.; Kona, Chandrababu N.; Ramana, V. Chepuri (New Journal of Chemistry, 2022)
The gold catalysed alkynediol spiroketalization to assemble the central spiro-bis-THF fragments (C22-C33 and C36-C47) of symbiospirols A-C is documented. The adopted chiral pool approach employed commercially available d-glucose and l-malic acid in the synthesis of key building blocks. In addition, two other possible diastereomers have been synthesized in order to establish the relative stereochemistry of the unassigned THF-center of symbiospirols B/C.

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

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

Tailoring diradicaloid properties of expanded isophlorinoids with systematic core-modification - Ambhore, Madan D.; Shukla, Pragati; Gonnade, Rajesh G.; Anand, Venkataramanarao G. (Chemical Communications, 2022)
Herein, we describe the synthesis, structural diversity and diradicaloid characteristics of 38 pi core-modified aromatic expanded isophlorins with eight heterocyclic rings. The diradicaloid character of expanded isophlorinoid macrocycles was engineered by systematic structural modification. Depending on the nature of the link between the heteroatoms, they adopt planar and non-planar conformations. This large structural variation with a significant difference in the extent of aromaticity is correlated with the magnitude of their respective diradical character.

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

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

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

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

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

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

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

Toughening poly(l-lactide) blends: effectiveness of sequence-controlled six-arm star-branched block copolymers of poly(L-lactide) and poly(epsilon-caprolactone) - Deokar, Megha D.; Garnaik, Baijayantimala; Sivaram, Swaminathan (ACS Omega, 2022)
Well-defined six-arm star-branched bio-degradable block copolymers of L-lactide and epsilon-caprolactone were prepared using controlled ring-opening polymerization and a sequential monomer addition method using dipentaerythritol as the initiator core and organocatalysts at low temperatures in solution. Sequence of enchainment was changed by reversing the order of monomer addition giving, either, a crystalline PLA block or an amorphous PCL block as the outer segment. Well-defined six-arm poly(epsilon-caprolactone-b-L-lactide, 6s-PCL-b-PLA) block copolymers were obtained with a range of segment molecular weights. However, in the case of six-arm poly(L-lactide-b-epsilon-caprolactone, 6s-PLA-b-PCL), disruption of the block structure was observed on account of competing transesterification reactions accompanying a chain-growth reaction. Such sequence-controlled block copolymers showed interesting phase morphologies, as evidenced by differential scanning calorimetry (DSC) studies. 6s-PCL-b-PLA showed two glass-transition temperatures and two melting temperatures characteristic of the amorphous and crystalline blocks. 6s-PCL-b-PLA and 6s-PLA-b-PCL with different segment chain lengths were solution blended (10 wt %) with a commercially sourced PLA. All the blends were highly transparent. The structure and properties of the blend were examined by DSC, measurement of mechanical properties, and scanning electron microscopy. The results show that a phase-separated 6s-PCL-b-PLA copolymer results in two- to three-fold improvement in tensile toughness without the loss of modulus. A possible hypothesis for the mechanism of tensile toughness in the blend has been proposed.

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

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

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

Tryptophan-cardanol fluorescent nanoparticles inhibit alpha-synuclein aggregation and disrupt amyloid fibrils - Sunny, Lisni P.; Srikanth, Priya; Sunitha, Anju Kunhiraman; Tembulkar, Niyoti; Abraham, Jancy Nixon (Journal of Peptide Science, 2022)
Protein misfolding and aggregation play a vital role in several human diseases such as Parkinson's, Alzheimer's, and prion diseases. The development of nanoparticles that modulate aggregation could be potential drug candidates for these neurodegenerative disorders. Parkinson's disease pathogenesis is closely associated with the accumulation of alpha-synuclein oligomers and fibrils in the substantia nigra of the brain. This report discusses the interactions of novel tryptophan-cardanol nanoparticles with alpha-synuclein protein monomers and fibrils. These nanoparticles could effectively disrupt alpha-synuclein fibrils and inhibit fibril formation at low concentrations such as 5 mu M. The tryptophan-cardanol nanoparticles inhibit fibril formation from unstructured protein resulting in spherical nanostructures. These nanoparticles could also disassemble amyloid fibrils; the complete disappearance of fibrils was evident after 48 h of incubation with tryptophan-cardanol. The transmission electron microscopy (TEM) micrographs after the incubation did not show any remnants of the peptide aggregates or oligomers. The thioflavin T fluorescence after the disassembly was diminished compared with that of fibrils also supports the inhibitory effect of the nanoparticles. Also, these nanoparticles did not reduce the viability of the SH-SY5Y cells. These findings suggest that the tryptophan-cardanol nanoparticles showed sufficiently high inhibitory activity and may have therapeutic potential for synucleinopathies.
Keywords: alpha-synuclein; amyloid fibrils; Cardanol; inhibitors; Tryptophan

Tuning of work function of ZnO by doping and co-doping: an investigation using X-ray photoelectron spectroscopy - Soumya, K.; Selvam, I. Packia; Vinod, C. P.; Potty, S. N. (Thin Solid Films, 2022)
The shift in the work function of the ZnO thin film upon varying codoping ratio has been investigated by X-ray photoelectron spectroscopy. A notable shift of 0.2 eV in the work function was achieved in the films when the Al: In doping ratio was changed from 0:10 to 10:0. The elemental composition of the dopants obtained from XPS analysis showed the presence of more amount of In dopant than Al in codoped ZnO films. In this way a clear understanding of the variation in electrical properties on dopant ratio is obtained. A decrease in work function was also observed with the increase in free carrier concentration when the codopant ratio is changed. The effects of Burstein moss, band narrowing, and band renormalization observed in the bandgap were explained by an upward and downward shift of valence band maxima of the corresponding thin films. The controllable work function of the codoped ZnO films by varying the doping ratio offers excellent potential advantages in optoelectronic devices.
Keywords: Indium -Aluminum co -doping; Spray coating; thin film; Work function; X-ray photoelectron spectroscopy; Zinc oxide

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

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

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

Ultrathin twisty PdNi alloy nanowires as highly active ORR electrocatalysts exhibiting morphology-induced durability over 200 K cycles - Sahoo, Lipipuspa; Garg, Reeya; Kaur, Komalpreet; Vinod, C. P.; Gautam, Ujjal K. (Nano Letters, 2022)
Even though the anion exchange membrane fuel cells have many advantages, the stability of their electrocatalysts for oxygen reduction reaction (ORR) has remained remarkably poor. We report here on the ultrathin twisty PdNi-alloy nanowires (NWs) exhibiting a very low reaction overpotential with an E1/2 ∼ 0.95 V versus RHE in alkaline media maintained over 200 K cycles, the highest ever recorded for an electrocatalyst. The mass activity of the used NWs is >10 times higher than fresh commercial Pt/C. Therein, Ni improves the Pd d-band center for a more efficient ORR, and its leaching continuously regenerates the surface active sites. The twisty nanowire morphology imparts multiple anchor points on the electrode surface to arrest their detachment or coalescence and extra stability from self-entanglement. The significance of the NW morphology was further confirmed from the high-temperature durability studies. The study demonstrates that tailoring the number of contact points to the electrode-surface may help realize commercial-grade stability in the highly active electrocatalysts.

Unravelling faradaic electrochemical efficiencies over Fe/Co spinel metal oxides using surface spectroscopy and microscopy techniques - Kashyap, Varchaswal; Pandikassala, Ajmal; Singla, Gourav; Khan, Tuhin Suvra; Haider, M. Ali; Vinod, C. P.; Kurungot, Sreekumar (Nanoscale, 2022)
Cobalt and iron metal-based oxide catalysts play a significant role in energy devices. To unravel some interesting parameters, we have synthesized metal oxides of cobalt and iron (i.e. Fe2O3, Co3O4, Co2FeO4 and CoFe2O4), and measured the effect of the valence band structure, morphology, size and defects in the nanoparticles towards the electrocatalytic hydrogen evolution reaction (HER), the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR). The compositional variations in the cobalt and iron precursors significantly alter the particle size from 60 to <10 nm and simultaneously the shape of the particles (cubic and spherical). The Tauc plot obtained from the solution phase ultraviolet (UV) spectra of the nanoparticles showed band gaps of 2.2, 2.3, 2.5 and 2.8 eV for Fe2O3, Co3O4, Co2FeO4 and CoFe2O4, respectively. Further, the valence band structure and work function analysis using ultraviolet photoelectron spectroscopy (UPS) and core level X-ray photoelectron spectroscopy (XPS) analyses provided better structural insight into metal oxide catalysts. In the Co3O4 system, the valence band structure favors the HER and Fe2O3 favors the OER. The composites Co2FeO4 and CoFe2O4 show a significant change in their core level (O 1s, Co 2p and Fe 2p spectra) and valence band structure. Co3O4 shows an overpotential of 370 mV against 416 mV for Fe2O3 at a current density of 2 mA cm(-2) for the HER. Similarly, Fe2O3 shows an overpotential of 410 mV against the 435 mV for Co3O4 at a current density of 10 mA cm(-2) for the OER. However, for the ORR, Co3O4 shows 70 mV improvement in the half-wave potential against Fe2O3. The composites (Co2FeO4 and CoFe2O4) display better performance compared to their respective parent oxide systems (i.e., Co3O4 and Fe2O3, respectively) in terms of the ORR half-wave potential, which can be attributed to the presence of the oxygen vacancies over the surface in these systems. This was further corroborated in density functional theory (DFT) simulations, wherein the oxygen vacancy formation on the surface of CoFe2O4(001) was calculated to be significantly lower (similar to 50 kJ mol(-1)) compared to Co3O4 (001). The band diagram of the nanoparticles constructed from the various spectroscopic measurements with work function and band gap provides in-depth understanding of the electrocatalytic process.

Versatile chemistry of six-membered NHC with boranes: bromination at sp(3) borane, activation of the B-H bond of HBpin, and ring expansion of NHC - Kundu, Gargi; Dixit, Ruchi; Tothadi, Srinu; Vanka, Kumar; Sen, Sakya S. (Dalton Transactions, 2022)
The NHC.borane chemistry has been majorly restricted to imidazol-2-ylidene classes of carbenes. In our previous communication, we reported the synthesis of 6-SIDipp center dot BH3 [6-SIDipp = 1,3-di(2,6-diisopropylphenyl) tetrahydropyrimidine-2-ylidene] and its electrophilic substitution reaction with iodine. Here, we have shown selective bromination of a 6-SIDipp stabilized sp(3) B-H bond. Treatment of 1.2 equivalents of N-bromosuccinamide with 6-SIDipp center dot BH3 gives a mixture of mono- and disubstituted products 6-SIDipp center dot BH2Br (1) and 6-SIDipp center dot BHBr2 (2). However, the reactions with alkyl bromides or carbon tetrabromide resulted in 6-SIDipp center dot BH2Br (1) selectively. Exploration of the chemistry of 6-SIDipp with BHCl2 and 9-BBN (9-borabicyclo[3.3.1]nonane) led to mono-6-SIDipp adducts 3 and 6a. Furthermore, 6a undergoes ring expansion to afford a seven-membered product, 6b, under mild conditions. Unlike BHCl2 or 9-BBN, the B-H bond of HBpin undergoes oxidative addition upon reaction with 6-SIDipp, epitomizing the first example (7) of a B-H bond insertion at NHCs. The analogous reactivity with HBcat led to a tetra-hydropyrimidinium salt with B(cat)(2) as a counteranion (8).

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

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

Wearable fabric supercapacitors based on CNTs and polyhedral ZnO with a wide potential window - Samuel, Edmund; Joshi, Bhavana; Park, Chanwoo; Aldalbahi, Ali; El-Newehy, Mohamed; Lee, Hae-Seok; Yoon, Sam S. (International Journal of Energy Research, 2022)
Wearable electronic devices such as health monitors, sensors, and e-skin can be powered by lightweight, high-power supercapacitors. Using a binder-free and low-temperature hydrothermal method, polyhedral ZnO nanoparticles were grown on carbon nanotube (CNT)-decorated cotton fabric, which is friendly to human skin and highly wearable, inexpensive, and thus commercially viable. The concentration of the starting material, zinc acetate, was varied to optimize the electrochemical performance. The evenly spaced polyhedral ZnO facilitated efficient permeation of the electrolyte into the active material. The fabric filaments were decorated with CNTs to enhance electron transfer and the overall electrochemical processes. The symmetric cell comprised of cotton fabric decorated with ZnO polyhedron/CNT showed no discernible change in the cyclic voltammetry curves even after 500 bending cycles, demonstrating the mechanical durability of the electrode. The potential window of 1.6 V using a Na2SO4/K2SO4 aqueous dual-ion electrolyte improved the long-term electrochemical stability and increased the energy storage capacity. The capacitance retention was 94% after 5000 cycles at a current density of 1 A center dot g(-1), indicating long-term electrochemical stability. A specific capacitance of 375 F center dot g(-1) at a current density of 5 A center dot g(-1) and energy density of 33.3 Wh center dot kg(-1) at a power density of 2000 W center dot kg(-1) were recorded for the optimized electrode. Highlights Polyhedral ZnO was grown on cotton fabric using a hydrothermal process. The electrochemical performance was optimized by varying the zinc acetate concentration. The highest specific capacitance was 375 F center dot g(-1) at a current density of 5 A center dot g(-1). Under optimal conditions, the capacitance retention was 94% at N = 5000 cycles. The energy density of the electrode was as high as 33.3 Wh center dot kg(-1).
Keywords: carbon nanotube; Cotton fabric; hydrothermal process; wearable supercapacitor; ZnO polyhedron

Well-defined calcium compound catalyzes trimerization of arylisocyanates into 1,3,5-triarylisocyanurates - Kumar, Rohit; Sharma, Vishal; Jain, Shailja; Sharma, Himanshu; Vanka, Kumar; Sen, Sakya S. (ChemCatChem, 2022)
We report the synthesis of a calcium complex (2) bearing a tetradentate monoanionic ligand with a diaminoethane core and phenolate and pyridine peripheral donors. Single crystal X-ray studies on 2 revealed that LiI was also co-crystallized, leading to a four-membered ring with four different elements. 2 was found to be an efficient catalyst for the cyclotrimerization of a variety of aromatic isocyanates under mild conditions.
Keywords: calcium; Cyclotrimerization; Isocyanurates; Tetradentate ligand

Well-defined hierarchical teddy bear sunflower-like NiCo2O4 electrocatalyst for superior water oxidation - Bodhankar, Pradnya M. M.; Dhawale, Dattatray S. S.; Giddey, Sarbjit; Kumar, Ravi; Sarawade, Pradip B. B. (Sustainable Energy & Fuels, 2022)
The development of a robust and efficient electrocatalyst for water oxidation is challenging due to the large overpotential requirement to transfer four electrons. Herein, a novel spinel-type hierarchical teddy bear sunflower-like NiCo2O4 electrocatalyst was synthesized through the facile solvothermal process and evaluated for the challenging and demanding oxygen evolution reaction (OER) in the water electrolysis process. The teddy bear sunflower-like NiCo2O4 supported on nickel foam (NF) delivers a current density of 50 mA cm(-2) at a small water oxidation overpotential (eta(50) = 319 mV) which is significantly lower than that of the corresponding spherical NiO/NF (eta(50) = 338 mV), and sea-urchin like Co3O4/NF (eta(50) = 357 mV). A large specific and electroactive surface area, as well as a high TOF value exhibited by the hierarchical teddy bear sunflower-like NiCo2O4 electrocatalyst, demonstrates the potential of NiCo2O4 to catalyze the water oxidation reaction efficiently. The impact of the near-Fermi-level d-orbital states in NiCo2O4 electrocatalyst for boosting OER activity was unveiled by the density functional theory calculation. The stable performance even after 16 h and high catalyst utilization of the hierarchical teddy bear sunflower-like NiCo2O4 through the OER indicates that the catalyst is highly suitable for the large-scale water oxidation process.

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

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

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

Activation of the olefinic C-H bond of NHC and NHO by perimidine-based silicon and germanium compounds - Gour, Kritika; Pramanik, Debjit; Dash, Soumya Ranjan; Tothadi, Srinu; Vanka, Kumar; Sen, Sakya S. (Organometallics, 2023)
In this manuscript, several backbonegermylene-functionalized zwitterioniccompounds were prepared conveniently from the corresponding N-heterocycliccarbenes or N-heterocyclic olefins in a single step through backboneC-H activation. Our initial motivation was to generate a silylenefrom C10H6(Me3SiN)(2)SiHCl(2) using ItBu [ItBu= (1,3-ditert-butyl)imidazol-2-ylidene], but instead, the reactionled to deprotonation from the imidazolium backbone of ItBu, forming the imidazolium salt with a silyl backbone at the C4position (3). We presumed that the reaction proceededthrough the generation of an ephemeral silylene. We subsequently preparedthe analogous germylene (4) and reacted it with IDipp[IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene], ItBu, and IDipp=CH2. Spectroscopic and crystallographicanalysis of these complexes revealed that, in all cases, there wasdeprotonation from the backbone and formation of zwitterionic products(5-7). When the hydrogen in the NHCbackbone was replaced with methyl groups such as IDipp(Me) (1,3-bis(2,6-diisopropylphenyl)-4,5-dimethylimidazol-2-ylidene),simple adduct formation occurred, exemplified by the isolation ofIDipp(Me)& BULL;Ge(NSiMe3)(2)C10H6 (8).

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

Aptamer tethered bio-responsive mesoporous silica nanoparticles for efficient targeted delivery of paclitaxel to treat ovarian cancer cells - Salve, Rajesh; Kumar, Pramod; Chaudhari, Bhushan P.; Gajbhiye, Virendra (Journal of Pharmaceutical Sciences, 2023)
Ovarian cancer is the leading cause of cancer deaths in female patients. The current therapeutics in ovarian cancer are limited and inefficient in curing the disease. To tackle this, we have synthesized tetrasulfide deriv-ative of silica doped, biodegradable, glutathione-responsive targeted mesoporous silica nanoparticles modi-fied with heterobifunctional polyethylene glycol as a linker and mucin-1 aptamer for triggered paclitaxel delivery to the ovarian cancer cells. Degradable mesoporous silica nanoparticles were synthesized by a modi-fied sol-gel method with tetraethyl orthosilicate and Bis (triethoxysilylpropyl) tetrasulfide. The degradable mesoporous silica nanoparticles were characterized by dynamic light scattering, Fourier-transform infrared spectroscopy, Scanning electron microscopy and Transmission electron microscopy. The degradable mesopo-rous silica nanoparticles had good paclitaxel encapsulation efficiency and glutathione-responsive paclitaxel release ability. The glutathione utilization assay and visual destruction observed within 10 days in transmis-sion electron microscopy images confirmed the degradation of the mesoporous silica nanoparticles in the tumor cell environment. The targeted degradable mesoporous silica nanoparticles were efficiently taken up by ovarian cancer cell lines OVACAR-3 and PA-1. The cytotoxicity of bare mesoporous silica nanoparticles evaluated on NIH-3T3 cell line showed good biocompatibility (>90% cell viability). Significant toxicity on OVACAR-3 (IC50 25.66 nM) and PA-1 (IC50 42.93 nM) cell lines was observed when treated with paclitaxel-loaded targeted degradable mesoporous silica nanoparticles. Results of this study demonstrated that mucin-1 targeted, glutathione-responsive mesoporous silica nanoparticles loaded with paclitaxel had a significant antitumor effect on ovarian cancer cells. All these findings demonstrated that developed nano-formulation could be suitable for ovarian cancer treatment. & COPY; 2023 American Pharmacists Association. Published by Elsevier Inc. All rights reserved.
Keywords: Degradable; GSH; Mesoporous silica nanoparticles; Mucin-1; Ovarian cancer; Paclitaxel; Stimuli-responsive

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

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

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

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

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

Bi(III)-catalyzed synthesis of substituted furans from hydroxy-oxetanyl ketones: application to unified total synthesis of shikonofurans J, D, E, and C - Kataria, Priyanka; Sahoo, Shubhranshu Shekhar; Kontham, Ravindar (Journal of Organic Chemistry, 2023)
We report an improved synthetic protocol for hydroxymethyl-derivedpolysubstituted furans employing Bi-(III)-catalyzed dehydrative cycloisomerizationof alpha-hydroxy oxetanyl ketones. This procedure provides rapidaccess (within 5 min) to highly substituted furans with exceptionalfunctional group diversity, excellent yields, generality, scalability,and operationally simple reaction conditions. Further, it demonstratedthe utility of this method in the first enantioselective total synthesisof furyl-hydroquinone-derived biologically potent natural productsshikonofurans J, D, E, and C in seven linear steps, starting fromreadily available building blocks of 2,5-dihydroxy acetophenone and3-oxetanone employing chiral-phosphoric acid (TRIP)-catalyzed asymmetricprenylation as a key step to induce the chirality.

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

Biosynthesis of gold nanoparticles by Penicillium rubens and catalytic detoxification of ochratoxin A and organic dye pollutants - Bhandari, Yogesh; Varma, Sanjana; Sawant, Amol; Beemagani, Sreelatha; Jaiswal, Neha; Chaudhari, Bhushan P.; Vamkudoth, Koteswara Rao (International Microbiology, 2023)
The environmental pollution caused by chemical dyes is a growing concern nowadays. Limitations of traditional methods opened the route for nanotechnology; owing to the versatile properties of nanomaterials, gold nanoparticles (AuNPs) became a potential strategy for different applications. In the present study, biosynthesis of gold nanoparticles (BioAuNPs) was carried out by reacting chloroauric acid (HAuCl4) with cell-free filtrate of Penicillium rubens sp. nov. NCIM 1937. The AuNPs were then characterized by UV-visible spectroscopy, HR-TEM, FTIR, and DLS analysis to further examine their efficacious biosynthesis and morphological properties including size, shape, and stability. The biogenic AuNPs are polydisperse in nature, with a mean size of 14.92 +/- 5 nm. These AuNPs exhibited promising antimicrobial activity against Escherichia coli NCIM-2065, Bacillus subtilis NCIM-2010, and Penicillium verrucosum MTCC 4935. In vitro quantitative HPLC results revealed that BioAuNPs significantly inhibited the biosynthesis of ochratoxin A (OTA). Microbial fuel cells (MFCs) are intriguing for power generation and wastewater treatment since they can directly transform chemical energy stored in organic matter to electricity by extracellular electron transfer (EET) via membrane proteins. AuNPs also showed excellent potential for dye degradation of organic pollutants, viz., methylene blue (MB), phenol red (PR), bromothymol blue (BTB), Congo red (CR), and 4-nitrophenol (4-NP). All dye removal efficiencies were estimated and fitted to pseudo-first-order processes using kinetic rate constants (Ka).The present study reveals a simple, original, and eco-friendly method for the synthesis of multifunctional biogenic AuNPs that could be effective in OTA detoxification in food products and organic pollutant removal during wastewater treatment for a sustainable environment.
Keywords: Catalytic organic dye degradation; gold nanoparticles; Ochratoxin A; Penicillium rubens; Penicillium verrucosum

Can Li atoms anchored on boron- and nitrogen-doped graphene catalyze dinitrogen molecules to ammonia? a DFT study - Verma, Tushar Singh; Samal, Pragnya Paramita; Selvaraj, Kaliaperumal; Krishnamurty, Sailaja (ChemPhysChem, 2023)
The most successful electrochemical conversion of ammonia from dinitrogen molecule reported to date is through a Li mediated mechanism. In the framework of the above fact and that Li anchored graphene is an experimentally feasible system, the present work is a computational experiment to identify the potential of Li anchored graphene as a catalyst for N-2 to NH3 conversion as a function of (a) minimum number of Li atoms needed for anchoring on graphene sheets and (b) the role of chemical modification of graphene surfaces. The studies bring forth an understanding that Li anchored graphene sheets are potential catalysts for ammonia conversion with preferential adsorption of N-2 through end-on configuration on Li atoms anchored on doped and pristine graphene surfaces. This mode of adsorption being characteristic of Nitrogen Reduction Reaction (NRR) through enzymatic pathway, examination of the same followed by analysis of electronic properties demonstrates that tri-Li atoms (Tri Atom Catalysts, TACs) are more efficient as catalysts for NRR as compared to two Li atoms (Di Atom Catalysts, DACs). Either way, the rate determining step was found to be *NH2 ->*NH3 step (mixed pathway) with Delta G(max)=1.02 eV and *NH2-*NH3 ->*NH2 step (enzymatic pathway) with Delta G(max)=1.11 eV for 1B doped TAC and DAC on graphene sheet, respectively. Consequently, this work identifies the viability of Li anchored graphene based 2-D sheets as hetero-atom catalyst for NRR.
Keywords: computational chemistry; Graphene Sheet; heterogeneous catalysis; Li Nanoparticles; Nitrogen Reduction Reaction

Can metal cations electrocatalyze sulfur redox reaction and suppress polysulfide shuttle? - Kumar, Subramani; Swain, Gitanjali; Krishnamoorthy, Kothandam (Batteries & Supercaps, 2023)
In lithium-sulfur (Li-S) batteries, sulfur undergoes various changes. It switches between cyclic structure and linear structure. The charge on the sulfur varies between a neutral state and a negative charge-bearing state. Due to these changes, the sulfur/polysulfide dissolves in the battery electrolyte. Furthermore, the kinetics of the sulfur redox reaction is sluggish. Therefore, a material that can suppress sulfur/polysulfide dissolution and electrocatalyze sulfur redox reaction is needed. We hypothesize that the polysulfide dissolution can be suppressed if the host exhibits polyvalent electrostatic attraction. Polysulfide is a negative charge-bearing molecule; hence the host must comprise multiple positive charges. Nickel cations with other heteroatoms have been explored as a host in Li-S batteries. The heteroatoms impart additional interactions. The easier way to circumvent the effect of heteroatoms is the addition of metal salts. However, metal salts can either exhibit monovalent or divalent attraction with polysulfides. Those interactions are weak and we must have polyvalent interaction. Towards this objective, we have designed and synthesized a material that comprises multiple divalent cations that is also devoid of heteroatoms. The Li-S batteries fabricated using the metal cation immobilized graphene showed a maximum specific capacity of 1022 mAh/g at 0.1 C rate. Among the metal cations, nickel cations showed better performance than cobalt cations. Thus, we demonstrate that metal cations immobilized on Graphene can efficiently electrocatalyze the sluggish sulfur redox reaction and suppress the polysulfide dissolution.
Keywords: electrocatalysis; graphene; lithium-sulfur batteries; metal cations; polysulfides

Carbohydrate recognition using metal-ligand assemblies - Ahamed, Rafiq; Venkatesh, Jayashree; Srithar, Rakshantha; Gaikwad, Sudhakar; Pramanik, Susnata (Organic & Biomolecular Chemistry, 2023)
Carbohydrate-binding proteins, known as lectins, play a wide range of vital roles in cellular and pathological processes. Mimicking lectins to achieve specific molecular recognition of carbohydrates in organic and aqueous media using artificial receptors is challenging due to the synthetic hurdles of receptors and structural similarities between sugars. Carbohydrate recognition using non-covalent interactions remains a vast topic. This review summarises the recognition of carbohydrates using metal-ligand assemblies, including metallosupramolecules, macrocycles, and cages. It also highlights the challenges and future directions in the field.

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

Carbon encapsulated NiCo2S4 nanoparticles with enhanced surface mediated charge storage for superior ultracapacitor electrodes - Chaturvedi, Vikash; Pawar, Meenakshi; Thripuranthaka, M.; Shivade, Rajkiran; Shelke, Manjusha V. V. (Chemistry-An Asian Journal, 2023)
Three different compositions of NiCo2S4 (NCS) materials were prepared using three solvents, named NCS HTDI (hydrothermal in DI water), NCS STEG (solvothermal in ethylene glycol), and a novel carbon-encapsulated NCS STFA (solvothermal in formamide). The structural and morphological properties of the prepared NCS HTDI, NCS STEG, and NCS HTDI materials were analyzed using various physical characterization techniques. As prepared, NCS materials were tested as an electrode for supercapacitor (SC) application using a 3-electrode system in a basic electrolyte (3 M KOH). NCS HTDI exhibits a specific capacitance of 2536 F g(-1), NCS STEG shows 1355 F g(-1), and NCS STFA shows 1178 F g(-1) at an input current density of 1 A g(-1). The SBN-PSC material is utilized as a counter electrode in the NCS STFA || SBN-PSC-based asymmetric SC device. The device exhibits exceptionally superior electrochemical performance with a specific capacitance of 172 F g(-1) at 10 A g(-1) input current density and 97% capacity retention after 5000 cycles in a voltage window of 1.6 V. The results confirm the superiority of NCS STFA||SBN-PSC deviceas an excellent high-energy and high-power SC.
Keywords: Asymmetric supercapacitor device; NiCo2S4; pseudocapacitor; Surface charge storage

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

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

Charge trapped CdS quantum dot embedded polymer matrix for a high speed and low power memristor - Betal, Atanu; Bera, Jayanta; Sharma, Ashish; Rath, Arup K. K.; Sahu, Satyajit (Physical Chemistry Chemical Physics, 2023)
The data storage requirement in the digital world is increasing day by day with the advancement of the internet of things. In this respect, nonvolatile resistive random-access memory is an option that provides high density and low power data storage capabilities. In this work, zero-dimensional colloidal CdS quantum dots and a polymer composite at an appropriate ratio were used to fabricate a memristive device. Comparison with a pristine CdS quantum dot-based device reveals that a surrounding matrix around the quantum dots is needed for observing memristive behavior. The quantum dots embedded in the polymer matrix device showed extremely stable electrical switching behavior that can be operated for more than 300 cycles and 60 000 seconds. Moreover, the device needs extremely low power to operate at a very high speed. The smooth surface morphology dictates a charge trapping mechanism for the switching phenomenon; however, an interplay between different charge transport mechanisms leads to the fast switching and high on-off ratio of the device.

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

Chemically modified graphene sheets as potential sensors for organophosphate compounds(pesticide): A DFT study - Shivankar, Bhavana R.; Singh, Chandrodai Pratap; Krishnamurty, Sailaja (Applied Surface Science, 2023)
Owing to the extensive use of pesticides in agriculture and the threat posed to the environment and humankind, attention is drawn toward the need for its remediation from various sources, in particular from water. The adsorption characteristics of hydrophobic graphene and its BN doped counterparts are evaluated using DFT methodology, to assess their sensing potential towards notable pesticide molecules (Organophosphate pesticides (OPs) such as chlorpyriphos, parathion, methyl-parathion, and fenitrothion). To accomplish this, various elec-tronic properties such as band structure, DOS, Bader charge analysis, and CDD have been calculated. Interest-ingly, exothermic interactions (-0.1 eV to-2 eV) have been noted for all the OPs with NB doped single vacancy defect induced graphene surfaces. With an exception of FTN, all the other OPs showed significant changes in the electronic properties of surfaces as apparent from the change in band gap and nature of the band from indirect to direct. The appreciable adsorption energy, higher charge transfer, and notable variation in the band gap are the decisive factors behind the strong interaction exhibited by NB doped surfaces especially dg-(NB-2)2 (except FTN). These findings demonstrate the suitability of NB doped single vacancy defect induced graphene sheets for the detection of the studied OPs.
Keywords: Adsorption; BN doped graphene surfaces; Charge density difference; Density functional theory; Organophosphate pesticides

Cofilin-membrane interactions: electrostatic effects in phosphoinositide lipid binding - Prakash, Shikha; Krishna, Anjali; Sengupta, Durba (ChemPhysChem, 2023)
The actin cytoskeleton interacts with the cell membrane primarily through the indirect interactions of actin-binding proteins such as cofilin-1. The molecular mechanisms underlying the specific interactions of cofilin-1 with membrane lipids are still unclear. Here, we performed coarse-grain molecular dynamics simulations of cofilin-1 with complex lipid bilayers to analyze the specificity of protein-lipid interactions. We observed the maximal interactions with phosphoinositide (PIP) lipids, especially PIP2 and PIP3 lipids. A good match was observed between the residues predicted to interact and previous experimental studies. The clustering of PIP lipids around the membrane bound protein leads to an overall lipid demixing and gives rise to persistent membrane curvature. Further, through a series of control simulations, we observe that both electrostatics and geometry are critical for specificity of lipid binding. Our current study is a step towards understanding the physico-chemical basis of cofilin-PIP lipid interactions.
Keywords: complex membrane; lipid clustering; Martini coarse-grain simulations; Molecular dynamics simulations; Protein-lipid interactions

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

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

On the competition between six-membered and five-membered NHC towards alane centered ring expansion - Balayan, Kajal; Sharma, Himanshu; Vanka, Kumar; Ravindranathan, Sapna; Gonnade, Rajesh G.; Sen, Sakya S. (Chemical Communications, 2023)
The combination of 6-SIDipp center dot AlH3 (1) and 5-IDipp resulted in the ring expansion of 6-NHC, while the five-membered NHC remained unchanged, which was subsequently explained by DFT studies. Besides, the substitution chemistry of 1 was also studied with TMSOTf and I-2, which gave rise to the substitution of a hydride by triflate or iodide ligands.

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

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

Comprehensive molecular and clinical investigation of approved Anti-HCV drugs repurposing against SARS-CoV-2 infection: a glaring gap between benchside and bedside medicine - Bansode, Sneha; Singh, Pawan Kumar; Tellis, Meenakshi; Chugh, Anita; Deshmukh, Narendra; Gupta, Mahesh; Verma, Savita; Giri, Ashok; Kulkarni, Mahesh; Joshi, Rakesh; Chaudhary, Dhruva (Vaccines, 2023)
The limited availability of effective treatment against SARS-CoV-2 infection is a major challenge in managing COVID-19. This scenario has augmented the need for repurposing anti-virals for COVID-19 mitigation. In this report, the anti-SARS-CoV-2 potential of anti-HCV drugs such as daclatasvir (DCV) or ledipasvir (LDP) in combination with sofosbuvir (SOF) was evaluated. The binding mode and higher affinity of these molecules with RNA-dependent-RNA-polymerase of SARS-CoV-2 were apparent by computational analysis. In vitro anti-SARS-CoV-2 activity depicted that SOF/DCV and SOF/LDP combination has IC50 of 1.8 and 2.0 mu M, respectively, comparable to remdesivir, an approved drug for COVID-19. Furthermore, the clinical trial was conducted in 183 mild COVID-19 patients for 14 days to check the efficacy and safety of SOF/DCV and SOF/LDP compared to standard of care (SOC) in a parallel-group, hybrid, individually randomized, controlled clinical study. The primary outcomes of the study suggested no significant difference in negativity after 3, 7 and 14 days in both treatments. None of the patients displayed any worsening in the disease severity, and no mortality was observed in the study. Although, the post hoc exploratory analysis indicated significant normalization of the pulse rate showed in SOF/DCV and SOF/LDP treatment vs. SOC. The current study highlights the limitations of bench side models in predicting the clinical efficacy of drugs that are planned for repurposing.
Keywords: antiviral; COVID-19; daclatasvir; ledipasvir; SARS-CoV-2; sofosbuvir