Characterization of multidrug resistance in Vibriospecies isolated from marine invertebrates from Andaman Sea - Kumari, Prabla; Poddar, Abhijit; Das, Subrata K. (3 Biotech, 2020)
This study describes the abundance of multidrug-resistantVibriosassociated with marine invertebrate hosts from the Andaman Sea, India. Thirty-eightVibriostrains were isolated from surface mucus layers of coralPorites,Goniastrea, Pocillopora, Fungia, and eggs of spiny lobster (Panulirus penicillatus). Phenotypically, the majority of strains exhibited growth at a wide range of temperatures, salt tolerance, and diverse nutritional requirements. All the strains had more than 97% 16S rRNA sequence similarity with type species of the genusVibriowhereVibrio fortis, andVibrio alginolyticuswere predominant. Multilocus Sequence Analysis (MLSA) using eight housekeeping genes namelyftsZ,gapA,gyrB,mreB,pyrH,recA,rpoA,andtopAdistributed the strains into 6 reported clades i.e.,Harveyi, Ponticus, Nereis, Orientalis, Splendidus,andMediterraneiwhere nearly half of the total strains represented the cladeHarveyi, followed by the cladeSplendidus.Likewise, the PFGE profile indicated genomic heterogeneity among the strains resulting in their distribution in five major clusters. Resistance to different antimicrobials was tested following the disc diffusion method where all strains were found susceptible to chloramphenicol (30 mu g) and resistant to streptomycin (10 mu g), vancomycin (30 mu g), sulfamethoxazole-trimethoprim (25 mu g). Moreover, the resistant phenotype to other antimicrobials confirmed the abundance of multidrug resistance strains in this marine environment.
Keywords: Drug-resistant; Genetic diversity; marine invertebrate; Multilocus sequence analysis; Vibrio

Chiron approach to formal synthesis of both antipodes of cis 3-hydroxypipecolic acid (vol 55, pg 6423, 2014) - Chavan, Subhash P.; Khairnar, Lalit B.; Chavan, Prakash N.; Dumare, Nilesh B.; Kalbhor, Dinesh B.; Gonnade, Rajesh G. (Tetrahedron Letters, 2020)

Co-gasification of high ash coal–biomass blends in a fluidized bed gasifier: - Tiwary, Shishir; Ghugare, Suhas B.; Chavan, Prakash D.; Saha, Sujan; Datta, Sudipta; Sahu, Gajanan; Tambe, Sanjeev S. (Waste and Biomass Valorization, 2020)
Co-gasification (COG) is a clean-coal technology that uses a binary blend of coal and biomass for generating the product gas; it is environment-friendly since it emits lesser quantities of pollutants compared to the coal gasification process. Although coals found in many countries contain high percentages of ash, co-gasification studies involving such coals, and the process modeling thereof, are rare. Accordingly, this study presents results of the co-gasification experiments conducted in a fluidized-bed gasifier (FBG) pilot plant using as a feed the blends of high ash Indian coals with three biomasses, namely, rice husk, press mud, and sawdust. Since the underlying physicochemical phenomena are complex and nonlinear, modeling of the COG process has been performed using three computational intelligence (CI)-based methods namely, genetic programming, artificial neural networks, and support vector regression. Each of these formalisms was employed separately to develop models predicting four COG performance variables, namely, total gas yield, carbon conversion efficiency, heating value of product gas, and cold gas efficiency. All the CI-based models exhibit an excellent prediction accuracy and generalization performance. The co-gasification experiments and their modeling presented here for a pilot-plant FBG can be gainfully utilized in the efficient design and operation of the corresponding commercial scale co-gasifiers utilizing high ash coals.

Combinatorial approach through in vitro regeneration and phytochemical profiling of ceropegia media (huber) ans.: a potential way forward in the conservation of an endangered medicinal plant from the western ghats in India - Pandey, Meena; Dholakia, Bhushan B.; Jayaramaiah, Ramesha H.; Punekar, Sachin A.; Giri, Ashok P. (Journal of Plant Growth Regulation, 2020)
Ceropegia mediais an endemic and endangered plant as its propagation through seeds is unreliable due to low germination, slow growth and seedling decay under natural conditions. Also, tubers of this plant are edible serving as carbohydrate source with medicinal values leading to severe population decline in the natural habitat. To provide a sustainable solution, an efficient in vitro propagation protocol along with phytochemical profiling was developed forC. media. Callus cultures were induced from seedling and wild leaf tissues using the most effective Murashige and Skoog's (MS) medium with 2,4-dichlorophenoxyacetic acid (2,4-D; 2 mu M) and sucrose (3%). Somatic embryos were acquired on MS medium with 1 mu M 6-Benzylaminopurine (BAP) and 1 mu M 2,4-D. Conversion into plantlets was attained only from tissue culture-derived seedling leaf (TCDSL) explant. Further, in vitro tuberization was achieved from TCDSL callus with BAP and Naphthalene acetic acid (NAA). AgNO(3)as an elicitor had a positive effect on both fresh and dry weights of callus. Successful acclimatization (58%) was attained after two months resulting in normal phenotype in pots. Further, metabolite profiles of ten different tissues from wild and in vitro plants were compared. Total 82 compounds comprising alkaloids, fatty acids, fatty acid ester, steroids, terpenes and hydrocarbons were identified. Overall, results suggested enhanced production of selected metabolites with in vitro propagation and AgNO3, alleviating the problem of unavailability of planting materials. Thus, the current study might offer potential ways for the conservation of such RED enlisted species asC. media. [GRAHICS]
Keywords: Ceropegia media; GC-MS; Microtuberization; Secondary metabolites; Silver nitrate; somatic embryogenesis

Comprehensive metagenomic insights into a unique mass gathering and bathing event reveals transient influence on a riverine ecosystem - Yadav, Rakeshkumar; Rajput, Vinay; Gohil, Kushal; Khairnar, Krishna; Dharne, Mahesh (Ecotoxicology and Environmental Safety, 2020)
The religious mass gathering and bathing can pose a multitude of significant public health challenges and lead to severe alterations in the river microbial ecology. The Pandharpur Wari is an annual pilgrimage of Maharashtra, India, where millions of devotees carry the footprints of the saint-poets and pay their obeisance to Lord Vitthal on the 11th day of moon's waxing phase (Ashadi Ekadashi). As a part of the ritual, the engrossed devotees, walk over 250 km, take a first holy dip in a sacred river Indrayani at Alandi and secondly in Bhima River at Pandharpur. The MinION-based shotgun metagenomic approach was employed to examine the impact of spiritual mass bathing on environmental changes (concerning the river microbial community structure and functions); and public health aspects (in terms of changes in the pathogenic potential and antibiotic resistance). The analysis of bathing and post-bathing samples of both the rivers revealed alterations in the alpha and beta diversity, indicating significant spatiotemporal variations in the overall microbial structure and function. Furthermore, the analysis revealed up to 80% of differences in the abundance of virulence genes between the bathing and post bathing samples. We observed parallel increase of priority skin and enteric pathogens (ranging from 11% to 80%) such as Acinetobacter baumannii, Staphylococcus aureus, Streptococcus pyogenes, Mycobacterium tuberculosis, and Pseudomonas aeruginosa during the bathing event. Moreover, we observed a significant increase in the antibiotic resistance in the bathing samples of Bhima and Indrayani rivers respectively. Altogether, this is the first comprehensive metagenomic study unravelling the influence of religious mass-bathing on the riverine ecosystem.
Keywords: Antibiotic resistance; Mass bathing; MinION sequencing; Priority pathogens; Virulence genes

Continuous interfacial centrifugal separation and recovery of silver nanoparticles - Deshpande, Jaydeep B.; Navale, Govinda R.; Dharne, Mahesh S.; Kulkarni, Amol A. (Chemical Engineering & Technology, 2020)
Continuous-flow separation and recovery of silver nanoparticles (AgNPs) using an annular centrifugal extractor (ACE) is demonstrated. Separation was achieved at the liquid-liquid interface based on the balance between centrifugal force and the solubility of the capping agent. A mathematical model is presented to understand the mechanism in greater detail. The separation of poly(vinylpyrrolidone) (PVP)-coated AgNPs in an ACE using a strong immiscible solvent was performed. The material accumulated at the interface was separated periodically without discontinuing the operation. The method is also suitable for separation of large particles or 1D/2D nanostructures even employing a single annular centrifugal extractor. Stable AgNPs were selected for a detailed antimicrobial activity study.
Keywords: Annular centrifugal extractor; Antimicrobial activity; Continuous-flow separation; Liquid-liquid interface; silver nanoparticles

Controlling and stabilization of Ru nanoparticles by tuning the nitrogen content of the support for enhanced H-2 production through aqueous-phase reforming of glycerol - Gogoi, Pranjal; Kanna, Narsimharao; Begum, Pakiza; Deka, Ramesh C.; Satyanarayana, C. V. V.; Raja, Thirumalaiswamy (ACS Catalysis, 2020)
The stable activity of catalysts is an important issue in catalysis, particularly aqueous-phase reforming (APR) of renewable oxygenates, of biomass origin, to get H-2. Sintering of metal nanoparticles on supports affects catalyst stability. To alleviate this problem, a series of highly stable Ru-supported catalysts with controlled metal nanoparticle sizes have been prepared via the easy incipient wetness impregnation method. These catalysts were used for APR of glycerol to produce H-2. Nitrogen-doped mesoporous carbons (NMCs) were utlized as supports and found to have a strong influence on the catalytic performance of the catalysts. Incorporation of nitrogen in the carbon framework significantly enhanced the catalytic activity compared to Ru catalysts on nitrogen-free supports. Notably, the catalyst (5 wt % Ru-NMC-3) with optimal N content (10.9 wt %) demonstrated improved stability and H-2 selectivity, which are better than those of many state-of-the-art catalysts. Nitrogen in the carbon framework has a dual relationship with the activity of the catalyst: (i) it creates basic environment over the catalysts support and (ii) it acts as an anchoring site for metal nanoparticles. Anchoring of metal nanoparticles has helped to curb their sintering, thus leading to better stability of the catalysts under APR reaction conditions. Various characterization techniques were employed to understand the nature of active catalytic sites responsible for higher H-2 production while minimizing CO formation. In situ CO-FTIR studies showed that the higher catalytic activity of 5 wt % Ru-NMC-3 catalyst was attributed to the enhanced WGS activity over this catalyst. Density functional theory calculations were performed to understand the stabilization of metal nanoparticles by different types of N present on the support and provide insights into the prefered sites of glycerol adsorption on the NMC support. Since S wt % Ru-NMC-3 was the relatively best catalyst, it was selected for the preparation of bimetallic catalysts. Accordingly, addition of Pt to this system helped to increase the stability of the catalyst. This bimetallic catalyst may, therefore, find application for wide use in APR of biomass oxygenates.
Keywords: aqueous-phase reforming; Glycerol; H-2 production; Ru/NMC catalyst; synergistic effect

Deciphering taxonomic and functional diversity of fungi as potential bioindicators within confluence stretch of Ganges and Yamuna Rivers, impacted by anthropogenic activities - Samson, Rachel; Rajput, Vinay; Shah, Manan; Yadav, Rakeshkumar; Sarode, Priyanka; Dastager, Syed G.; Dharne, Mahesh S.; Khairnar, Krishna (Chemosphere, 2020)
<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">River confluences are interesting ecological niche with limited information in respect of the structure and the functions of diverse microbial communities. Fungi are gaining global attention as promising biological spectacles for defining the trophic status of riverine systems. We condense existing knowledge in confluence diversity in two Indian rivers (i.e. Ganges and Yamuna), by combining sediment metagenomics using long read aided MinION nanopore sequencing. A total of 63 OTU’s were observed, of which top 20 OTU’s were considered based on relative abundance of each OTU at a particular location. Fungal genera such as <em style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">Aspergillus, Penicillium<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">, <em style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">Kluveromyces, Lodderomyces,<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;"> and <em style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">Nakaseomyces<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;"> were deciphered as potential bio indicators of river pollution and eutrophication in the confluent zone. <em style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">In silico<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;"> functional gene analysis uncovered hits for neurodegenerative diseases and xenobiotic degradation potential, supporting bioindication of river pollution in wake of anthropogenic intervention.

DFT/NMR approach for the configuration assignment of groups of stereoisomers by the combination and comparison of experimental and predicted sets of data - Lauro, Gianluigi; Das, Pronay; Riccio, Raffaele; Reddy, D. Srinivasa; Bifulco, Giuseppe (Journal of Organic Chemistry, 2020)
Quantum mechanical/nuclear magnetic resonance (NMR) approaches are widely used for the configuration assignment of organic compounds generally comparing one cluster of experimentally determined data (e.g., C-13 NMR chemical shifts) with those predicted for all possible theoretical stereoisomers. More than one set of experimental data, each related to a specific stereoisomer, may occur in some cases, and the accurate stereoassignments can be obtained by combining the experimental and computed data. We introduce here a straightforward methodology based on the simultaneous analysis, combination, and comparison of all sets of experimental/calculated C-13 chemical shifts for aiding the correct configuration assignment of groups of stereoisomers. The comparison of the differences between the calculated/experimental chemical shifts instead of the shifts themselves led to the advantage of avoiding errors arising from calibration procedures, reducing systematic errors, and highlighting the most diagnostic differences between calculated and experimental data. This methodology was applied on a tetrad of synthesized cladosporin stereoisomers (cladologs) and further corroborated on a tetrad of pochonicine stereoisomers, obtaining the correct correspondences between experimental and calculated sets of data. The new MAE(Delta Delta delta) parameter, useful for indicating the best fit between sets of experimental and calculated data, is here introduced for facilitating the stereochemical assignment of groups of stereoisomers.

Differential modulation in metabolites revealed with the improvement in the shelf-life of alphonso fruits - Dar, M. Saleem; Dholakia, Bhushan B.; Shanmugam, Haripriya; Gupta, Vidya S.; Subramanian, K. S.; Subramanian, J.; Giri, Ashok P. (Molecular Biotechnology, 2020)
Globally farmers have difficulty in extending the shelf-life of the tropical fruits due to their perishable nature. The present study aimed to assess the effect of hexanal nano-formulation treatment (NFT) on the shelf-life of Alphonso mango. Further, volatilomics was performed to explore the molecular basis of such effect. Untreated and treated fruits were sampled starting from 5th to 21st day after NFT at an interval of 4 days. Moderate changes in visual and digital colour parameters were evident from the intact and dissected fruits of NFT set compared to untreated fruits. Biochemical assays affirmed the phenotypic differences with significant changes in the colour imparting compounds like carotenoids and anthocyanins among them. Further, gas chromatography-mass spectrometry analysis revealed significant qualitative and quantitative variations in the different classes of compounds like lactones, furanones, esters, aldehydes and alcohols. Some of the key metabolites showed differential modulations among the NFT and untreated fruit sets indicating their potential role in various processes, which ultimately might have resulted in delayed ripening of the mango. Overall, this study has demonstrated the beneficial effect of hexanal and identified important metabolites with the enhanced shelf-life in Alphonso that could be useful for farmers and mango-based food/flavour industries.
Keywords: Alphonso; GC-MS; Metabolites; Nano-biotechnology; Nano-formulation; Shelf-life; Volatilomics

Dioxolanone-anchored poly(allyl ether)-based cross-linked dual-salt polymer electrolytes for high-voltage lithium metal batteries - Vijayakumar, Vidyanand; Diddens, Diddo; Heuer, Andreas; Kurungot, Sreekumar; Winter, Martin; Nair, Jijeesh Ravi (ACS Applied Materials & Interfaces, 2020)
Novel cross-linked polymer electrolytes (XPEs) are synthesized by free-radical copolymerization induced by ultraviolet (UV)-light irradiation of a reactive solution, which is composed of a difunctional poly(ethylene glycol) diallyl ether oligomer (PEGDAE), a monofunctional reactive diluent 4-vinyl-1,3-dioxolan-2-one (VEC), and a stock solution containing lithium salt (lithium bis(trifluoromethanesulfonyl)imide, LiTFSI) in a carbonate-free nonvolatile plasticizer, poly(ethylene glycol) dimethyl ether (PEGDME). The resulting polymer matrix can be represented as a linear polyethylene chain functionalized with cyclic carbonate (dioxolanone) moieties and cross-linked by ethylene oxide units. A series of XPEs are prepared by varying the [O]/[Li] ratio (24 to 3) of the stock solution and thoroughly characterized using physicochemical (thermogravimetric analysis-mass spectrometry, differential scanning calorimetry, NMR, etc.) and electrochemical techniques. In addition, quantum chemical calculations are performed to elucidate the correlation between the electrochemical oxidation potential and the lithium ion-ethylene oxide coordination in the stock solution. Later, lithium bis(fluorosulfonyl)imide (LiFSI) salt is incorporated into the electrolyte system to produce a dual-salt XPE that exhibits improved electrochemical performance, a stable interface against lithium metal, and enhanced physical and chemical characteristics to be employed against high-voltage cathodes. The XPE membranes demonstrated excellent resistance against lithium dendrite growth even after reversibly plating and stripping lithium ions for more than 1000 h with a total capacity of 0.5 mAh cm(-2). Finally, the XPE films are assembled in a lab-scale lithium metal battery configuration by using carbon-coated LiFePO4 (LFP) or LiNi0.8Co0.15Al0.05O2 (NCA) as a cathode and galvanostatically cycled at 20, 40, and 60 degrees C. Remarkably, at 20 degrees C, the NCA-based lithium metal cells displayed excellent cycling stability and good capacity retention (>50%) even after 1000 cycles.
Keywords: cross-linked polymer electrolyte; dual-salt electrolyte; high-voltage cathode; lithium metal battery; solvent-free photopolymerization

Directed holey and ordered g-C(3)N(4.5)nanosheets by a hard template nanocasting approach for sustainable visible-light hydrogen evolution with prominent quantum efficiency - Antil, Bindu; Ranjan, Ravi; Gopinath, Chinnakonda S.; Deka, Sasanka (Journal of Materials Chemistry A, 2020)
It is desirable yet challenging to synthesize a highly ordered holey carbon nitride material with excess nitrogen atoms for a sustainable solar H(2)evolution. Herein, we report the development of directed highly ordered nitrogen-rich honeycomb-like mesoporous carbon nitride nanosheets by using a novel synthetic approach for this purpose. The unique formation route, surface structure and charge carrier dynamics of the two dimensional holey nanosheets are comprehensively monitored and confirmed by SAXS, HRTEM, AFM, BET, XPS and TRPL analyses. Non-stoichiometric high nitrogen content mesoporous nanosheets with the final stoichiometry of g-C(3)N(4.5)acquiring a high specific surface area (382 m(2)g(-1)), remarkable pore size (7.2 nm) and sheet thickness similar to 5-6 nm are realized in this first report. This elegant material possesses unique low band-gap energy (2.42 eV). Remarkably, the as-synthesized g-C(3)N(4.5)NSs exhibit a record high photocatalytic H(2)evolution rate of 8180 mu mol g(-1)h(-1)under the present light irradiation (420 <=lambda <= 510 nm) condition. The apparent quantum efficiency is found to be as high as 27.14% at 420 nm and retains its photocatalytic activity for longer consecutive catalytic cycles. Bigger pore size and pore volume, and thin walls leading to shortening of the path length of exciton pairs, efficient charge separation and the prolonged average life time of the charge carriers, and lone electron pairs associated with the excess nitrogen content are found to be the reasons behind the excellent visible light driven water splitting reaction.

Discovery of 3-(benzofuran-2-ylmethyl)-1H-indole derivatives as potential autophagy inducers in cervical cancer cells - Siddiqui, Shaziyaparveen K.; SahayaSheela, Vinodh J.; Kolluru, Srinivas; Pandian, Ganesh N.; Santhoshkumar, Thankayyan R.; Dan, Vipin M.; Ramana, V, Chepuri (Bioorganic & Medicinal Chemistry Letters, 2020)
In this manuscript we have documented the identification of a novel anticancer scaffold 3-(benzofuran-2-yl-methyl)-1H-indole. This scaffold has been designed by tweaking the known bisindolylmethane scaffold of natural products that display a wide range of biological activities. A series of 24 new conjugates have been synthesized and among them 5 derivatives exhibited IC50 values less than 40 mu M against two cervical cancer cell lines SiHa and C33a. Further mechanistic studies of two compounds 3eb and 3ec revealed that the toxicity of these compounds was due to the effective induction of autophagy mediated cell death. The autophagy induction was confirmed by the progressive conversion of LC3I to LC3II and downregulation of p62 in cervical cancer cells.
Keywords: Autophagy; Benzofuran; Bisindolylmethane; Cervical cancer; Friedel-Crafts alkylation

Distinct metabolic states of a cell guide alternate fates of mutational buffering through altered proteostasis - Verma, Kanika; Saxena, Kanika; Donaka, Rajashekar; Chaphalkar, Aseem; Rai, Manish Kumar; Shukla, Anurag; Zaidi, Zainab; Dandage, Rohan; Shanmugam, Dhanasekaran; Chakraborty, Kausik (Nature Communications, 2020)
Metabolic changes alter the cellular milieu; can this also change intracellular protein folding? Since proteostasis can modulate mutational buffering, if change in metabolism has the ability to change protein folding, arguably, it should also alter mutational buffering. Here we find that altered cellular metabolic states in E. coli buffer distinct mutations on model proteins. Buffered-mutants have folding problems in vivo and are differently chaperoned in different metabolic states. Notably, this assistance is dependent upon the metabolites and not on the increase in canonical chaperone machineries. Being able to reconstitute the folding assistance afforded by metabolites in vitro, we propose that changes in metabolite concentrations have the potential to alter protein folding capacity. Collectively, we unravel that the metabolite pools are bona fide members of proteostasis and aid in mutational buffering. Given the plasticity in cellular metabolism, we posit that metabolic alterations may play an important role in cellular proteostasis.

Dual mode selective detection and differentiation of TNT from other nitroaromatic compounds - Patil, Goudappagouda; Dongre, Sangram D.; Das, Tamal; Babu, Sukumaran Santhosh (Journal of Materials Chemistry A, 2020)
Selective detection of explosives, especially TNT, is a highly desirable area of research and various explosives detection devices including fluorescent sensors are already in place. However, multi-mode sensors will be more useful and reliable than conventional fluorescent ``Turn Off'' sensors. One of the challenges is the development of selective sensors to prevent illegal transport of commonly used explosive TNT through on-the-spot analysis. In this context, we report a fluorescent polymer-based selective detection of TNT using both fluorometric and colorimetric signals. In addition, colorimetric differentiation of TNT from other nitroaromatic compounds is made possible by complexing with various amines. Even though many other sensors are available for TNT, the current demonstration is unique in terms of selectivity, sensitivity, reliability, portability, and rapidity of results. The as-developed explosive detection kit can be useful in both civilian and military operations to trace the illegal transport of TNT as well as for post-explosion analysis.

Dual responsive cellulose microspheres with high solid-state fluorescence emission - Yadav, Prashant; Prajitha, K. P.; Dhaware, Vinita; Subramani, Mohan; Joy, Pattayil; Asha, S. K.; Shanmuganathan, Kadhiravan (Colloids and Surfaces A-Physicochemical and Engineering Aspects, 2020)
Materials that respond to multiple stimuli such as magnetic field and light are attractive for security and medical diagnostic applications. One of the major challenges in dual functional microspheres is that the presence of magnetic nanoparticles can quench fluorescence emission. Also, there is a probability of solid-state quenching due to the proximity of the fluorophore. We report here a facile approach to prepare cellulose microspheres with high solid-state fluorescence using 40 % tetrabutylammonium hydroxide (TBAH). The fluorescence quenching effect due to the presence of Fe3O4 nanoparticles and solid-state quenching due to aggregation of fluorophore was systematically investigated. Microspheres with the detectable magnetic response and fluorescence quantum yield as high as 0.57 (FMB 414) was obtained by optimizing the reaction conditions. Such a high quantum yield has not been reported before for dual stimuli-responsive fluorescent microspheres. The magnetic and fluorescent properties were found to be durable even after multiple washing cycles. These dual responsive cellulose microspheres can be added as security features to authenticate documents such as passports, degree certificates, currency notes, financial documents etc.
Keywords: Fluorescent; Magnetic; Microcrystalline cellulose; microspheres; Stimuli responsive microspheres; Tetrabutylammonium hydroxide

Effect of aromatic rings and substituent on the performance of lithium batteries with rylene imide cathodes - Aher, Jagdish; Graefenstein, Alexander; Deshmukh, Gunvant; Subramani, Kumar; Krueger, Bastian; Haensch, Mareike; Schwenzel, Julian; Krishnamoorthy, Kothandam; Wittstock, Gunther (ChemElectroChem, 2020)
Rylene imides (RIs) are attractive organic battery materials because of the inherent modularity of the molecules. While strong aggregation of RIs is disadvantageous for fast lithium-ion transport in the organic active material, decreasing the solubility of the RIs in battery electrolytes is essential to avoid performance fading. Therefore, the design and synthesis of RIs for lithium batteries is a non-trivial task that must, among other considerations, balance lithium-ion transport in the solid material vs. low solubility by controlling aggregation and packing. We have chosen triphenylamine (TPA) as a substituent which disrupts the aggregation but maintains a low solubility due to increased aromaticity of TPA. We have synthesized three RIs with one, two, and four aromatic units in the core. All of them showed stable specific capacity over 300 charge-discharge cycles. The batteries also showed specific capacities close to their theoretical capacities with 97-99 % coulombic efficiency. The maximum specific energy and specific power were 197 mWh g(-1) and 37 mW g(-1), respectively.
Keywords: lithium-ion batteries; organic cathode material; rylene imides; solubility; triphenylamine

Effect of melatonin on tau aggregation and tau-mediated cell surface morphology - Das, Rashmi; Balmik, Abhishek Ankur; Chinnathambi, Subashchandrabose (International Journal of Biological Macromolecules, 2020)
Aggregation of Microtubule-associated protein Tau and its deposition in the form of neurofibrillary tangles (NFTs) is one of the pathological hallmarks of Alzheimer's disease (AD). Tau aggregation inhibition has been targeted in various studies including natural compounds and synthetic small molecules. Here, we have studied neurohormone- Melatonin against in vitro Tau aggregation and observed its effect on membrane topology, tubulin network and Tau phosphorylation in Neuro2A and N9 cell lines. The aggregation and conformation of Tau was determined by ThT fluorescence and CD spectroscopy respectively. The morphology of Tau aggregates in presence and absence of Melatonin was studied by transmission electron microscopy. Melatonin was found to reduce the formation of higher order oligomeric structures without affecting the overall aggregation kinetics of Tau. Melatonin also modulates and helps to maintain membrane morphology, independent on tubulin network as evidenced by FE-SEM and immunofluorescence analysis. Overall, Melatonin administration shows mild anti-aggregation and cytoprotective effects. (C) 2020 Elsevier B.V. All rights reserved.
Keywords: Alzheimer's disease; Cell surface morphology; melatonin; Paired helical filaments; tau protein; Tauopathies

Efficient method for the synthesis of quinoxaline derivatives catalyzed by titanium silicate-1 - Chandrachood, Pranav S.; Jadhav, Amol R.; Garud, Dinesh R.; Deshpande, Nirmala R.; Puranik, Vedavati G.; Kashalkar, Rajashree V. (Research on Chemical Intermediates, 2020)
A series of quinoxaline derivatives were efficiently synthesized by convenient and simple procedure in excellent yields using 1 wt.% of titanium silicate (TS-1) catalyzed reaction of 1,2-diamines and 1,2-diketones in methanol at room temperature. This reaction is scalable to multigram scale and the catalyst is recyclable. [GRAPHICS] .
Keywords: 2-Diketones; Aromatic 1; o-Phenylenediamine; Quinoxaline; Room temperature; Titanium silicate-1

EGCG impedes human Tau aggregation and interacts with Tau - Sonawane, Shweta Kishor; Chidambaram, Hariharakrishnan; Boral, Debjyoti; Gorantla, Nalini Vijay; Balmik, Abhishek Ankur; Dangi, Abha; Ramasamy, Sureshkumar; Marelli, Udaya Kiran; Chinnathambi, Subashchandrabose (Scientific Reports, 2020)
Tau aggregation and accumulation is a key event in the pathogenesis of Alzheimer's disease. Inhibition of Tau aggregation is therefore a potential therapeutic strategy to ameliorate the disease. Phytochemicals are being highlighted as potential aggregation inhibitors. Epigallocatechin-3-gallate (EGCG) is an active phytochemical of green tea that has shown its potency against various diseases including aggregation inhibition of repeat Tau. The potency of EGCG in altering the PHF assembly of full-length human Tau has not been fully explored. By various biophysical and biochemical analyses like ThS fluorescence assay, MALDI-TOF analysis and Isothermal Titration Calorimetry, we demonstrate dual effect of EGCG on aggregation inhibition and disassembly of full-length Tau and their binding affinity. The IC50 for Tau aggregation by EGCG was found to be 64.2 mu M.

Electrochemical performance of pre-lithiated ZnMoO4 and r-GO@ZnMoO4 composite anode for lithium-ion battery application - Bin Masood, Khalid; Parte, Golu; Jain, Neha; Dwivedi, Pravin K.; Kumar, Pushpendra; Shelke, V, Manjusha; Patel, Rp; Singh, Jai (Journal of the Taiwan Institute of Chemical Engineers, 2020)
Exploring a safer replacement of Li metal anode is crucial for technological, and fundamental importance. Li-metal is a preferred choice as anode material for lithium-ion battery (LIB) applications. However, parasitic dendritic growth on the Li metal surface during cycling causes instability and safety dreads. In the present study, we have investigated that the pre-lithiated ZnMoO4 is superior to its carbon-based counterparts (r-GO@ZnMoO4), moreover safer and sustainable than Li metal anode. The pre-lithiated ZnMoO4 delivers a better reversible capacity (similar to 1000 mAhg(-1) at 0.1 Ag-1), superior rate capability (similar to 400 mAh g(-1) at 2 Ag-1), and excellent cycling stability over 300 cycles at 0.1 Ag-1, as compared to bare ZnMoO4 and r-GO@ZnMoO4 composite. The present investigation is an attempt to provide a substitute for commonly used Li-metal/carbon anodes with better performance. (C) 2020 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: Cycling stability; Electrochemistry; Li-ion battery; Nyquist plot; Rate performance; ZnMoO4 nanocomposites

Electrospun fibers and sorbents as a possible basis for effective composite wound dressings - Saul Alvarez-Suarez, Alan; Dastager, Syed G.; Bogdanchikova, Nina; Grande, Daniel; Pestryakov, Alexey; Carlos Garcia-Ramos, Juan; Lizeth Perez-Gonzalez, Graciela; Juarez-Moreno, Karla; Toledano-Magana, Yanis; Smolentseva, Elena; Antonio Paz-Gonzalez, Juan; Popova, Tatiana; et al. (Micromachines, 2020)
Skin burns and ulcers are considered hard-to-heal wounds due to their high infection risk. For this reason, designing new options for wound dressings is a growing need. The objective of this work is to investigate the properties of poly (epsilon-caprolactone)/poly (vinyl-pyrrolidone) (PCL/PVP) microfibers produced via electrospinning along with sorbents loaded with Argovit (TM) silver nanoparticles (Ag-Si/Al2O3) as constituent components for composite wound dressings. The physicochemical properties of the fibers and sorbents were characterized using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and inductively coupled plasma optical emission spectroscopy (ICP-OES). The mechanical properties of the fibers were also evaluated. The results of this work showed that the tested fibrous scaffolds have melting temperatures suitable for wound dressings design (58-60 degrees C). In addition, they demonstrated to be stable even after seven days in physiological solution, showing no macroscopic damage due to PVP release at the microscopic scale. Pelletized sorbents with the higher particle size demonstrated to have the best water uptake capabilities. Both, fibers and sorbents showed antimicrobial activity against Gram-negative bacteria Pseudomona aeruginosa and Escherichia coli, Gram-positive Staphylococcus aureus and the fungus Candida albicans. The best physicochemical properties were obtained with a scaffold produced with a PCL/PVP ratio of 85:15, this polymeric scaffold demonstrated the most antimicrobial activity without affecting the cell viability of human fibroblast. Pelletized Ag/Si-Al2O3-3 sorbent possessed the best water uptake capability and the higher antimicrobial activity, over time between all the sorbents tested. The combination of PCL/PVP 85:15 microfibers with the chosen Ag/Si-Al2O3-3 sorbent will be used in the following work for creation of wound dressings possessing exudate retention, biocompatibility and antimicrobial activity.
Keywords: electrospinning; poly (epsilon-caprolactone); poly (vinyl pyrrolidone); silver sorbents; wound dressings

Electrospun nanofibers of Tin phosphide (SnP0.94) nanoparticles encapsulated in a carbon matrix: a tunable conversion-cum-alloying lithium storage anode - Yadav, Poonam; Malik, Wahid; Dwivedi, Pravin Kumari; Jones, Lathe A.; Shelke, Manjusha V. (Energy & Fuels, 2020)
Anodes with improved Li storage capability are required for next-generation lithium batteries. In this work we report a convenient synthesis strategy, based on electrospinning followed by reduction and phosphorization, to prepare a tin phosphide (SnP0.94) phase in a carbon nanofiber matrix. The layered structure offered by the SnP0.94 phase, along with its small size (5-20 nm) encapsulated in the conducting carbon matrix, leads to promising electrochemical Li storage characteristics. This composite has a capacity of 750 mAh g(-1) at 100 mA g(-1) with good cycling and rate stability. Electrochemical studies revealed a faster diffusion coefficient (1.86 x 10(-11) cm(2) s(-1)) for Li in the composite compared to the bare SnP0.94 (8.57 x 10(-14) cm(2) s(-1)), confirming the promise of this class of materials for cation storage in battery anodes.

Electrospun poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/polyethylene oxide (PEO) microfibers reinforced with ZnO nanocrystals for antibacterial and antibiofilm wound dressing applications - Mahamuni-Badiger, Pranjali P.; Patil, Pooja M.; Patel, Pratikshkumar R.; Dhanavade, Maruti J.; Badiger, V. Manohar; Marathe, Yogesh N.; Bohara, Raghvendra A. (New Journal of Chemistry, 2020)
Biocompatible and biodegradable polymers are extensively used in designing wound dressing materials. The present investigation deals with the preparation of a unique blend of zinc oxide (ZnO) nanoparticles incorporated in poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV)/polyethylene oxide (PEO) microfibersviaan electrospinning technique for antibacterial, antibiofilm and wound dressing applications. This composite was prepared by incorporating previously synthesized ZnO NPs with better antibacterial and antibiofilm activity in PHBV-PEO (4 : 1) polymers in chloroform solution. Scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR) spectroscopy confirmed that ZnO NPs were incorporated in the PHBV-PEO microfibers. The synthesized microfibers exhibited enhanced mechanical properties after the incorporation of ZnO NPs. The results of antibacterial and antibiofilm activity of the prepared microfibers revealed that the incorporated ZnO NPs in different concentrations (1%, 3%, and 5%) showed different degrees of antibacterial activity against pathogenic Gram-positiveStaphylococcus aureus(NCIM 2654) and Gram-negativePseudomonas aeruginosa(NCIM 5032), which are the main bacteria found in wound infections. The PHBV-PEO-ZnO microfibers exhibited excellent hemocompatibility with improved swelling behavior after the incorporation of ZnO NPs.In vitrocytotoxicity assays revealed the non-toxic nature of the prepared PHBV-PEO-ZnO microfibers. The current work confirms that utilizing a unique blend of the biodegradable, biocompatible, thermoplastic and hydrophobic natural polymer PHBV with hydrophobic, biodegradable, non-toxic and synthetic polymer PEO with ZnO NPs holds great potential for use as an antibacterial and antibiofilm material for wound dressing applications.

Enantio- and diastereocontrolled conversion of chiral epoxides to trans-cyclopropane carboxylates: application to the synthesis of cascarillic acid, grenadamide and L-(-)-CCG-II (vol 10, pg 6987, 2012) - Kumar, Pradeep; Dubey, Abhishek; Harbindu, Anand (Organic & Biomolecular Chemistry, 2020)

Engineering pore morphology using silica template route over mesoporous cobalt oxide and its implications in atmospheric pressure carbon dioxide hydrogenation to olefins - Gupta, Sharad; Ciotonea, Carmen; Royer, Sebastien; Dacquin, Jean-Philippe; Vinod, C. P. (2020)
Highly ordered mesoporous cobalt oxides (denoted as m-Co-KIT-6 and m-Co-SBA-15) with three dimensional and two dimensional pore morphology respectively have been synthesized using 3D KIT-6, and 2D SBA-15 as silica template via nanocasting route. CO2 hydrogenation activity was evaluated for these mesoporous materials under atmospheric pressure conditions. In comparison to nanoparticles of cobalt oxide (Co3O4-nano), mesoporous catalysts showed excellent activity for CO2 hydrogenation due to their higher number of exposed active sites and lower mass diffusion limitations. The ordered mesoporous structure of Co3O4 catalysts favored the chain growth of carbon atoms for the production of C2+ hydrocarbons while Co3O4 nanoparticles showed strong selectivity toward CH4. High selectivity for C2+ (similar to 25%) was obtained for both m-Co-KIT-6 and m-Co-SBA-15 catalysts at 320 degrees C. In addition, the 3D pore structure of m-Co-KIT-6 catalyst exclusively formed more olefins (54.9%) fraction. (C) 2020 Published by Elsevier Ltd.
Keywords: CO2 hydrogenation; Mesoporous CO3O4; Olefin fraction; Pore morphology; Silica hard template

Enhanced anti-ageing and wound healing properties of Ficus religiosa L. bark, leaf and aerial root extract in human keratinocytes cell line (HaCaT) - Pandey, Prem; Seo, Hyo Hyun; Kim, Hye-In; Ryu, Seung Hwan; Dingre, Medini; Moh, Sang Hyun; Kulkarni, Atul; Parasharami, Varsha A. (Vegetos, 2020)
<span style="color: rgb(51, 51, 51); font-family: Georgia, Palatino, serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; background-color: rgb(252, 252, 252);">Plants have played a vital role in curative and preventive healthcare. <i style="box-sizing: inherit; color: rgb(51, 51, 51); font-family: Georgia, Palatino, serif; font-size: 18px; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; background-color: rgb(252, 252, 252);">Ficus religiosa<span style="color: rgb(51, 51, 51); font-family: Georgia, Palatino, serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; background-color: rgb(252, 252, 252);"> L., a medicinally important tree has been used as a traditional medicine to treat various ailments and skin diseases. However, its skin anti-ageing properties are not yet scientifically evaluated. Here we report the comparison of <i style="box-sizing: inherit; color: rgb(51, 51, 51); font-family: Georgia, Palatino, serif; font-size: 18px; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; background-color: rgb(252, 252, 252);">F. religiosa<span style="color: rgb(51, 51, 51); font-family: Georgia, Palatino, serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; background-color: rgb(252, 252, 252);"> bark (FRAqB), leaf (FRAqL) and aerial-roots (FRAqAR) extracts for skin anti-ageing and wound healing properties. FRAqB, FRAqL and FRAqAR extracts preparation, cell culture, RNA isolation, real time PCR, astringent activity and wound healing assay were carried out using standard methods. Axio Observer FL-microscope and ImageJ software were used for wound healing assay analysis. The real time PCR study reveals that matrix metalloproteinase-1 (MMP) RNA was downregulated to 75% and 95% for FRAqB and FRAqAR, respectively. For procollagen C-endopeptidase enhancer 1 (PCOLCE), FRAqB and FRAqL enhanced RNA levels by 500% and 300%, respectively. FRAqB and FRAqL increased wound healing area to about 60% and FRAqAR by 50%. All three extracts demonstrated astringent activity which is significant for skin tightening. The study proves that extracts of <i style="box-sizing: inherit; color: rgb(51, 51, 51); font-family: Georgia, Palatino, serif; font-size: 18px; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; background-color: rgb(252, 252, 252);">F. religiosa<span style="color: rgb(51, 51, 51); font-family: Georgia, Palatino, serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; background-color: rgb(252, 252, 252);"> are prominent candidates for pharmaceutical and cosmetic applications such as skin anti-ageing and wound healing.

Enteric pH responsive cargo release from PDA and PEG coated mesoporous silica nanoparticles: a comparative study in Drosophila melanogaster - Sapre, Nidhi; Chakraborty, Rusha; Purohit, Poorvi; Bhat, Suresh; Das, Gaurav; Bajpe, Sneha R. (RSC Advances, 2020)
Physiological stimulus-specific cargo release from nanoparticle carriers is a holy grail of drug delivery research. While the majority of such work is carried out in vitro with cell lines, widespread use of common mammalian model systems - mice and rats - is difficult due to the associated cost and regulatory restrictions. Here we use the inexpensive, easily reared, excellent genetic model system Drosophila melanogaster to test pH responsive cargo release from widely used mesoporous silica nanoparticles (MSNs) coated with pH sensitive polydopamine (PDA) and polyethylene glycol (PEG) polymers. We synthesized 650 +/- 75 nm diameter PDA or PEG coated mesoporous silica nanoparticles loaded with a fluorescent dye and fed to individual adult flies. Subsequently, the passage of the particles were monitored through the fly gut. As in mammals, the fly intestine has multiple pH specific zones that are easily accessible for imaging and also genetic, biochemical or physiological manipulations. We observed that both the species of MSNs ruptured around the acidic (pH < 4.0) middle midgut of the flies. PEG coated particles showed sharper specificity of release in the acidic middle midgut of flies than the PDA coated ones and had less tendency to clump together. Our results clearly show that the Drosophila gut can be used as a model to test pH responsive biocompatible materials in vivo. Our work paves the way for greater use of Drosophila as an in vivo complete systemic model in drug delivery and smart materials research. It also suggests that such specific delivery of chemical/biological cargo can be exploited to study basic biology of the gut cells and their communication with other organs.

Evaluation of biomolecular interactions and cytotoxic activity of organometallic binuclear Ru(II) complexes of ferrocenyl thiosemicarbazones - Khanvilkar, Priyanka; Dash, Soumya R.; Vohra, Alisagar; Devkar, Ranjitsinh; Chakraborty, Debjani (Journal of Biomolecular Structure & Dynamics, 2020)
{Four new ferrocenyl substituted thiosemicarbazone ligands (L1-L4) and their corresponding binuclear ruthenium(II) arene complexes of the general type [(eta(6)-pcym)(L)Ru(mu-im)Ru(L)(eta(6)-p-cym)]Cl (C1-C4) and [(eta(6)-pcym)(L)Ru(mu-azpy)Ru(L)(eta(6)-p-cym)]Cl-2(C5-C8) (cym = cymene
Keywords: binuclear ruthenium(II) complexes; BSA binding interactions; DNA; Ferrocenyl thiosemicarbazone; HeLa human cervical carcinoma

Experimental and theoretical investigations of the effect of heteroatom-doped carbon microsphere supports on the stability and storage capacity of nano-Co3O4 conversion anodes for application in lithium-ion batteries - Dwivedi, Pravin K.; Nair, Aathira; Mehare, Rupali S.; Chaturvedi, Vikash; Joshi, Kavita; Shelke, V, Manjusha (Nanoscale Advances, 2020)
Conversion-type anode materials have been intensely studied for application in Li-ion batteries (LIBs) due to their potentially higher capacities than current graphite-based anodes. This work reports the development of a high-capacity and stable anode from a nanocomposite of N and S co-doped carbon spheres (NSCSs) with Co3O4 (NSCS-Co3O4). A hydrothermal reaction of saccharose withl-cysteine was carried out, followed by its carbonization. CSs when used as supports for conversion-type materials provide efficient electron/ion transfer channels, enhancing the overall electrochemical performance of the electrodes. Additionally, the heteroatoms doped in a carbon matrix alter the electronic properties, often increasing the reactivity of the carbon surface, and they are reported to be effective for anchoring metal oxide nanoparticles. Consequently, the NSCS-Co3O4 nanocomposites developed in this work exhibit enhanced and stable reversible specific capacity over several cycles. Stable cycling behavior was observed at 1 A g(-1)with 1285 mA h g(-1) of specific capacity retained after 350 cycles along with more than 99% of coulombic efficiency. This material shows excellent rate capability with a specific capacity of 745 mA h g(-1) retained even at a high current density of 5 A g(-1). Detailed DFT-based calculations revealed the role of doped supports in controlling the volume expansion upon lithiation.

Exploring magnetic XY behavior in a quasi-2D anisotropic triangular lattice of Cu(II) by functionalized graphene - Gupta, Kriti; Dadwal, Arun; Jha, Plawan Kumar; Jain, Anil; Yusuf, S. M.; Joy, Pattayil A.; Ballav, Nirmalya (Inorganic Chemistry, 2020)
Study on magnetism in two-dimensional (2D) spin-lattices is advancing rapidly. In this work, phase-pure botallackite (Bo) (Cu-2(OH)(3)Br), a quasi-2D S = 1/2 anisotropic triangular spin-lattice is stabilized over 2D reduced graphene oxide (rGO) nanosheets via simple oxidation-reduction reaction chemistry. In comparison to polycrystalline Bo, such an anchoring resulted in the oriented growth of Bo crystallites in the Bo-rGO system. The Bo-rGO nanocomposite was found to be magnetically active with a Neel transition at 8.9 K, crossing over to possible XY anisotropy at similar to 5 K-as revealed by complementary dc and ac susceptibility measurements-an unprecedented observation in the field assigned to an interfacial effect. This work demonstrates the potential usage of nonmagnetic 2D functionalized graphene to significantly modulate the magnetic properties of 2D spin-lattices.

Five concomitant polymorphs of a green fluorescent protein chromophore (GFPc) analogue: understanding variations in photoluminescence with pi-stacking interactions - Mali, Bhupendra P.; Dash, Soumya Ranjan; Nikam, Shrikant B.; Puthuvakkal, Anisha; Vanka, Kumar; Manoj, Kochunnoonny; Gonnade, Rajesh G. (Acta Crystallographica Section B-Structural Science Crystal Engineering and Materials, 2020)
The synthetically modified green fluorescent protein chromophore analogue 3,4,5-trimethoxybenzylidene imidazolinone (1) yielded five polymorphs (I, II, III, IV, V) concomitantly irrespective of the solvent used for crystallization. The pentamorphic modification of 1 is solely due to the interplay of iso-energetic weak intermolecular interactions in molecular associations as well as the conformational flexibility offered by a C-C single bond, which connects the electron-deficient moiety imidazolinone with the electron-rich trimethoxybenzylidene group. A common structural feature observed in all the polymorphs is the formation of a `zero-dimensional' centrosymmetric dimeric unit through a short and linear C-H center dot center dot center dot O hydrogen bond engaging phenyl C-H and imidazolinone carbonyl oxygen. However, the networking of these dimeric units showed a subtle difference in all the polymorphs. The 2D isostructurality was observed between polymorphs I, II and III, while the other two polymorphs IV and V revealed only `zero-dimensional' isostructurality. The different fluorescence emissions of Form I (blue) and Forms II to V (yellow) were attributed to the differences in pi-stacking interactions. It shows that one can modulate the photophysical properties of these smart materials by slightly altering their crystal structure. Such an approach will aid in developing new multi-colour organic fluorescent materials of varying crystal structures for live-cell imaging and fluorescent sensing applications.
Keywords: green fluorescent protein; hydrogen bonds; isostructurality; photoluminescence; pi-stacking; Polymorphs

General and concise asymmetric synthesis of sphingosine, safingol and phytosphingosines via tethered aminohydroxylation (vol 8, pg 5074, 2010) - Kumar, Pradeep; Dubey, Abhishek; Puranik, Vedavati G. (Organic & Biomolecular Chemistry, 2020)

Generation of novelties in the genus Ocimum as a result of natural hybridization: a morphological, genetical and chemical appraisal - Gurav, Tanuja P.; Jayaramaiah, Ramesha H.; Punekar, Sachin A.; Dholakia, Bhushan B.; Giri, Ashok P. (Industrial Crops and Products, 2020)
The genus Ocimum is a boutique of a diverse set of specialized metabolites such as terpenoids and phenylpropanoids. Each Ocimum species and its cultivars represent a characteristic chemical profile. The present study explored the two interspecific Ocimum hybrids originating through a serendipitous natural cross between O. kilimandscharicum and O. basilicum. These two novel Ocimum hybrids exhibited intermediate morphological features of two parental species. Inter simple sequence repeats (ISSR) analysis and DNA barcoding with the plastid non-coding trnH-psbA intergenic spacer region reaffirmed unambiguous parental identification and differentiation of these natural hybrids from other available Ocimum species. Consequently, gas chromatographymass spectrometry-based metabolite profiling of two hybrids identified them as specific chemotypes with the presence of a unique blend of specialized metabolites from the parental species, which are either rich in terpenes or phenylpropanoids. Additionally, expression analysis of key genes from terpenoid and phenylpropanoid pathways corroborated with differential metabolite accumulation. Thus, these two Ocimum hybrids represented the novel chemotypes, which could be useful in commercial cultivation to produce novel essential oil and bioactive constituents. Further, the resulting metabolite diversity could have potential industrial applications in the areas of healthcare, bioremediation, and crop protection.
Keywords: Chemotype; DNA barcoding; Inter Simple Sequence Repeats; Interspecific hybrid; O. basilicum; O. kilimandscharicum; Ocimum

Geometrical isomerism directed electrochemical sensing - Kottaichamy, Alagar Raja; Begum, Shabbah; Devendrachari, Mruthyunjayachar Chattanahalli; Bhat, Zahid Manzoor; Thimmappa, Ravikumar; Kotresh, Harish Makri Nimbegondi; Vinod, Chathakudath Prabhakaran; Thotiyl, Musthafa Ottakam (Analytical Chemistry, 2020)
We report the independent role of isomerism of secondary sphere substituents over their nature, a factor often overlooked in molecular electrocatalysis pertaining to electrochemical sensing, by establishing that isomerism redefines the electronic structure at the catalytic reaction center via geometrical factors. UV-vis spectroscopy and X-ray photoelectron spectroscopy suggest that a substituent's isomerism in molecular catalysts conjoins molecular planarity and catalytic activation through competing field effects and resonance effects. As a classical example, we demonstrate the influence of isomerism of the -NO2 substituents for the electrocatalytic multi electron oxidation of As(III), a potentially important electrochemical pathway for water remediation and arsenic detection. The isomerism dependent oxidative activation of catalytic center leads to a nonprecious molecular catalyst capable for direct As(III) oxidation with an experimental detection limit close to WHO guidelines. This work opens up an unusual approach in analytical chemistry for developing various sensing platforms for challenging chemical and electrochemical reactions.

HDAC6 ZnF UBP as the modifier of tau structure and function - Balmik, Abhishek Ankur; Chidambaram, Hariharakrishnan; Dangi, Abha; Marelli, Udaya Kiran; Chinnathambi, Subashchandrabose (Biochemistry, 2020)
Histone deacetylase 6 is a class H histone deacetylase primarily present in the cytoplasm and involved in the regulation of various cellular functions. It consists of two catalytic deacetylase domains and a unique zinc finger ubiquitin binding protein domain, which sets it apart from other HDACs. HDAC6 is known to regulate cellular activities by modifying the function of microtubules, HSP90, and cortactin through deacetylation. Apart from the catalytic activity of HDAC6, it interacts with other proteins through either the SE14 domain or the ZnF UBP domain to modulate their functions. Here, we have studied the role of the HDAC6 ZnF UBP domain as a modifier of Tau aggregation by its direct interaction with the polyproline region/repeat region of Tau. Interaction of HDAC6 ZnF UBP with Tau was found to reduce the propensity of Tau to self-aggregate and to disaggregate preformed aggregates in a concentration-dependent manner and also bring about the conformational changes in Tau protein. The interaction of HDAC6 ZnF UBP with Tau results in its degradation, suggesting either proteolytic activity of HDAC6 ZnF UBP or its role in enhancing autoproteolysis of Tau.

Hierarchical nanoflower arrays of Co9S8-Ni3S2 on nickel foam: a highly efficient binder-free electrocatalyst for overall water splitting - Illathvalappil, Rajith; Walko, Priyanka S.; Kanheerampockil, Fayis; Bhat, Suresh K.; Devi, R. Nandini; Kurungot, Sreekumar (Chemistry-A European Journal, 2020)
Hydrogen production is vital for meeting future energy demands and managing environmental sustainability. Electrolysis of water is considered as the suitable method for H-2 generation in a carbon-free pathway. Herein, the synthesis of highly efficient Co9S8-Ni3S2 based hierarchical nanoflower arrays on nickel foam (NF) is explored through the one-pot hydrothermal method (Co9S8-Ni3S2/NF) for overall water splitting applications. The nanoflower arrays are self-supported on the NF without any binder, possessing the required porosity and structural characteristics. The obtained Co9S8-Ni3S2/NF displays high hydrogen evolution reaction (HER), as well as oxygen evolution reaction (OER), activities in 1 m KOH solution. The overpotentials exhibited by this system at 25 mA cm(-2) are nearly 277 and 102 mV for HER and OER, respectively, in 1 m KOH solution. Subsequently, the overall water splitting was performed in 1 m KOH solution by employing Co9S8-Ni3S2/NF as both the anode and cathode, where the system required only 1.49, 1.60, and 1.69 V to deliver the current densities of 10, 25, and 50 mA cm(-2), respectively. Comparison of the activity of Co9S8-Ni3S2/NF with the state-of-the-art Pt/C and RuO2 coated on NF displays an enhanced performance for Co9S8-Ni3S2/NF both in the half-cell as well as in the full cell, emphasizing the significance of the present work. The post analysis of the material after water electrolysis confirms that the surface Co(OH)(2) formed during the course of the reaction serves as the favorable active sites. Overall, the activity modulation achieved in the present case is attributed to the presence of the open-pore morphology of the as formed nanoflowers of Co9S8-Ni3S2 on NF and the simultaneous presence of the surface Co(OH)(2) along with the highly conducting Co9S8-Ni3S2 core, which facilitates the adsorption of the reactants and subsequently its conversion into the gaseous products during water electrolysis.
Keywords: cobalt sulfide; electrocatalysts; Hydrogen evolution; overall water splitting; oxygen evolution

Highly durable Li-ion battery anode from Fe3O4 nanoparticles embedded in nitrogen-doped porous carbon with improved rate capabilities - Deshmukh, Ashvini B.; Dwivedi, Pravin K.; Nalawade, Archana C.; Qureshi, Mohammed S.; Shelke, Manjusha V. (Journal of Materials Science, 2020)
For next generation, lithium-ion batteries (LIBs) developing high capacity anode materials are crucial with increasing demand of large-scale application. Conversion-type anode materials are promising if stable cycling behavior could be achieved. In this work, a nitrogen-doped porous carbon-Fe3O4(NPC-Fe3O4) nanocomposite is synthesized via a simple and scalable approach. Composite is prepared by pyrolysis of polymer silica hybrid PolyHIPE (high internal phase emulsion) into NPC, and Fe3O4 nanoparticles (NPs) are anchored on its surface via hydrothermal synthesis. As-prepared NPC-Fe3O4 nanocomposite delivers high reversible capacity of around 1001 mAhg(-1)at 0.1 Ag-1 current density and rate capabilities and displays excellent cycling stability as high as 95% capacity retention even after 400 cycles. Superior electrochemical performance of NPC-Fe3O4 is attributed to the hierarchical porous structure and nitrogen doping of carbon which shorten the diffusion path of Li+ and provide ample space to prevent aggregation of Fe3O nanoparticles. [GRAPHICS] .

High-throughput metabolomic and transcriptomic analyses vet the potential route of cerpegin biosynthesis in two varieties of Ceropegia bulbosa Roxb. - Gharat, Sachin A.; Shinde, Balkrishna A.; Mule, Ravindra D.; Punekar, Sachin A.; Dholakia, Bhushan B.; Jayaramaiah, Ramesha H.; Ramaswamy, Gopalakrishna; Giri, Ashok P. (Planta, 2020)
Ceropegia bulbosa is an important medicinal plant, used in the treatment of various ailments including diarrhea, dysentery, and syphilis. This is primarily attributed to the presence of pharmaceutically active secondary metabolites, especially cerpegin. As this plant belongs to an endemic threatened category, genomic resources are not available hampering exploration on the molecular basis of cerpegin accumulation till now. Therefore, we undertook high-throughput metabolomic and transcriptomic analyses using different tissues from two varieties namely, C. bulbosa var. bulbosa and C. bulbosa var. lushii. Metabolomic analysis revealed spatial and differential accumulation of various metabolites. We chemically synthesized and characterized the cerpegin and its derivatives by liquid chromatography tandem-mass spectrometry (LC-MS/MS). Importantly, these comparisons suggested the presence of cerpegin and 5-allyl cerpegin in all C. bulbosa tissues. Further, de novo transcriptome analysis indicated the presence of significant transcripts for secondary metabolic pathways through the Kyoto encyclopedia of genes and genomes database. Tissue-specific profiling of transcripts and metabolites showed a significant correlation, suggesting the intricate mechanism of cerpegin biosynthesis. The expression of potential candidate genes from the proposed cerpegin biosynthetic pathway was further validated by qRT-PCR and NanoString nCounter. Overall, our findings propose a potential route of cerpegin biosynthesis. Identified transcripts and metabolites have built a foundation as new molecular resources that could facilitate future research on biosynthesis, regulation, and engineering of cerpegin or other important metabolites in such non-model plants.
Keywords: 5-Allyl cerpegin; Ceropegia; Cerpegin; LC-MS; metabolite; Transcriptome

Identification and expression analysis of miRNAs and elucidation of their role in salt tolerance in rice varieties susceptible and tolerant to salinity - Parmar, Shaifaly; Gharat, Sachin Ashruba; Tagirasa, Ravichandra; Chandra, Tilak; Behera, Lambodar; Dash, Sushant Kumar; Shaw, Birendra Prasad (PloS One, 2020)
Soil salinization is a serious problem for cultivation of rice, as among cereals rice is the most salt sensitive crop, and more than 40% of the total agricultural land amounting to approximately 80 million ha the world over is salt affected. Salinity affects a plant in a varieties of ways, including ion toxicity, osmotic stress and oxidative damage. Since miRNAs occupy the top place in biochemical events determining a trait, understanding their role in salt tolerance is highly desirable, which may allow introduction of the trait in the rice cultivars of choice through biotechnological interventions. High throughput sequencing of sRNAs in the root and shoot tissues of the seedlings of the control and NaCl treated Pokkali, a salt-tolerant rice variety, identified 75 conserved miRNAs and mapped 200 sRNAs to the rice genome as novel miRNAs. Expression of nine novel miRNAs and two conserved miRNAs were confirmed by Northern blotting. Several of both conserved and novel miRNAs that expressed differentially in root and/or shoot tissues targeted transcription factors like AP2/EREBP domain protein, ARF, NAC, MYB, NF-YA, HD-Zip III, TCP and SBP reported to be involved in salt tolerance or in abiotic stress tolerance in general. Most of the novel miRNAs expressed in the salt tolerant wild rice Oryza coarctata, suggesting conservation of miRNAs in taxonomically related species. One of the novel miRNAs, osa-miR12477, also targeted L- upon salt treatment, which was confirmed by DAB staining. Thus, salt tolerance might involve miRNA-mediated regulation of 1) cellular abundance of the hormone signaling components like EREBP and ARF, 2) synthesis of abiotic stress related transcription factors, and 3) antioxidative component like LAO for mitigation of oxidative damage. The study clearly indicated importance of osa-miR12477 regulated expression of LAO in salt tolerance in the plant.

Imines as acceptors and donors in N-heterocyclic carbene (NHC) organocatalysis - Das, Tamal Kanti; Biju, Akkattu T. (Chemical Communications, 2020)
The synthetic potential of imines as electrophiles or as a source of nucleophilic coupling partner in N-heterocyclic carbene (NHC) catalysis for the synthesis of various nitrogen heterocycles and functionalized amines is highlighted in this Feature Article. Electrophilic imines are suitable candidates for intercepting the NHC-derived acyl anions, homoenolate equivalents, and (di)enolates for the synthesis of alpha-amino ketones and a variety of lactam derivatives. Moreover, enamines generated from imines bearing alpha-hydrogen could be trapped with alpha,beta-unsaturated acylazoliums for the synthesis of functionalized dihydropyridinones. NHCs are also useful for the umpolung of imines for the generation of aza-Breslow intermediates thus leading to the synthesis of indoles, quinolines, dihydroquinoxalinesetc.A concise account of the diverse reactivity of imines in NHC catalysis has been presented.

In situ cross-linked nonaqueous polymer electrolyte for zinc-metal polymer batteries and hybrid supercapacitors - Vijayakumar, Vidyanand; Ghosh, Meena; Kurian, Maria; Torris, Arun; Dilwale, Swati; Badiger, V. Manohar; Winter, Martin; Nair, Jijeesh Ravi; Kurungot, Sreekumar (Small, 2020)
This work reports the facile synthesis of nonaqueous zinc-ion conducting polymer electrolyte (ZIP) membranes using an ultraviolet (UV)-light-induced photopolymerization technique, with room temperature (RT) ionic conductivity values in the order of 10(-3)S cm(-1). The ZIP membranes demonstrate excellent physicochemical and electrochemical properties, including an electrochemical stability window of >2.4 V versus Zn|Zn(2+)and dendrite-free plating/stripping processes in symmetric Zn||Zn cells. Besides, a UV-polymerization-assisted in situ process is developed to produce ZIP (abbreviated i-ZIP), which is adopted for the first time to fabricate a nonaqueous zinc-metal polymer battery (ZMPB; VOPO4|i-ZIP|Zn) and zinc-metal hybrid polymer supercapacitor (ZMPS; activated carbon|i-ZIP|Zn) cells. The VOPO(4)cathode employed in ZMPB possesses a layered morphology, exhibiting a high average operating voltage of approximate to 1.2 V. As compared to the conventional polymer cell assembling approach using the ex situ process, the in situ process is simple and it enhances the overall electrochemical performance, which enables the widespread intrusion of ZMPBs and ZMPSs into the application domain. Indeed, considering the promising aspects of the proposed ZIP and its easy processability, this work opens up a new direction for the emergence of the zinc-based energy storage technologies.
Keywords: nonaqueous electrolytes; polymer electrolytes; postlithium batteries; Supercapacitors; zinc-metal batteries

Inhibition of quorum sensing, motility and biofilm formation ofpseudomonas aeruginosaby copper oxide nanostructures - Desai, Dnyanada G.; Swarali, H.; Navale, Govinda R.; Prabhune, A.; Late, Dattatray J.; Dharne, Mahesh S.; Walke, Pravin S. (Journal of Cluster Science, 2020)
Quorum sensing (QS) is the communication between bacterial cells governed by their population density and regulated by the genes controlling virulence factors and biofilm formation. Multiple mechanisms of biofilms are resistive to antimicrobial chemotherapy; therefore novel strategies are required to overcome its limitations. Here, we report the effect of various copper oxide nanostructures (CuO-NSs) on quorum sensing inhibition. The two-dimensional CuO-NSs such as interlaced nanodiscs, nanodiscs and leaf-shaped nanosheets are prepared via a simple chemical method. The Quorum sensing inhibition (QSI) activity of all the CuO-NS are examined using reporter strainChromobacterium violaceumCV026 andEscherichia colipSB1142. We found that the CuO-interlaced nanodisc structures exhibit better QSI activity than nanodiscs and leaf-shaped sheets. The interlaced nanodisc structures are inhibited various long-chainN-acyl homoserine lactones (AHLs) mediated QS individually and confirmed by other QS-associated phenomena forPseudomonas aeruginosa, including biofilm inhibition, inhibition of virulence factors such as pyocyanin, protease production and swarming motility. Thus QSI activity of CuO-NSs is solely dependent on specific shape offering large surface area and more active sites. The CuO-NS is effective quorum sensing inhibitors, which has potential clinical applications in the management ofP. aeruginosaassociated infections.
Keywords: aeruginosa; Biofilm; Nanostructures; P; quorum sensing; Virulence factors

Integrating structurally perfect s=1/2 kagome-lattice with reduced graphene oxide - Gupta, Kriti; Dadwal, Arun; Ninawe, Pranay; Joy, Pattayil A.; Ballav, Nirmalya (Journal of Physical Chemistry C, 2020)
S = 1/2 kagome-lattice hydroxychlorides are promising candidates for realizing the elusive quantum spin liquid (QSL) state. Herbertsmithite [Cu3Zn(OH)(6)Cl-2], a naturally occurring hydroxychloride mineral from the class of atacamites {[Cu-4-xMx(OH)(6)X-2] where M = Zn, Cu, Co, Ni and X = Cl, Br, I}, is one of the most appealing systems to study the QSL state because of the presence of a structurally perfect S = 1/2 kagome-lattice. It is an electrical insulator. However, realizing phase-pure herbertsmithite without imposing harsh reaction conditions remained synthetically challenging. In this work, for the first time, we have synthesized phase-pure herbertsmithite as well as its structural analogue paratacamite, [ZnxCu4-x(OH)(6)Cl-2; 0.33 = x < 1], at ambient reaction conditions. Furthermore, taking graphene oxide (GO) as an additional precursor in the reaction mixture, we have successfully integrated phase-pure crystallites of herbertsmithite (H) and paratacamite (P) with nanosheets of semiconducting and diamagnetic reduced graphene oxide (rGO) by in situ oxidation-reduction reaction. The isolated H-rGO and P-rGO systems were found to be magnetic semiconductors inheriting strong spin frustration from H and P, and semiconductivity from rGO. The H-rGO system in particular exhibited negative Seebeck coefficient (n-type semiconductor) with a thermoelectric power factor of 0.1 mu W center dot m(-1)center dot K-2 at 400 K. We anticipate the simple chemical principles outlined in this work to be useful for studying a variety of complex QSLs including electron doping. Also, semiconducting and rather unconventional materials of such metal oxochlorides with rGO isolated here need further exploration in view of thermoelectric applications.

Interaction of Tau with the chemokine receptor, CX3CR1 and its effect on microglial activation, migration and proliferation - Chidambaram, Hariharakrishnan; Das, Rashmi; Chinnathambi, Subashchandrabose (Cell and Bioscience, 2020)
Alzheimer's disease (AD) is a neurodegenerative disease that leads to progressive loss of memory and dementia. The pathological hallmarks of AD include extracellular accumulation of amyloid-beta peptides forming senile plaques and intracellular accumulation of Tau oligomers and filamentous species. Tau is a microtubule-binding protein that stabilizes tubulin to form microtubules under physiological condition. In AD/ pathological condition, Tau detaches from microtubules and aggregates to form oligomers of different sizes and filamentous species such as paired helical filaments. Microglia are the resident brain macrophages that are involved in the phagocytosis of microbes, cellular debris, misfolded and aggregated proteins. Chemokine receptor, CX3CR1 is mostly expressed on microglia and is involved in maintaining the microglia in a quiescent state by binding to its ligand, fractalkine (CX3CL1), which is expressed in neurons as both soluble or membrane-bound state. Hence, under physiological conditions, the CX3CR1/CX3CL1 axis plays a significant role in maintaining the central nervous system (CNS) homeostasis. Further, CX3CR1/CX3CL1 signalling is involved in the synthesis of anti-inflammatory cytokines and also has a significant role in cytoskeletal rearrangement, migration, apoptosis and proliferation. In AD brain, the expression level of fractalkine is reduced, and hence Tau competes to interact with its receptor, CX3CR1. In microglia, phagocytosis and internalization of extracellular Tau species occurs in the presence of a chemokine receptor, CX3CR1 which binds directly to Tau and promotes its internalization. In this review, the pathophysiological roles of CX3CR1/fractalkine signalling in microglia and neurons at different stages of Alzheimer's disease and the possible role of CX3CR1/Tau signalling has been widely discussed.
Keywords: Alzheimer's disease; CX3CR1 receptor; Fractalkine; microglia; Neuron; Tau

Isolation of potent alpha-glucosidase inhibitor from a novel marine bacterium Arthrobacter enclensis - Mawlankar, Rahul B.; Dharne, Mahesh S.; Dastager, Syed G. (SN Applied Sciences, 2020)
Alpha-glucosidases are involved in the hydrolyzation of glycosidic bond of di- or oligo-saccharides into mono-saccharides, thus help in the breakdown and absorption of sugars. Inhibition of alpha-glucosidases by inhibitors tend to slow break down and release of sugars into the bloodstream and can be used as therapeutic agents in the treatment of diabetes and obesity. In particular, some of the inhibitors are used in the treatment mainly acarbose, voglibose, and miglitol. In this study, we have reported the alpha-glucosidase inhibitory compound from a newly described marine bacterium Arthrobacter enclensis. The purified compound from A. enclensis was identified by HPLC, and further FTIR and tandem mass spectrometry (MS/MS) methods. The purified compound was annotated and identified by a Web tool CFM-ID (Competitive Fragmentation Modeling for Metabolite Identification). From analysis it was found that the compound showed high similarity with acarbose which is a C7N aminocyclitol compound. Further, we analyze the draft genome of A. enclensis using anti-SMASH. We observed that it matches the homology with biosynthetic gene cluster of acarviostatin and acarbose with 11% and 7% respectively. We demonstrated that, the purified compound from A. enclensis shows the inhibitory activity against alpha-glucosidase with an IC50 value of 500 ± 0.142 μg/ml as compared to standard acarbose, which showed an IC50 value of 200 ± 0.012 μg/ml. This result suggests that A. enclensis has a tendency to produce a C7N aminocyclitol like molecule which matched to acarbose and it uses different biosynthetic gene cluster for the synthesis of C7N aminocyclitol like molecule, which can be further used for the production and treatment purpose.

Kinetics of hydroformylation of camphene using rhodium-phosphite catalyst - Pagar, Nitin S.; Rajurkar, Kalpendra B.; Deshpande, Raj M. (International Journal of Chemical Kinetics, 2020)
Kinetics of hydroformylation of camphene was investigated in the presence of [Rh(CO)(2)(acac)]/P(OPh)(3) catalyst in a temperature range of 363-383 K. The influence of parameters such as stirring speed, camphene, catalyst, ligand concentrations, and partial pressures of H-2 and CO on the activity and selectivity of the catalyst has been studied. The rate showed a first-order dependence with respect to catalyst and camphene concentrations. The effect of partial pressure of hydrogen showed fractional order dependence. The plots of rate versus excess ligand, that is, (P(OPh)(3)) concentration and rate versus CO partial pressure passed through maxima and showed typical substrate/ligand inhibited kinetics. An empirical rate equation has been proposed and found to be in good agreement with the observed rate data. The kinetic parameters and activation energy were also evaluated.
Keywords: camphene; homogeneous; Hydroformylation; kinetics; rhodium-phosphite

Magnetism in bimetallic NiII-CoII coordination polymer - Gupta, Kriti; Dadwal, Arun; Joy, Pattayil; Ballav, Nirmalya (AIP Conference Proceedings, 2020)
Co-BDC ([Co2(OH)2BDC], H2BDC = 1,4-benzenedicarboxylic acid) is known to possess metamagnetism originating from the antiparallel spins and high magneto crystalline anisotropy of Co(II).1 Herein, we have introduced a bimetallic concept by incorporating Ni(II) along with Co(II) in the same coordination polymer to modulate the magneto crystalline anisotropy in the lattice which in turn, affects the overall magnetic response of the coordination polymer. The Curie-Weiss equation fit suggested antiparallel arrangement of the spins (θ ≈ -62.5 K) of Ni(II) and Co(II) arranged in alternate fashion. The cusp in magnetization was observed at 7 K (Tc) with a significant coercive field of ∼750 Oe at 5 K.

Mechanistic aspects of methanol electro-oxidation reaction through cyclic voltammetry: is it correct to blame carbon monoxide for catalyst poisoning? - Deshpande, Pooja S.; Chaudhari, Vijay R.; Prasad, Bhagavatula L. V. (Energy Technology, 2020)
The mechanism of the methanol oxidation reaction is revisited using systematic cyclic voltammetric studies. These studies clearly indicate that the peak during the cathodic scan belongs mainly to electro-oxidation of the carbon monoxide, and that only a fraction of this carbon monoxide remains adsorbed on the electrode, contrary to what previous reports suggested. More details can be found in article number by Bhagavatula L. V. Prasad and co-workers.
Keywords: carbon monoxide; cyclic voltammetry; electrocatalysts; electrode poisoning; Methanol oxidation

Melatonin interacts with repeat domain of Tau to mediate disaggregation of paired helical filaments - Balmik, Abhishek Ankur; Das, Rashmi; Dangi, Abha; Gorantla, Nalini Vijay; Marelli, Udaya Kiran; Chinnathambi, Subashchandrabose (Biochimica Et Biophysica Acta-General Subjects, 2020)
Tau is the major neuronal protein involved in the stabilization of microtubule assembly. In Alzheimer's disease, Tau self-assembles to form intracellular protein aggregates which are toxic to cells. Various methods have been tried and tested to restrain the aggregation of Tau. Most of the agents tested for this purpose have limitations in their effectiveness and availability to neuronal cells. We have tested melatonin, a neurohormone secreted by pineal gland and a well-known anti-oxidant, for its ability to interact with the repeat domain of Tau using ITC and NMR. In aggregation inhibition and disaggregation studies of repeat Tau, melatonin was found to modulate the aggregation propensity of repeat Tau at a concentration of 5000 mu M and was more effective in dissolving preformed aggregates rather than acting as an aggregation inhibitor. However, there were no major conformational changes in Tau in presence of melatonin as observed by CD spectroscopy. On the basis of our findings, we are proposing a mechanism by which melatonin can interact with the repeat domain of Tau and exhibit its disaggregation effect.
Keywords: Alzheimer's disease; Disaggregation; melatonin; Paired helical filaments; tau protein; Tauopathies

Melatonin reduces GSK3 beta-mediated tau phosphorylation, enhances Nrf2 nuclear translocation and anti-inflammation - Das, Rashmi; Balmik, Abhishek Ankur; Chinnathambi, Subashchandrabose (ASN Neuro, 2020)
Alzheimer's disease is a neuropathological condition with abnormal accumulation of extracellular Amyloid-beta plaques and intracellular neurofibrillary tangles of Microtubule-associated protein Tau (Tau) in the brain. In pathological conditions, Tau undergoes post-translational modifications such as hyperphosphorylation by the activity of cellular kinases, which eventually leads to protein aggregation in neurons. Melatonin is a neuro-hormone that is mainly secreted from the pineal gland and functions to modulate the cellular kinases. In our study, we have checked the neuroprotective function of Melatonin by MTT and LDH assay, where Melatonin inhibited the Tau aggregates-mediated cytotoxicity and membrane leakage in Neuro2A cells. The potency of Melatonin has also been studied for the quenching of intracellular reactive oxygen species level by DCFDA assay and caspase 3 activity. Melatonin was shown to reduce the GSK3 beta mRNA and subsequent protein level as well as the phospho-Tau level (pThr181 and pThr212-pSer214) in okadaic acid-induced Neuro2A cells, as observed by western blot and immunofluorescence assay. Further, Melatonin has increased the cellular Nrf2 level and its nuclear translocation as an oxidative stress response in Tauopathy. The Melatonin was found to induce pro- and anti-inflammatory cytokines levels in N9 microglia. The mRNA level of cellular kinases such as as-GSK3 beta, MAPK were also studied by qRT-PCR assay in Tau-exposed N9 and Neuro2A cells. The immunomodulatory effect of Melatonin was evident as it induced IL-10 and TGF-beta cytokine levels and activated MAP3K level in Tau-exposed microglia and neurons, respectively. Melatonin also downregulated the mRNA level of pro-inflammatory markers, IL-1 beta and Cyclooxygenase-2 in N9 microglia. Together, these findings suggest that Melatonin remediated the cytokine profile of Tau-exposed microglia, reduced Tau hyperphosphorylation by downregulating GSK3 beta level, and alleviated oxidative stress via Nrf2 nuclear translocation.
Keywords: Alzheimer’ Anti-inflammatory; GSK3β melatonin; microglia; neurodegeneration; Nrf2; s disease; Tau hyperphosphorylation

Metagenome sequencing to unveil microbial community composition and prevalence of antibiotic and metal resistance genes in hypersaline and hyperalkaline Lonar Lake, India - Chakraborty, Jaya; Sapkale, Vibhavari; Shah, Manan; Rajput, Vinay; Mehetre, Gajanan; Agawane, Sachin; Kamble, Sanjay; Dharne, Mahesh (Ecological Indicators, 2020)
Lonar Lake (India) is a hyperalkaline and hypersaline soda lake encompassing unique microbial composition and functions. This ecosystem has not been explored for taxonomic diversity and functional aspects (with emphasis on antibiotic and metal resistance genes) using whole metagenome sequencing for multiple years. Bacterial diversity analysis during year 2013, 2016, and 2018 depicted differences in the dominance of Proteobacteria, Firmicutes and Bacteroidetes. For archaeal diversity, a similar pattern persisted with higher abundance of Euryarchaeota. Functional metagenome analyses, indicated presence of antibiotic resistance gene (ARG) and metal resistance gene (MRG) profiles in the lake. A wider continuum of resistance genes with dominant ARG types as multidrug resistance efflux pumps and beta-lactams were also observed. The lake resistome demonstrated fluoroquinolone and acriflavine resistance genes indicating sewage water contamination in the lake. The MRGs linked with resistance to toxic metals (arsenic, cobalt, cadmium, copper, and zinc) and cation efflux protein CusA and cobalt-zinc-cadmium resistance protein revealed metal contamination. This study could be a baseline for understanding prevalence of antibiotic and metal resistance mechanisms resulting from various anthropogenic activities nearby lake, and find integrated approaches for conservation of the precious Lonar Lake ecosystem.
Keywords: Archaeal diversity; ARGs; Bacterial diversity; Illumina sequencing; Lonar lake; MRGs

Mizoroki-Heck reaction of 1,2-disubstituted aryl alkenes: variables of synthesis, solvent and ligand modulation of reactivity - Bangar, Pronnoy G.; Jawalkar, Priyanka R.; Dumbre, Swapnil R.; Raut, Pallavi K.; Patil, Dharmaraj J.; Tv, Neethu; Sudhakaran, Shana; Iyer, Suresh (Synthetic Communications, 2020)
Reaction of aryl iodides with 1,2-disubstituted aryl alkenes in the presence of TBABr/TBACl gave high yields of the Mizoroki-Heck product. Phosphine ligands were used for the modulation of reactivity and stereoselectivity, for the reaction of 4-iodoanisole with cinnamaldehyde. tert-Bu3P.HBF(4)gave the highest E:Z ratio of 1:0.08. The use of PEG-200 and PEG-400 as solvent could activate the reaction of aryl iodides with various 1,2-disubstituetd aryl alkenes.
Keywords: 12-Disubstituted aryl alkenes; 400; ligand effect; Mizoroki-Heck reaction; PEG 200; TBABr

Molecular networking and whole-genome analysis aid discovery of an angucycline that inactivates mTORC1/C2 and induces programmed cell death - Dan, Vipin Mohan; Vinodh, J. S.; Sandesh, C. J.; Sanawar, Rahul; Lekshmi, Asha; Kumar, R. Ajay; Kumar, T. R. Santhosh; Marelli, Uday Kiran; Dastager, Syed G.; Pillai, M. Radhakrishna (ACS Chemical Biology, 2020)
Rediscovery of known compounds and time consumed in identification, especially high molecular weight compounds with complex structure, have let down interest in drug discovery. In this study, whole-genome analysis of microbe and Global Natural Products Social (GNPS) molecular networking helped in initial understanding of possible compounds produced by the microbe. Genome data revealed 10 biosythethic gene clusters that encode for secondary metabolites with anticancer potential. NMR analysis of the pure compound revealed the presence of a four-ringed benz[a]anthracene, thus confirming angucycline; molecular networking further confirmed production of this class of compounds. The type II polyketide synthase gene identified in the microbial genome was matched with the urdamycin duster by BLAST analysis. This information led to ease in identification of urdamycin E and a novel natural derivative, urdamycin V, purified from Streptomyces sp. OA293. Urdamycin E (Urd E) induced apoptosis and autophagy in cancer cell lines. Urd E exerted anticancer action through inactivation of the mTOR complex by preventing phosphorylation at Ser 2448 and Ser 2481 of mTORC1 and mTORC2, respectively. Significant reduction in phosphorylation of the major downstream regulators of both mTORC1 (p70s6k and 4e-bp1) and mTORC2 (Akt) were observed, thus further confirming complete inhibition of the mTOR pathway. Urd E presents itself as a novel mTOR inhibitor that employs a novel mechanism in mTOR pathway inhibition.

Morphological evolution of two-dimensional porous hexagonal trimesic acid framework - Tothadi, Srinu; Koner, Kalipada; Dey, Kaushik; Addicoat, Matthew; Banerjee, Rahul (ACS Applied Materials & Interfaces, 2020)
Hexagonal single crystal structure (Form II) of trimesic acid (TMA) has been isolated by dissolving the interpenetrated Form I of TMA in tetrahydrofuran. Form II (hexagonal) was converted to Form I (interpenetrated) at room temperature through some intermediate structures. A detailed time-dependent FESEM study shows that the external morphology of Form II (hexagonal) is a hollow hexagonal tube that mimics its crystal structure. The block-shaped (morphology) of Form I (interpenetrated) was converted to the hollow hexagonal tube through some intermediate morphologies which are corresponding to particular crystal structures. Here, we have established a strong correlation between crystal structures with the morphology. These hollow tubes have been employed for Rhodamine B dye adsorption studies and showed an uptake of 82%, much more significant than Form I (interpenetrated) (39%) due to the presence of a pore channel in the crystal structure.
Keywords: dye adsorption; hollow hexagonal rod; hydrogen-bonded organic framework; morphology evaluation; trimesic acid

Naftopidil molecular salts with improved dissolution and permeation - Mannava, M. K. Chaitanya; Dandela, Rambabu; Tothadi, Srinu; Solomon, K. Anand; Nangia, Ashwini K. (Crystal Growth & Design, 2020)
Naftopidil (NFPD) is a alpha 1 adrenoceptor antagonist drug. Low solubility and low permeability are the major drawbacks of this drug. The synthesis of multicomponent crystalline forms of this amine functional group drug with carboxylic acid coformers, both achiral and chiral acids, provides a solution to improve its solubility as well as permeability. Nine molecular salts were crystallized by liquid-assisted grinding followed by isothermal crystallization. Single-crystal X-ray diffraction analysis of the molecular salts showed that the structures are stabilized by strong N-H center dot center dot center dot O and O-H center dot center dot center dot O and weak C-H center dot center dot center dot O hydrogen bonds in the solid state. The bulk phase purity of new solid forms was confirmed by powder X-ray diffraction (PXRD), and the crystalline products were further characterized by IR spectroscopy and thermal analytical techniques (differential scanning calorimetry). The molecular salts exhibit superior dissolution rates compared to pure NFPD. However, during dissolution, NFPD showed decrease in concentration after 60 min for all salts due to precipitation. The supersaturation occurred due to salt disproportionation, which generates insoluble NFPD, as confirmed by PXRD of the residue. The salts reach high saturation concentration before 60 min, which is indicative of immediate release formulation to achieve fast onset of therapeutic activity. Moreover, the salts exhibit high saturation in phosphate buffer saline media and improved permeability compared to the pure drug. Finally, the D,L-malic acid racemate of NFPD shows enhanced dissolution and permeability compared to all other salts and pure NFPD.

Nanoparticle size-fractionation through self-standing porous covalent organic framework films - Dey, Kaushik; Kunjattu, Shebeeb H.; Chahande, Anurag M.; Banerjee, Rahul (Angewandte Chemie-International Edition, 2020)
Covalent organic frameworks (COFs) have attracted attention due to their ordered pores leading to important industrial applications like storage and separation. Combined with their modular synthesis and pore engineering, COFs could become ideal candidates for nanoseparations. However, the fabrication of these microcrystalline powders as continuous, crack-free, robust films remains a challenge. Herein, we report a simple, slow annealing strategy to construct centimeter-scale COF films (Tp-Azo and Tp-TTA) with micrometer thickness. The as-synthesized films are porous (SA(BET)=2033 m(2) g(-1) for Tp-Azo) and chemically stable. These COFs have distinct size cut-offs (ca. 2.7 and ca. 1.6 nm for Tp-Azo and Tp-TTA, respectively), which allow the size-selective separation of gold nanoparticles. Unlike, other conventional membranes, the durable structure of the COF films allow for excellent recyclability (up to 4 consecutive cycles) and easy recovery of the gold nanoparticles from the solution.
Keywords: covalent organic frameworks; films; nanofilter; Nanoparticles; size-selective separation

Nanoscale interplay of membrane composition and amyloid self-assembly - Menon, Sneha; Sengupta, Neelanjana; Das, Payel (Journal of Physical Chemistry B, 2020)
Cell membranes are complex assemblies of lipids and proteins exhibiting lipid compositional heterogeneity between the inner and outer leaflets of the bilayer. Aberrant protein aggregation, implicated in a number of neurodegenerative diseases including Alzheimer's, is known to result in both extracellular and intracellular deposits with divergent pathophysiological effects. Mounting evidence substantiates membrane-mediated amyloid effects and indicates membrane composition, particularly gangliosides, as a plausible factor influencing the fibrillation process. By employing exhaustive molecular dynamics simulations using a coarse-grained model, we probed the assembly behavior of amyloidogenic A beta(12-28) peptides on the chemically heterogeneous extracellular (outer) and cytosolic (inner) leaflets of a mammalian plasma membrane. Our results indicate that the compositional nature of the membrane has a crucial impact on the peptide self-assembly. Peptide oligomerization is hindered on the outer leaflet relative to the inner leaflet due to a competition between interpeptide and peptide-membrane interactions, resulting in higher population of smaller oligomers. The weaker associations among peptides on the outer membrane can be attributed to the favorable interactions of the peptides with gangliosides (GM) that characterize the extracellular membrane. At a higher peptide:GM ratio, we observe enhanced nanoclustering of GM lipids mediated by preferential GM-A beta binding. Interaction between peptide and GM further impacts local membrane curvature; there is a concomitant loss in membrane concavity due to looser GM packing. Our simulations provide molecular insights into the role of membrane composition on A beta aggregation and lend credence to earlier reports of ganglioside-mediated A beta aggregation in the outer membrane. We also demonstrate the effects of local peptide assemblies on the membrane structure and dynamics.

New TBAF complex, highly stable, facile and selective source for nucleophilic fluorination: applications in batch and flow chemistry - Said, Madhukar S.; Khonde, Nilesh S.; Thorat, Meghana N.; Atapalkar, Ranjit S.; Kulkarni, Amol A.; Gajbhiye, Jayant; Dastager, Syed G. (Asian Journal of Organic Chemistry, 2020)
Natural polysaccharides supported tetrabutylammonium fluoride (TBAF) complexes are prepared and found to be highly stable and selective fluoride source for well-renowned nucleophilic (SN2 type) fluorination reactions for the first time. Bacterial cellulose, plant cellulose, pectin, and starch derived TBAF complexes are synthesized, characterized (using SEM, TEM, and NMR techniques) and studied for their stability and reactivity. Heterogeneous bacterial cellulose-TBAF complex (NBu4(Bac-cell-OH)F) 1 was found to be highly stable and non-hygroscopic among all complexes, which gave high yields of fluorinated products in multi-gram scale in shorter reaction time. The primarily developed batch protocol was extended to solid-solid continuous flow reaction using an in-house built screw reactor, which furnished products in a few seconds of residence time (tR=20-25 sec) and excellent yields.
Keywords: Flow synthesis; fluorination; green chemistry; Sustainable Chemistry

N-heterocyclic carbene catalysis exploiting oxidative imine umpolung for the generation of imidoyl azoliums - Das, Tamal Kanti; Madica, Krishnaprasad; Krishnan, Jagadeesh; Marelli, Udaya Kiran; Biju, Akkattu T. (Journal of Organic Chemistry, 2020)
Although NHC-catalyzed umpolung of imines are known, the related reactions under oxidative conditions are limited. Described herein is the two-step process involving the initial formation of aldimines from the corresponding aldehydes and 2-amino benzyl alcohols followed by NHC-catalyzed cyclization proceeding via the imidoyl azoliums under oxidative conditions. The reaction allowed the synthesis of trifluoromethylated 3,1-benzoxazines in good yields and broad scope. The role of NHC in the intramolecular cyclization and preliminary mechanistic experiments are also provided.

N-heterocyclic carbene (NHC)-catalyzed transformations for the synthesis of heterocycles - Das, Tamal Kanti; Biju, Akkattu T. (Progress in Heterocyclic Chemistry, 2020)
N-heterocyclic carbene (NHC)-based organocatalysis has been widely used for unconventional access to various target molecules. The use of chiral NHCs in the process results in the enantioselective synthesis of various heterocycles. The underlying principle of many of the NHC-catalyzed reactions is the remarkable ability of NHCs to reverse the normal mode of reactivity of aldehydes (umpolung). NHCs can catalyze transformations proceeding via the umpolung or nonumpolung mode for the synthesis of various functionalized molecules. The recent advances in the application of NHCs for the synthesis of various heterocyclic compounds are highlighted in this chapter.
Keywords: aldehyde umpolung; Aldimine umpolung; benzoin reaction; Breslow intermediates; Enantioselective synthesis; Heterocyclic synthesis; N-Heterocyclic carbene; Stetter reaction

Novel cilengitide-based cyclic RGD peptides as alpha nu beta(3) integrin inhibitors - Meena, Chhuttan L.; Singh, Dharmendra; Weinmueller, Michael; Reichart, Florian; Dangi, Abha; Marelli, Udaya Kiran; Zahler, Stefan; Sanjayan, Gangadhar J. (Bioorganic & Medicinal Chemistry Letters, 2020)
In this letter, we report a series of five new RGD-containing cyclic peptides as potent inhibitors to alpha nu beta(3) integrin protein. We have incorporated various unnatural lipophilic amino acids into the cyclic RGD framework of cilengitide, which is selective for alpha nu beta(3) integrin. All the newly synthesized cyclic peptides were evaluated in vitro solid phase binding assay and investigated for their binding behaviour towards integrin subtypes. All the cyclic peptides were synthesized in excellent yield following solution-phase coupling strategy. The cyclic RGD peptides 1a-e exhibited IC50 of 9.9, 5.5, 72, 11 and 3.3 nM, respectively, towards a alpha nu beta(3) integrin protein. This finding offers further opportunities for the introduction unusual amino acids into the cyclic peptide framework of cilengitide.
Keywords: Anticancer drugs; Cilengitide; Integrins; RGD cyclicpeptides

One pot hydrogenation of furfural to 2-methyl tetrahydrofuran over supported mono- and Bi-metallic catalysts - Date, Nandan S.; Hengne, Amol M.; Huang, K. -W.; Chikate, Rajeev C.; Rode, Chandrashekhar V. (ChemistrySelect, 2020)
2-Methyltetrahydrofuran is a valuable commercial product that can be obtained by direct hydrogenation of furfural. In the present study, among several carbon supported bimetallic Ir-Ni catalysts with different loadings screened, 4% Ir-4% Ni/C catalyst showed excellent activity in terms of direct conversion (99%) to 2-MeTHF with a maximum selectivity of similar to 74% at 220 degrees C and 750 psig, suppressing the formation of side chain as well as ring opening products. The catalytic activity was found to be mainly affected by catalyst preparation methods, metal loadings, surface composition, temperature, pressure and catalyst loading. HR-TEM and STEM revealed well dispersed Ir-Ni NPs having the particle sizes in the range of 2 to 5 nm. Different phases of Ir i. e. Ir degrees and IrO(2)as well as oxygen vacancies were found to be responsible for hydrogenation of furfural to 2-methyl furan while, Ni degrees and NiO were responsible for further hydrogenation to 2-MeTHF. The synergic effect between Ir and Ni was established through XPS, H-2-TPR analysis. With the help of some control experiments, the plausible reaction pathway was also proposed. The catalyst prepared by co-impregnation method found more effective than prepared by sequential addition method. At lower Ni loadings of 1% and 2%, low temperature of 160 degrees C as well as at low H(2)pressure of 250 psig, mixture of furfuryl alcohol and 2-methyl furan were formed selectively. Catalyst could be successfully reused up to 3 times without leaching of metals.
Keywords: 2-Methyltetrahydrofuran; Bimetallic catalyst; furfural; Hydrogenation; OER type mechanism

Palladium-catalyzed insertion of ethylene and 1,1-disubstituted difunctional olefins: an experimental and computational study - Gaikwad, Shahaji R.; Patel, Ketan; Deshmukh, Satej S.; Mote, Nilesh R.; Birajdar, Rajkumar S.; Pandole, Satish P.; Chugh, Jeetender; Chikkali, Samir H. (ChemPlusChem, 2020)
Insertion or coordination copolymerization of ethylene with di-substituted olefins is challenging and the choice of di-substituted mono-functional olefin versus di-substituted di-functional olefin (DDO) appears to be decisive. Here we show that DDO-inserted species are amenable to ethylene insertion and polymerization. DDOs such as 2-acetamidoacrylic acid (AAA), methyl 2-acetamidoacrylate (MAAA), and ethyl 2-cyanoacrylate (ECA) were treated with palladium complex [P perpendicular to OPdMe(L)] (P perpendicular to O=kappa(2)-P,O-Ar2PC6H4SO2O with Ar=2-MeOC6H4; L=C2H6OS) and the existence of respective insertion intermediates in moderate yield (up to 37 %) was established. These intermediates were exposed to ethylene and corresponding ethylene-inserted products were isolated and characterized. A careful comparison with three model compounds confirmed ethylene insertion and polymerization. Thus, the combined experimental and computational investigations show that DDO-inserted species can undergo ethylene insertion and polymerization.
Keywords: Homogeneous catalysis; insertion copolymerization; Olefins; Palladium; Polyethylene

Pan-genomics of Ochrobactrum species from clinical and environmental origins reveals distinct populations and possible links - Gohil, Kushal; Rajput, Vinay; Dharne, Mahesh (Genomics, 2020)
Ochrobactrum genus is comprised of soil-dwelling Gram-negative bacteria mainly reported for bioremediation of toxic compounds. Since last few years, mainly two species of this genus, O. intermedium and O. anthropi were documented for causing infections mostly in the immunocompromised patients. Despite such ubiquitous presence, study of adaptation in various niches is still lacking. Thus, to gain insights into the niche adaptation strategies, pan-genome analysis was carried out by comparing 67 genome sequences belonging to Ochrobactrum species. Pan-genome analysis revealed it is an open pan-genome indicative of the continuously evolving nature of the genus. The presence/absence of gene clusters also illustrated the unique presence of antibiotic efflux transporter genes and type IV secretion system genes in the clinical strains while the genes of solvent resistance and exporter pumps in the environmental strains. A phylogenomic investigation based on 75 core genes depicted better and robust phylogenetic resolution and topology than the 16S rRNA gene. To support the pan-genome analysis, individual genomes were also investigated for the mobile genetic elements (MGE), antibiotic resistance genes (ARG), metal resistance genes (MRG) and virulence factors (VF). The analysis revealed the presence of MGE, ARG, and MRG in all the strains which play an important role in the species evolution which is in agreement with the pan-genome analysis. The average nucleotide identity (ANI) based on the genetic relatedness between the Ochrobactrum species indicated a distinction between individual species. Interestingly, the ANI tool was able to classify the Ochrobactrum genomes to the species level which were assigned till the genus level on the NCBI database.
Keywords: Antibiotic resistance; Average nucleotide identity; Clinical and environmental strains; Core genes; MinION; Virulence factors

Particle size effect in different base fluids on the thermal conductivity of fatty acid coated magnetite nanofluids - Dadwal, Arun; Joy, P. A. (Journal of Molecular Liquids, 2020)
The effect of particle size on the thermal conductivity of nanofluids is studied by dispersing myristic acid coated magnetite (Fe3O4) nanoparticles in two different base fluids; toluene and kerosene. Magnetite nanoparticles of three different sizes 4, 7 and 10 nm dispersed in toluene and kerosene showed a linear increase in the thermal conductivity with increasing concentration of the nanopartides, above a critical concentration. The critical concentration below which the thermal conductivity remained unchanged with the concentration of the nanopartides is found to be lower for the kerosene-based fluids. The variation of thermal conductivity with particle size is without any clear trend. However, within the measurement errors (+/- 1%), the toluene-based fluids showed a decrease in the thermal conductivity with increasing particle size, whereas the opposite trend is observed for the kerosene-based fluids. Also, the kerosene-based fluids at similar concentrations of the nanopartides showed relatively larger enhancement in the thermal conductivity than the toluene-based fluids. The observed role of the base fluid in enhancing the thermal conductivity is correlated with the difference in the solvent-surfactant interactions which in turn affect the interfacial thermal resistance at the particle-fluid interface. The thermal conductivity of the nanofluids in toluene and kerosene is also found to show different trends with the size of the particles in the presence of an external magnetic field. The difference in the enhancement of thermal conductivity of the fluids in a magnetic field is explained in terms of the differences in the magnetic dipolar interactions, clustering/ agglomeration, and magnetic characteristics of the samples as well as the characteristics of the base fluid. (C) 2020 Elsevier B.V. All rights reserved.

Pd-iminocarboxylate complexes and their behavior in ethylene polymerization - Deshmukh, Satej S.; Gaikwad, Shahaji R.; Gonnade, Rajesh G.; Pandole, Satish P.; Chikkali, Samir H. (Chemistry-An Asian Journal, 2020)
Designing co-catalyst-free late transition metal complexes for ethylene polymerization is a challenging task at the interface of organometallic and polymer chemistry. Herein, a set of new, co-catalyst-free, single-component catalytic systems for ethylene polymerization have been unraveled. Treatment of anthranilic acid with various aldehydes produced four iminocarboxylate ligands (L1-L4) in very good to excellent yield (75-92 %). The existence of 2-((2-methoxybenzylidene)amino) benzoic acid (L1) has been unambiguously demonstrated using NMR spectroscopy, MS and single-crystal X-ray diffraction. A neutral Pd-iminocarboxylate complex [N OPdMe(L1)] (N O=kappa(2)-N,O-ArCHNC6H4CO2 with Ar=2-MeOC6H4) C1 was prepared by treating stoichiometric amount of L1.Na with palladium precursor. The identity of C1 was confirmed by 1-2D NMR spectroscopy and single-crystal X-ray diffraction studies. Along the same lines, palladium complexes C2-C4 were prepared from ligands L2-L4 respectively. In-situ high-pressure NMR investigations revealed that these Pd complexes are amenable to ethylene insertion and undergo facile beta-H elimination to produce propylene. These palladium complexes were then evaluated in ethylene polymerization reaction and various reaction parameters were screened. When C1-C4 were exposed to ethylene pressures of 10-50 bar, formation of low-molecular-weight polyethylene was observed.
Keywords: imine; Imine-carboxylate; Insertion polymerization; Pd complexes; Polyethylene

Phagocytosis of full-length Tau oligomers by Actin-remodeling of activated microglia - Das, Rashmi; Balmik, Abhishek Ankur; Chinnathambi, Subashchandrabose (Journal of Neuroinflammation, 2020)
Background Alzheimer's disease is associated with the accumulation of intracellular Tau tangles within neurons and extracellular amyloid-beta plaques in the brain parenchyma, which altogether results in synaptic loss and neurodegeneration. Extracellular concentrations of oligomers and aggregated proteins initiate microglial activation and convert their state of synaptic surveillance into a destructive inflammatory state. Although Tau oligomers have fleeting nature, they were shown to mediate neurotoxicity and microglial pro-inflammation. Due to the instability of oligomers, in vitro experiments become challenging, and hence, the stability of the full-length Tau oligomers is a major concern. Methods In this study, we have prepared and stabilized hTau40(WT) oligomers, which were purified by size-exclusion chromatography. The formation of the oligomers was confirmed by western blot, thioflavin-S, 8-anilinonaphthaalene-1-sulfonic acid fluorescence, and circular dichroism spectroscopy, which determine the intermolecular cross-beta sheet structure and hydrophobicity. The efficiency of N9 microglial cells to phagocytose hTau40(WT) oligomer and subsequent microglial activation was studied by immunofluorescence microscopy with apotome. The one-way ANOVA was performed for the statistical analysis of fluorometric assay and microscopic analysis. Results Full-length Tau oligomers were detected in heterogeneous globular structures ranging from 5 to 50 nm as observed by high-resolution transmission electron microscopy, which was further characterized by oligomer-specific A11 antibody. Immunocytochemistry studies for oligomer treatment were evidenced with A11(+) Iba1(high) microglia, suggesting that the phagocytosis of extracellular Tau oligomers leads to microglial activation. Also, the microglia were observed with remodeled filopodia-like actin structures upon the exposure of oligomers and aggregated Tau. Conclusion The peri-membrane polymerization of actin filament and co-localization of Iba1 relate to the microglial movements for phagocytosis. Here, these findings suggest that microglia modified actin cytoskeleton for phagocytosis and rapid clearance of Tau oligomers in Alzheimer's disease condition.
Keywords: Actin; activation; Alzheimer's disease; microglia; migration; neurodegeneration; Tau Oligomers; Tauopathy

Phosphorous-doped graphitic material as a solid acid catalyst for microwave-assisted synthesis of beta-ketoenamines and baeyer-villiger oxidation - Maity, Sayantan; Ram, Farsa; Dhar, Basab Bijayi (ACS Omega, 2020)
Synthesis of phosphorous-doped graphitic materials (P-Gc) using phytic acid as a precursor was done in a microwave oven in a cost- and time-effective green way. The material was used as a solid acid catalyst for microwave (MW)-assisted synthesis of beta-ketoenamines and Baeyer-Villiger (By) oxidation. In the case of BV oxidation, hydrogen peroxide (H2O2) was used as a green oxidant. For beta-ketoenamines, in most cases, 100% conversion with an similar to 95% yield was achieved in ethyl acetate medium. In solvent-free conditions, the yield of beta-ketoenamines was similar to 75%. A kinetic study suggested that the resonance stabilization of the positive reaction center happens in the transition state for beta-ketoenamine synthesis. In BV oxidation, cyclic ketones were converted to their corresponding cyclic esters in good to high yields (similar to 80% yield) in a shorter reaction time (6-20 min). As per our knowledge, this is the first report of BV oxidation catalyzed by a heteroatom-doped graphitic material. For BV oxidation, the phosphoric acid functional groups present in P-Gc might increase the electrophilicity of the carbonyl group of the ketones to compensate for the weakness of H2O2 as a nucleophile and a spiro-bisperoxide intermediate has been identified in high-resolution mass spectrometry.

Photodynamic exposure of Rose-Bengal inhibits Tau aggregation and modulates cytoskeletal network in neuronal cells - Dubey, Tushar; Gorantla, Nalini Vijay; Chandrashekara, Kagepura Thammaiah; Chinnathambi, Subashchandrabose (Scientific Reports, 2020)
The intracellular Tau aggregates are known to be associated with Alzheimer's disease. The inhibition of Tau aggregation is an important strategy for screening of therapeutic molecules in Alzheimer's disease. Several classes of dyes possess a unique property of photo-excitation, which is applied as a therapeutic measure against numerous neurological dysfunctions. Rose Bengal is a Xanthene dye, which has been widely used as a photosensitizer in photodynamic therapy. The aim of this work was to study the protective role of Rose Bengal against Tau aggregation and cytoskeleton modulations. The aggregation inhibition and disaggregation potency of Rose Bengal and photo-excited Rose Bengal were observed by in-vitro fluorescence, circular dichroism, and electron microscopy. Rose Bengal and photo-excited Rose Bengal induce minimal cytotoxicity in neuronal cells. In our studies, we observed that Rose Bengal and photo-excited Rose Bengal modulate the cytoskeleton network of actin and tubulin. The immunofluorescence studies showed the increased filopodia structures after photo-excited Rose Bengal treatment. Furthermore, Rose Bengal treatment increases the connections between the cells. Rose Bengal and photo-excited Rose Bengal treatment-induced actin-rich podosome-like structures associated with cell membranes. The in-vivo studies on UAS E-14 Tau mutant Drosophila suggested that exposure to Rose Bengal and photo-excited Rose Bengal efficiency rescues the behavioural and memory deficit in flies. Thus, the overall results suggest that Rose Bengal could have a therapeutic potency against Tau aggregation.

Phytochemicals in cancer treatment: from preclinical studies to clinical practice - Choudhari, Amit S.; Mandave, Pallavi C.; Deshpande, Manasi; Ranjekar, Prabhakar; Prakash, Om (Frontiers in Pharmacology, 2020)
Cancer is a severe health problem that continues to be a leading cause of death worldwide. Increasing knowledge of the molecular mechanisms underlying cancer progression has led to the development of a vast number of anticancer drugs. However, the use of chemically synthesized drugs has not significantly improved the overall survival rate over the past few decades. As a result, new strategies and novel chemoprevention agents are needed to complement current cancer therapies to improve efficiency. Naturally occurring compounds from plants known as phytochemicals, serve as vital resources for novel drugs and are also sources for cancer therapy. Some typical examples include taxol analogs, vinca alkaloids such as vincristine, vinblastine, and podophyllotoxin analogs. These phytochemicals often act via regulating molecular pathways which are implicated in growth and progression of cancer. The specific mechanisms include increasing antioxidant status, carcinogen inactivation, inhibiting proliferation, induction of cell cycle arrest and apoptosis; and regulation of the immune system. The primary objective of this review is to describe what we know to date of the active compounds in the natural products, along with their pharmacologic action and molecular or specific targets. Recent trends and gaps in phytochemical based anticancer drug discovery are also explored. The authors wish to expand the phytochemical research area not only for their scientific soundness but also for their potential druggability. Hence, the emphasis is given to information about anticancer phytochemicals which are evaluated at preclinical and clinical level.
Keywords: Anticancer; clinical; medicinal plants; phytochemicals; preclinical

Phytochemicals in cancer treatment: from preclinical studies to clinical practice (vol 10, 1614, 2020) - Choudhari, Amit S.; Mandave, Pallavi C.; Deshpande, Manasi; Ranjekar, Prabhakar; Prakash, Om (Frontiers in Pharmacology, 2020)
Keywords: Anticancer; clinical; medicinal plants; phytochemicals; preclinical

Plant probiotic bacterial endophyte, alcaligenes faecalis, modulates plant growth and forskolin biosynthesis incoleus forskohlii - Mastan, Anthati; Rane, Digeshwar; Dastager, Syed G.; Vivek Babu, Chikkarasanahalli Shivegowda (Probiotics and Antimicrobial Proteins, 2020)
Coleus forskohliiis an herb, well-known for its medicinal compound forskolin present in its roots, with wide range of pharmaceutical applications. Here, we report, for the first time, the role of plant-probiotic bacterial endophytes ofC. forskohlii, CFLB1 and CFRB1, isolated from leaf and root, which regulate plant growth andin plantforskolin content. Native bacterial endophyte, CFRB1 (Alcaligenes faecalis), significantly modulates primary plant productivity and forskolin content under pot and field conditions. Under field conditions, CFRB1 endophyte application significantly enhanced photosynthetic pigments and reduced the severity of root-knot and root rot diseases. Expression analyses of functional genes involved in the forskolin biosynthesis inC. forskohliiplants treated with CFRB1 endophyte under field conditions revealed differential upregulation of fourC. forskohliiditerpene synthases (CfTPSs),CfTPS1,CfTPS2,CfTPS3andCfTPS4, along with cytochrome P450 (CfCYP76AH15) and acyltransferase (CfACT1-8) genes. CFRB1 treatment reduced the severity of nematode infection and root rot inC. forskohliiplants by 81 and 78%, respectively. Overall, we demonstrate that cross-talk of plant-endophyte interaction inC. forskohliiis beneficial, leading to enhanced forskolin content through modulation of forskolin biosynthetic pathway genes along with increased plant yield and reduced disease incidence. Thus, endophytic isolate,A. faecalis(CFRB1), could be deployed as a novel bio-stimulant for enhancingin plantaforskolin content during cultivation ofC. forskohlii.
Keywords: Alcaligenes faecalis; CfACT1-8; CfCYP76AH15; CfTPSs; Coleus forskohlii; Forskolin; Plant-probiotic bacterial endophyte

Polymer nanorings with uranium specific clefts for selective recovery of uranium from acidic effluents via reductive adsorption - Kushwaha, Shilpi; Mane, Manoj; Ravindranathan, Sapna; Das, Amitava (ACS Sensors, 2020)
Nanostructured polymeric materials, functionalized with an appropriate receptor, have opened up newer possibilities for designing a reagent that shows analyte-specific recognition and efficient scavenging of an analyte that has either a detrimental influence on human physiology and environment or on its recovery for further value addition. Higher active surface area, morphological diversity, synthetic tunability for desired surface functionalization, and the ease of regeneration of a nanostructured material for further use have provided such materials with a distinct edge over conventional reagents. The use of a biodegradable polymeric backbone has an added significance owing to the recent concern over the impact of polymers on the environment. Functionalization of biodegradable sodium alginate with AENA (6.85% grafting) as the receptor functionality led to a unique open framework nanoring (NNRG) morphology with a favorable spatial orientation for specific recognition and efficient binding to uranyl ions (U) in an aqueous medium over a varied pH range. Nanoring morphology was confirmed by transmission electron microscopy and atomic force microscopy images. The nanoscale design maximizes the surface area for the molecular scavenger. A combination of all these features along with the reversible binding phenomenon has made NNRG a superior reagent for specific, efficient uptake of UO22+ species from an acidic (pH 3-4) solution and compares better than all existing UO22+-scavengers reported till date. This could be utilized for the recovery of uranyl species from a synthetic acidic effluent of the nuclear power. The results of the U uptake experiments reveal a maximum adsorption capacity of 268 mg of U per g of NNRG in a synthetic nuclear effluent. X-ray photoelectron spectroscopy studies revealed a reductive complexation process and stabilization of U(IV)-species in adsorbed uranium species (U@NNRG).
Keywords: biodegradable polymeric backbone; molecular recognition; nanostructured material; sodium alginate; uranium; uranyl-specific receptor

Porphyrin-based conducting polymer hydrogel for supercapacitor application - Das, Debasree; Kurungot, Sreekumar (Energy Technology, 2020)
Herein, the electrochemical properties and energy storage capability of a flexible, all-solid-state supercapacitor based on the supramolecular assembly of polypyrrole (PPy) and the anion of 5,10,15,20-tetrakis(4-sulfonatophenyl)-21H,23H-porphine manganese(III) chloride (MnTSPP) are reported. The electrode material consists of a conductive polymer hydrogel formed through the gelation initiated by cross-linking of the dopant MnTSPP anion in the PPy chains. The morphology of the cross-linked polymer hydrogel is that of a particle-decorated nanofiber, which can perform as a flexible supercapacitor electrode material with a specific capacitance of 300 Fg(-1) and capacitance retention of 78% up to 10 000 cycles. The anion of MnTSPP plays a pivotal role in enhancing the charge storage capability by facilitating the electron transfer between the polymer interchains. In addition, the steric hindrance due to the large size of the dopant counter ions of MnTSPP reduces the counterion drain effect and structural pulverization of PPy, thereby improving the capacitive retention.
Keywords: conductive hydrogels; energy storage devices; Flexible Supercapacitors; nanofibers; porphyrin-based polymers

Proteomic analysis detects deregulated reverse cholesterol transport in human subjects with ST-segment elevation myocardial infarction (vol 222, 103796, 2020) - Das, Apabrita Ayan; Choudhury, Kamalika Roy; Jagadeeshaprasad, M. G.; Kulkarni, Mahesh J.; Mondal, Prakash Chandra; Bandyopadhyay, Arun (Journal of Proteomics, 2020)

Proteomic analysis detects deregulated reverse cholesterol transport in human subjects with ST-segment elevation myocardial infarction - Das, Apabrita Ayan; Choudhury, Kamalika Roy; Jagadeeshaprasad, M. G.; Kulkarni, Mahesh J.; Mondal, Prakash Chandra; Bandyopadhyay, Arun (Journal of Proteomics, 2020)
Reverse cholesterol transport (RCT) plays a critical role in removing cholesterol from the arterial wall. However, very few reports directly relate chronic inflammation and RCT with atherosclerosis. The present study was undertaken to investigate clinical implications of significantly altered circulating proteins in subjects with ST-segment elevation myocardial infarction (STEMI) in the manifestation of atherosclerotic events. Using a casecontrol design, more than 2500 proteins in both STEMI and healthy control subjects were identified by Orbitrap mass spectrometer. Quantitative proteomics study revealed downregulation of 26 proteins while expression of 38 proteins increased significantly in STEMI subjects compared to healthy controls. Pathway enrichment analyses indicated that most of the identified proteins were related to chronic inflammation, atherosclerosis, and RCT. Altered proteins such as AZGP1, ABCA5, Calicin, PGLYRP2, HAVCR2 and C17ORF57 were further validated by Western blotting analysis of human plasma. Pathophysiological significance was studied using macrophage derived foam cell for their critical role in RCT which indicated the imbalance of RCT via the interaction of AZGP1 with CD36. In summary, this study revealed a unique relationship of some novel proteins apparently responsible for impaired RCT and chronic inflammation leading to atherothrombosis and myocardial infarction. Significance: In the present study we identified >= 2500 unique circulating proteins in healthy control and clinically diagnosed STEMI subjects among which 423 proteins were found to be common in both the groups. We further show 64 proteins significantly different between healthy control and STEMI subjects. Proteomic analyses reveal a panel of proteins associated with atherosclerosis and STEMI. One of the proteins, AZGP1, an adipokine, is likely to act as the missing link between chronic inflammation and cholesterol transport. Deregulation of reverse cholesterol transport might be orchestrated by AZGP1, CD36, ABCA5, and PPARy in STEMI subjects. The present study employs shotgun and quantitative proteomics followed by in vitro validations demonstrating a biochemical basis for reverse cholesterol transport in the local milieu of the luminal wall of the artery which are critical for plaque build-up and atherosclerosis.
Keywords: Atherosclerosis; AZGP1; CD36; Plasma proteomics; Reverse cholesterol transport; STEMI

Residue-based propensity of aggregation in the Tau amyloidogenic hexapeptides AcPHF6*and AcPHF6 - Dangi, Abha; Balmik, Abhishek Ankur; Ghorpade, Archana Kisan; Gorantla, Nalini Vijay; Sonawane, Shweta Kishor; Chinnathambi, Subashchandrabose; Marelli, Udaya Kiran (RSC Advances, 2020)
In Alzheimer's disease and related tauopathies, the aggregation of microtubule-associated protein, Tau, into fibrils occursviathe interaction of two hexapeptide motifs PHF*(275)VQIINK(280)and PHF(306)VQIVYK(311)as beta-sheets. To understand the role of the constituent amino acids of PHF and PHF* in the aggregation, a set of 12 alanine mutant peptides was synthesized by replacing each amino acid in PHF and PHF* with alanine and they were characterized by nuclear magnetic resonance (NMR) spectroscopy, circular dichroism (CD), transmission electron microscopy (TEM) and ThS/ANS fluorescence assay. Our studies show that while the aggregation was suppressed in most of the alanine mutant peptides, replacement of glutamine by alanine in both PHF and PHF* enhanced the fibrillization.

Role of B site ions in bifunctional oxygen electrocatalysis: a structure-property correlation study on doped Ca(2)Fe(2)O(5)brownmillerites - Thundiyil, Shibin; Vinod, C. P.; Kurungot, Sreekumar; Devi, R. Nandini (Physical Chemistry Chemical Physics, 2020)
The role of B site doping with transition metals in brownmillerites, a perovskite related family of compounds, in bifunctional oxygen electrocatalysis,viz., simultaneous reduction and evolution reactions, is analysed. Ca2Fe1.9M0.1O5(M = Mn, Co, Ni, and Cu) is synthesised and structurally characterised by powder XRD and Rietveld refinement. Valence states of the surface B site ions are identified by X-ray photoelectron spectroscopy. Bifunctional oxygen electrochemistry is studied with the RDE and RRDE techniques and correlated with the structural and electronic parameters like oxygen non-stoichiometry and B site catalytic activity. Since the widely accepted electronic descriptors like e(g)filling may not be sufficient for explaining the bifunctional activity, B site electron donating capability as well as the extent of oxygen vacancies enhancing O(2)adsorption is also considered. Such structural parameters are also found to influence both the ORR and OER and based on this, Ni doping is proposed as advantageous for the bifunctional activity.

Role of dietary fatty acids in microglial polarization in Alzheimer's disease - Desale, Smita Eknath; Chinnathambi, Subashchandrabose (2020)
Microglial polarization is an utmost important phenomenon in Alzheimer's disease that influences the brain environment. Polarization depends upon the types of responses that cells undergo, and it is characterized by receptors present on the cell surface and the secreted cytokines to the most. The expression of receptors on the surface is majorly influenced by internal and external factors such as dietary lipids. Types of fatty acids consumed through diet influence the brain environment and glial cell phenotype and types of receptors on microglia. Reports suggest that dietary habits influence microglial polarization and the switching of microglial phenotype is very important in neurodegenerative diseases. Omega-3 fatty acids have more influence on the brain, and they are found to regulate the inflammatory stage of microglia by fine-tuning the number of receptors expressed on microglia cells. In Alzheimer's disease, one of the pathological proteins involved is Tau protein, and microtubule-associated protein upon abnormal phosphorylation detaches from the microtubule and forms insoluble aggregates. Aggregated proteins have a tendency to propagate within the neurons and also become one of the causes of neuroinflammation. We hypothesize that tuning microglia towards anti-inflammatory phenotype would reduce the propagation of Tau in Alzheimer's disease.
Keywords: Fatty acids; Microglial polarization; Omega-3 fatty acids; Tau inflammation; Tau phagocytosis; Tau spreading; Tauopathy

Scalable synthesis of manganese-doped hydrated vanadium oxide as a cathode material for aqueous zinc-metal battery - Ghosh, Meena; Dilwale, Swati; Vijayakumar, Vidyanand; Kurungot, Sreekumar (ACS Applied Materials & Interfaces, 2020)
Rechargeable aqueous zinc-metal batteries (ZMBs) are considered as potential energy storage devices for stationary applications. Despite the significant developments in recent years, the performance of ZMBs is still limited due to the lack of advanced cathode materials delivering high capacity and long cycle life. In this work, we report a low-temperature and scalable synthesis method following a surfactant-assisted route for preparing manganese-doped hydrated vanadium oxide (MnHVO-30) and its application as the cathode material for ZMB. The as-prepared material possesses a porous architecture and expanded interlayer spacing. Therefore, the MnHVO-30 cathode offers fast and reversible insertion of Zn2+ ions during the charge/discharge process and delivers 341 mAh g(-1) capacity at 0.1 A g(-1). Moreover, the MnHVO-30 parallel to Zn cell retains 82% of its initial capacity over 1200 stability cycles, which is higher compared to that of the undoped system. Besides, a quasi-solid-state home-made pouch cell with an area of 3.3 x 1.6 cm(2) and 3.6 mg cm(-2) loading is assembled, achieving 115 mAh g(-1) capacity over 100 stability cycles. Therefore, this work provides an easy and attractive way for preparing efficient cathode materials for aqueous ZMBs.
Keywords: anionic surfactant; hydrated vanadium pentoxide; Nafion ionomer membrane; post-lithium battery; quasi-solid-state battery

Selective, bifunctional Cu-WOx/Al2O3 catalyst for hydrodeoxygenation of fatty acids - Janampelli, Sagar; Sethia, Govind; Darbha, Srinivas (Catalysis Science & Technology, 2020)
Selective hydrodeoxygenation of oleic acid (OA; in a batch reactor, at 300 degrees C, 30 bar H-2 pressure, reaction time of 1 h and reactant-to-catalyst weight ratio of 2 g OA/0.2 g) forming n-octadecane in yields as high as 93% over a non-noble metal, sulfur-free, bimetallic Cu-WOx/Al2O3 catalyst is reported for the first time. Several Cu-WOx/Al2O3 compositions were prepared by a sequential wet-impregnation method and evaluated. A catalyst with 10 wt% Cu and 4 wt% W enabled the highest activity and selectivity. Upon adding WOx, the amount of moderate and strong acid sites increased and more Cu in the catalyst was in reduced electron-rich metallic (Cu-0) state. The crystallite size and dispersion of Cu were little affected. WOx promoted the fatty acid hydrodeoxygenation activity of Cu. While a monometallic Cu catalyst (10Cu/Al2O3) yielded n-octadecane and n-heptadecane along with high amounts of intermediate octadecanol and octadecanal products, the bimetallic catalyst (10Cu-4WO(x)/Al2O3) gave mainly n-octadecane. Acidity and the high amount of reduced Cu-0 species are responsible for the high catalytic hydrodeoxygenation performance of this bimetallic catalyst.

Shotgun metagenome guided exploration of anthropogenically driven resistomic hotspots within Lonar soda lake of India - Chakraborty, Jaya; Sapkale, Vibhavari; Rajput, Vinay; Shah, Manan; Kamble, Sanjay; Dharne, Mahesh (Ecotoxicology and Environmental Safety, 2020)
Anthropogenic activities mediated antibiotic resistance genes (ARGs) in the pristine aquatic bodies (lakes) is raising concern worldwide. Long read shotgun sequencing was used to assess taxonomic diversity, distribution of ARGs and metal resistance genes (MRGs) and mobile genetic elements (MGEs) in six sites within hypersaline Lonar soda lake (India) prone to various anthropogenic activities. Proteobacteria and Euryarchaeota were dominant phyla under domain Bacteria and Archaea respectively. Higher abundance of Bacteroidetes was pragmatic at sites 18LN5 and 18LN6. Functional analysis indicated 26 broad-spectrum ARGs types, not reported earlier in this ecosystem. Abundant ARG types identified were multidrug efflux, glycopepetide, bacitracin, tetracycline and aminogylcoside resistance. Sites 18LN1 and 18LN5 depicted 167 and 160 different ARGs subtypes respectively and rpoB2, bcrA, tetA(48), mupA, ompR, patA, vanR and multidrug ABC transporter genes were present in all samples. The rpoB2 gene was dominant in 18LN1, whereas bcrA gene in 18LN2-18LN6 sites. Around 24 MRGs types were detected with higher abundance of arsenic in 18LN1 and copper in 18LN2-18LN6, signifying metal contamination linked to MRGs. The bacterial taxa Pseudomonas, Thioalkalivibrio, Burkholderia, Clostridium, Paenibacillus, Bacillus and Streptomyces were significantly associated with ARGs. This study highlights the resistomic hotspots in the lake for deploying policies for conservation efforts.
Keywords: ARGs; diversity; Lonar lake; MGEs; MRGs; Nanopore sequencing

Silk fibroin 3D microparticle scaffolds with bioactive ceramics: chemical, mechanical, and osteoregenerative characteristics - Parekh, Nimisha A.; Deshpande, V. Rucha; Shukla, Swati G.; Nisal, Anuya A. (Advanced Engineering Materials, 2020)
Preparation of 3D scaffolds for bone tissue engineering (BTE) is a challenging task as it requires appropriate pore size and porosities, mechanical properties, and controlled bioerosion rate. The focus of this work is the fabrication of silk fibroin (SF) 3D microparticle scaffolds with the incorporation of hydroxyapatite (HA) and calcium sulfate (CaS) as bioceramics. Physicochemical characterization shows approximate to 30% filler loading and approximate to 40% optimum porosity with >100 mu m pore size for these filled/unfilled scaffolds. Nanoindentation studies show improved Young's modulus at microparticle level with the incorporation of bioceramics. SF-HA scaffolds showed three fold increase in Young's modulus, whereas SF-CaS showed two fold increase. In vitro bioerosion study results in early bioerosion with SF-CaS scaffold, whereas prolonged bioerosion with SF-HA scaffold. In vitro osteoregenerative potential is analyzed by estimating alkaline phosphatase (ALP), bone morphogenetic protein-2 (BMP-2), and osteocalcin (OCN). SF CaS supports early stage differentiation while SF 50% HA predominantly supports late stage. The expression of TNF-alpha suggests a reduced risk of immune rejection. This work, therefore, concludes that although SF supports bone tissue regeneration, the choice of bioceramic enhances the applicability in various clinical scenarios by providing a controlled bioerosion rate, tunable speed of osteoregeneration, and improved load bearing capacities.
Keywords: bioceramics; bioerosion; osteogenic differentiation; Silk fibroin; stem cells

Simultaneous identification and estimation of glycyrrhizin, glabridin, and 18β‐glycyrrhetinic acid in de‐glycyrrhized Ayurvedic lipid‐based formulation of Glycyrrhiza glabra using dual wavelength reverse phase‐high‐performance liquid chromatography - Kumbhalkar, Bhagyashri; Walunj, Tanhaji; Chavan, Sandeep; Gupta, Vidya; Deshmukh, Vineeta; Sardeshmukh, Sadanand (Separation Science Plus, 2020)
Plant‐based Ayurvedic formulations such as medicated oils, confectioneries, etc. are developed with a rationale of selecting specific compounds for targeted action and minimal side effects. It is imperative to develop an analytical method to simultaneously identify and quantify the targeted compounds for good resolution with low retention time. The present assay using reverse phase‐high‐performance liquid chromatography is optimized to resolve glycyrrhizin, glabridin, and 18β‐glycyrrhetinic acid simultaneously at retention times of 6.6, 8.1, and 10.2 min, respectively, using acidified mobile phase from Glycyrrhiza glabra utilized in Ayurvedic lipid (cow's ghee and sesame oil) based formulations. Raw material, its decoction, and residues formed during preparation steps were extracted in methanol while lipid formulations were extracted using a binary solvent system of methanol and n‐hexane. The separation was performed on Hypersil gold column maintained at 40°C using 0.2% ortho‐phosphoric acid with pH 3.5 in water and acetonitrile as binary gradient mobile phase. The compounds were detected at wavelengths 230 (glabridin) and 254 (glycyrrhizin and 18β‐glycyrrhetinic acid) nm. The method revealed de‐glycyrrhized finished products containing glabridin and 18β‐glycyrrhetinic acid having medicinal value.

Site speci fic nitrogen incorporation in reduced graphene oxide using imidazole as a novel reducing agent for ef ficient oxygen reduction reaction and improved supercapacitive performance - Roy, Dipayan; Sarkar, Saikat; Bhattacharjee, Kaustav; Panigrahi, Karamjyoti; Das, Bikram Kumar; Sardar, Kausik; Sarkar, Sourav; Chattopadhyay, Kalyan Kumar (Carbon, 2020)

Solid catalysts for conversion of furfural and its derivatives to alkanediols - Enjamuri, Nagasuresh; Darbha, Srinivas (Catalysis Reviews-Science and Engineering, 2020)
Alkanediols with five and six carbon atoms (1,2- & 1,5-pentanediols and 1,2- & 1,6-hexanediols, respectively) are an important class of industrial chemicals having wide application. Their production from lignocellulosic biomass-derived furfural and its derivatives using solid catalysts is a sustainable and attractive approach. Several bifunctional catalysts with metal (for hydrogenation/hydrogenolysis) and acid/base (for ring opening) functionalities have been reported. Effective and selective conversion of furfurals to a desired diol is still a challenge. This review discusses the recent advances in catalyst development for pentane- and hexanediols. The reaction pathways, active sites, and possible reaction mechanisms over the solid catalysts are discussed. A comparative catalytic activity data of the known catalysts are reported.
Keywords: 5-hydroxymethylfurfural (HMF); Alkanediol; furfural (FAL); hexanediol; pentanediol; solid catalyst

Stress-induced electronic structure modulation of manganese-incorporated Ni2P leading to enhanced activity for water splitting - Sarkar, Shreya; Dheer, Lakshay; Vinod, C. P.; Thapa, Ranjit; Waghmare, V. Umesh; Peter, Sebastian C. (ACS Applied Energy Materials, 2020)
The cornerstone of the emerging hydrogen economy is hydrogen production by water electrolysis with concomitant oxygen generation. Incorporating a third element in metal phosphides can tune the crystalline and electronic structure, hence improving the electrocatalytic properties. In this work, Mn-doped Ni2P with varying ratios of Mn and Ni has been explored as excellent catalysts for water splitting. A complete cell made of the best catalyst Ni1.5Mn0.5P electrodes showed low voltage of 1.75 V at a current density of 10 mA cm(-2) due to enhanced electrical conductivity, induction of tensile stress, enhanced electrochemical surface area, and increased electric dipole upon Mn incorporation.
Keywords: Electronic Structure; hydrogen evolution reaction; Oxygen Evolution Reaction; phosphides; water splitting

Structural and electrical characterization studies for ternary composite of polypyrrole - Megha, R.; Ravikiran, Y. T.; Kumari, S. C. Vijaya; Prakash, H. G. Raj; Revanasiddappa, M.; Manjunatha, S.; Dastager, Syed G.; Thomas, S. (Journal of Materials Science-Materials in Electronics, 2020)
In this work, temperature dependence of alternate current (AC) and direct current (DC) conductivities of optimized polypyrrole/silver-tantalum oxide (PPy/Ag-Ta2O5), a ternary conducting polymer composite is comparatively studied with those of PPy and PPy/Ag. For the purpose, silver (Ag) nanoparticles were encapsulated with polypyrrole (PPy) by in situ oxidative polymerization to form core-shell structured PPy/Ag composite for which Ag nanoparticles were extracted from green tea. The PPy/Ag composite was then mechanically mixed with tantalum pentoxide (Ta2O5) to form PPy/Ag-Ta(2)O(5)ternary composite. Increase in depth of delocalization band of PPy in ternary composite as compared to those of PPy/Ag composite and PPy, indicating its increased AC conductivity confirmed from the comparative FTIR analyses. Interaction between PPy/Ag composite and Ta(2)O(5)in the ternary composite was confirmed from XRD studies. The formation of core-shell structured PPy/Ag composite and Ta(2)O(5)particles embedded in such PPy/Ag composite to form PPy/Ag-Ta(2)O(5)ternary composite confirmed from TEM and Raman studies. The frequency- and temperature-dependent electrical conductivity studies revealed increase in AC conductivity of the ternary composite as compared to those of PPy/Ag composite and pure PPy attributed mainly to interfacial effects. The charge transport in these samples predicted to be due to correlated barrier hopping of charges was confirmed by calculating their respective AC and DC activation energies.

Surface functionalization: an efficient alternative for promoting the catalytic activity of closed shell gold clusters - Joshi, Krati; Krishnamurty, Sailaja; Dar, Manzoor Ahmad (Physical Chemistry Chemical Physics, 2020)
{Surface functionalization through adsorption of ligands or non-metal atoms is considered to be an interesting and viable approach for tuning the physicochemical properties of gold clusters. Highly stable and magic numbered electronic configurations of thiolate protected gold clusters such as Au-25(SR)(18), Au-38(SR)(24)etc. with intriguing properties are the direct manifestation of the rich chemistry of the Au-S interface. The present investigation discerns the CO oxidation activity of structurally well characterized sulphur functionalized gold cluster anions AumS4-

SWATH-MS based quantitative proteomics analysis to evaluate the antileishmanial effect of Commiphora wightii- Guggul and Amphotericin B on a clinical isolate of Leishmania donovani - Bar Routaray, Chinmayee; Bhor, Renuka; Bai, Shakuntala; Kadam, Nitin Suryakant; Jagtap, Surabhi; Doshi, Pooja Jignesh; Sundar, Shyam; Sawant, Sangeeta; Kulkarni, Mahesh J.; Pai, Kalpana (Journal of Proteomics, 2020)
The present study provides comprehensive proteomics analyses of the response of L. donovani parasite to pharamacological stress in vitro. Identification of differentially expressed proteins with associated molecular functions and metabolic pathways, clearly provides an insight into the potential mechanism of the antileishmanial effects as well as a comparative response of the parasite to Guggul and AmB. Treatment of parasite with AmB results in an enhanced modulatory mechanism to counteract the drug induced stress which may have contributed to relapse. In the case of Guggul treatment, an effective antipromastigote activity was observed, which is being reported for the first time. Thus, a deeper understanding of the molecular pathways in the Leishmania parasite in response to pharmacological stress would help in designing novel and effective strategies in targeting the key molecules essential for parasite survival. It will also help in screening of new lead molecules targeting these vital pathways which could be used as an adjunct therapy along with the limited repertoire of antileishmanial drugs.

Synthesis, characterization and catalytic study of mesoporous carbon materials prepared via mesoporous silica using non-surfactant templating agents - Pagar, Nitin S.; Karandikar, Prashant R.; Chandwadkar, Asha J.; Deshpande, Raj M. (Journal of Porous Materials, 2020)
Mesostructured silica materials with surface area in the range of similar to 700-900 m(2)/g have been prepared using hydroxy-carboxylic acid compounds such as tartaric acid, malic acid and citric acid (low cost non-surfactant template/pore forming agents) and tetraethylorthosilicate (TEOS) as silica source by sol-gel reaction. The templates were removed by either soxhlet extraction or calcination method. Mesoporous carbon molecular sieves were then prepared by carbonizing sucrose inside the pores of the above prepared mesoporous silica using sulfuric acid as a catalyst. The materials were characterized by FTIR spectroscopy, powder X-ray diffraction (XRD), N-2-sorption studies, microanalysis, thermal analysis and transmission electron microscopy (TEM). The resulting carbon material shows relatively higher surface area (similar to 1100 m(2)/g), narrow pore size distribution and pore diameter of 4-5 nm. The mesoporosity of carbon material arises from interconnecting channels arrangements of mesoporous silica template. The mesoporous carbon material was used as a support for the immobilization of rhodium complex [HRhCO(TPPTS)(3)] by ossification method. The prepared catalyst has been tested for the hydroformylation of higher olefins. The activity of the catalyst was improved by 20-30% as compared to the catalyst prepared from a conventional activated carbon support.
Keywords: Carbonization; Hydroformylation; Immobilization; Low cost templates; mesoporous carbon; Mesoporous silica

Synthesis of novel of 2, 5-disubstituted 1, 3, 4-oxadiazole derivatives and their in vitro anti-inflammatory, anti-oxidant evaluation, and molecular docking study - Kashid, Bharat B.; Salunkhe, Pravin H.; Dongare, Balasaheb B.; More, Kishor R.; Khedkar, Vijay M.; Ghanwat, Anil A. (Bioorganic & Medicinal Chemistry Letters, 2020)
A series of novel 2, 5-disubstituted 1, 3, 4-Oxadiazole derivatives as a potential anti-inflammatory, and antioxidant agent were synthesized via cyclisation. Hydrazide molecule treated with substituted acids in the presence of phosphorus oxychloride (POCl3) as an efficient reagent as well as solvent by conventional method with shorter reaction time and excellent yield. The newly synthesized 1, 3, 4-oxadiazole derivatives exhibited excellent to good anti-inflammatory and anti-oxidant activities compaired to the standard drugs. Molecular docking study on the crucial anti-inflammatory target-cyclooxygenase-2 (COX-2) revealed the ability of the scaffold to correctly recognize the active site and achieve significant bonded and non-bonded interactions with key residues therein. This study could identify potential compounds which can be pertinent starting points for structure-based drug design to obtain newer anti-inflammatory agents.
Keywords: 1; 3; 4-Oxadiazole; Anti-inflammatory; Anti-Oxidant; Biological activity; computational chemistry

Synthesis of phospho-polypeptides via phosphate-containing N-carboxyanhydride: application in enzyme-induced self-assembly, and calcium carbonate mineralization - Mondal, Basudeb; Das, Soumen; Panda, Sidharth; Dutta, Tahiti; Sen Gupta, Sayam (ChemPlusChem, 2020)
An easy synthetic strategy was developed to synthesize the phosphate-functionalized amino acid N-carboxyanhydride (NCA), using simple primary amine initiators to obtain homo and block phospho-polypeptides with controlled molecular weight and molecular weight distribution. The methodology was extended to the synthesis of the end-functionalized homo polypeptides (15 to 50 repeat unit) and block co-polypeptides with PEG (0.7 K, 2 K, and 5 K) and glycopolypeptide (15-unit mannose glycopolypeptide) as one of the blocks. The deprotected fully water-soluble anionic phosphate-based polypeptides showed pH-dependent helical conformation with a helical content of 20 %, which further changed to beta-sheets upon addition of the enzyme alkaline phosphatase (ALP) due to dephosphorylation. The block co-polypeptide containing PEG as one of the blocks led to its self-assembly into colloidal structures, such as vesicles with a hydrodynamic diameter of similar to 250 nm, due to the formation of amphiphilic block co-polymer upon dephosphorylation. The nature of the colloidal structures formed can be temporally controlled by the extent of dephosphorylation. Finally, the phospho-polypeptides serve as a template for the mineralization of calcium carbonate with varying polymorphs and morphologies.
Keywords: Biomineralization; enzymes; phosphopolypeptides; Proteins; Self-assembly

Tale of biphenyl and terphenyl substituents for structurally diverse ketiminato magnesium, calcium and germanium complexes - Kumar, Rohit; Yadav, Sandeep; Gour, Kritika; Sangtani, Ekta; Ranjan Dash, Soumya; Raja, Abhishekram; Vanka, Kumar; Gonnade, Rajesh G.; Sen, Sakya S. (Chemistry-An Asian Journal, 2020)
In this paper, we have used two N,O-ketiminato ligands (L1 and L2) with biphenyl and terphenyl substituent on the nitrogen atom. Deprotonation of L1 with KN(SiMe3)(2) and subsequent reaction with MgI2 led to a homoleptic dinuclear magnesium complex (1) with a Mg2O2 four-membered ring. Deprotonation with nBuLi and subsequent reaction with MgI2 afforded a unusual dinuclear magnesium complex (2) with a Mg2O2 ring. Extension of the ligand for calcium resulted in a trinuclear calcium complex (3) with six four-membered Ca2O2 rings. We could not isolate any chelating complex when L2 was used as a ligand, and only oxygen bound magnesium (4) and calcium (5) adducts were isolated. DFT studies were performed to understand this dissimilar behavior. More diverse results were obtained when lithiated L1 and L2 were treated with germanium dichloride. We were able to stabilize a monomeric germylene monochloride (7) with L1. However, with L2, an unusual ligand scrambling, and a C-C coupling take place, leading to the formation of a secondary carbocation with GeCl3- as a counter-anion (8). Besides, a germanium dichloride adduct (9) bound to the oxygen center of the ligand was obtained as the minor product.
Keywords: calcium; Germylene; ligand; Magnesium; X-ray Structure

Total synthesis and absolute configuration determination of Ktedonoketone, a benzenoid metabolite from Thermophilic bacterium - Dandawate, Monica; Choudhury, Rahul; Krishna, Gamidi Rama; Reddy, D. Srinivasa (Tetrahedron Letters, 2020)
The successful total synthesis of both enantiomers of ktedonoketone allowed us to decipher an unambiguous assignment of absolute configuration of the natural product. The concise synthesis highlights Wacker oxidation and aldol condensation as key steps. In addition to this, the current synthetic route is suitable to access a library of compounds on the similar skeleton as one can use readily available amino acids and Grignard reagents as variants. (C) 2020 Elsevier Ltd. All rights reserved.
Keywords: Absolute configuration; Ktedonoketone; Total synthesis; Wacker oxidation

Total synthesis of (-)-2-methoxy-2-butenolide-3-cinnamate and its antimicrobial potentials - Said, Madhukar S.; Udavant, Rohini; Sahu, Amit Kumar; Khan, Abujunaid; Nayak, Rashmi; Dastager, Syed G.; Kumar, Pradeep; Gajbhiye, Jayant (Natural Product Research, 2020)
The first total synthesis of (-)-2-methoxy-2-butenolide-3-cinnamate (butenolide cinnamate) was achieved using commercially available starting material. The synthesized compound was found to have promising antibacterial activity against Gram-negative strainsEscherichia coli(ATCC 8739),Salmonella typhimurium(ATCC 23564) andPseudomonas aeruginosa(ATCC 19154) with a minimum inhibitory concentration of 2.0 mu g/mL, 1.0 mu g/mL and 2.0 mu g/mL, respectively. Notably, the compound was more potent against Gram-negative test strains than the Gram-positive test strains.
Keywords: antibacterial activity; butenolide cinnamate; Total synthesis

Total synthesis of beshanzuenone D and its epimers and abiespiroside A - Borade, Balasaheb R.; Dixit, Ruchi; Kontham, Ravindar (Organic Letters, 2020)
A unified and protecting-group-free six-step total synthesis of bisabolane-type sesquiterpenoid beshanzuenone D and its stereoisomers and abiespiroside A using S-(+)-carvone as a common chiral-pool building block is disclosed. This synthetic route features chemoselective allylic chlorination of carvone, Au(I)-catalyzed cydoisomerization induced construction of furan from homopropargylic diol, substrate-controlled selective hydroxylation using Davis-oxaziridine, and dye-sensitized photo-oxidation (through O-1(2)) of hydroxyalkyl tethered furan to access oxaspirolactone as key transformations. A comprehensive set of NMR data along with DFT calculations, ECD spectra, and optical rotation measurements of the synthesized beshanzuenone D and its epimers were obtained to confirm absolute configurations.

Transient alpha-helix in the N-terminal RNA recognition motif of polypyrimidine tract binding protein senses RNA secondary structure - Maris, Christophe; Jayne, Sandrine; Damberger, Fred F.; Beusch, Irene; Dorn, Georg; Ravindranathan, Sapna; Allain, Frederic H-T (Nucleic Acids Research, 2020)
The polypyrimidine tract binding protein (PTB) is a multi-domain protein involved in alternative splicing, mRNA localization, stabilization, polyadenylation and translation initiation from internal ribosome entry sites (IRES). In this latter process, PTB promotes viral translation by interacting extensively with complex structured regions in the 5'-untranslated regions of viral RNAs at pyrimidine-rich targets located in single strand and hairpin regions. To better understand how PTB recognizes structured elements in RNA targets, we solved the solution structure of the N-terminal RNA recognition motif (RRM) in complex with an RNA hairpin embedding the loop sequence UCUUU, which is frequently found in IRESs of the picornovirus family. Surprisingly, a new three-turn alpha 3 helix C-terminal to the RRM, folds upon binding the RNA hairpin. Although alpha 3 does not mediate any contacts to the RNA, it acts as a sensor of RNA secondary structure, suggesting a role for RRM1 in detecting pyrimidine tracts in the context of structured RNA. Moreover, the degree of helix formation depends on the RNA loop sequence. Finally, we show that the alpha 3 helix region, which is highly conserved in vertebrates, is crucial for PTB function in enhancing Encephalomyocarditis virus IRES activity.

Transition metal nickel prevents Tau aggregation in Alzheimer's disease - Gorantla, Nalini Vijay; Das, Rashmi; Balaraman, Ekambaram; Chinnathambi, Subashchandrabose (International Journal of Biological Macromolecules, 2020)
Alzheimer's disease is the leading cause of dementia, effecting majority of aged people worldwide. The multifaceted effectors of Alzheimer's disease primarily include Tau, amyloid-beta along with hyper activation of kinases, oxidative stress and mutations etc., makes it challenging to design therapeutics. Tau is a microtubule-associating protein, which is subjected to cellular stress resulting in the formation of neurofibrillary tangles, leading to loss of affinity for microtubules. This causes loss of microtubule stability and in turn alters axonal integrity. In the present work, emphasis towards understanding interaction of nickel with Tau was made. Metals such as iron, zinc, copper and lead etc., are known to modulate Tau conformation and enhance its aggregation. Our results showed the deliverance of Tau aggregation by nickel and its synthetic morpholine conjugate. Nickel prevents aggregation by inducing degradation of Tau as evidenced by SDS-PAGE and TEM. Nickel and the synthetic conjugate being non toxic to neuro2a cells and prevent Tau aggregation, might direct these complexes to overcome AD. (C) 2019 Published by Elsevier B.V.
Keywords: Aggregation; Alzheimer's disease; metals; Morpholine; Nickel chloride; Tau

Transmetallation vs adduct: diverse reactivity of N,O-ketiminato germylene with [Cp*MCl2](2) (M = Rh or Ir; Cp* = eta(5)-C5Me5) and MCl5 (M = Nb and Ta) - Raghavendra, Beesam; Bakthavachalam, K.; Das, Tamal; Roisnel, Thierry; Sen, Sakya S.; Vanka, Kumar; Ghosh, Sundargopal (Journal of Organometallic Chemistry, 2020)
The reactions of the germylenes, [(Dipp)NCMeCHCORGeCl] (1a: R = Me, 1b: R = Ph) with [Ir2Cl2(mu-Cl)(2)(eta(5)-Cp*)(2)] led to the formation of the adducts [(Dipp)NCMeCHCORGeClIrCl2Cp*] (3a: R = Me and 3b: R = Ph). On the other hand, [Rh2Cl2(mu-Cl)(2)(eta(5)-Cp*)(2)] does not react with the germylenes (1a and 1b). When the reactions of 1a and 1b are carried out with [Cp*TaCl4], the reaction led to decomposition. The reaction of 1a or 1b with TaCl5 yielded the transmetallated products [(Dipp)NCMeCHCORTaCl4] (4a: R = Me, 4b: R = Ph) with the extrusion of GeCl2. Our theoretical studies show that for, the insertion of TaCl5 to 1a and the formation of 4a with concomitant elimination of GeCl2 is energetically favourable. Extrusion of SnCl2 is also observed when the corresponding stannylene, [(Dipp)NCMeCHCOMeSnCl] was reacted with TaCl5. All these compounds have been characterized by H-1 and C-13 NMR spectroscopy, elemental analysis and the constitution of compounds 1b, 3b, and 4a were confirmed by single-crystal X-ray crystallography. (C) 2020 Elsevier B.V. All rights reserved.
Keywords: Adduct formation; Germylenes; Iridium; Ketoiminate; Tantalum; Transmetallation

Tris-heteroleptic ruthenium(II) polypyridyl complexes: Synthesis, structural characterization, photophysical, electrochemistry and biological properties - Bhat, Satish S.; Kumbhar, Avinash S.; Purandare, Neeraja; Khan, Ayesha; Grampp, Gunter; Loennecke, Peter; Hey-Hawkins, Evamarie; Dixit, Ruchi; Vanka, Kumar (Journal of Inorganic Biochemistry, 2020)
{Three water-soluble tris-heteroleptic ruthenium(II) polypyridyl complexes [Ru(bpy)(phen)(bpg)](2+) (1), [Ru (bpy)(dppz)(bpg)]2+ (2), and [Ru(phen)(dppz)(bpg)]2+ (3) (where bpy = 2,2'-bipyridine
Keywords: Circular dichroism; Cytotoxicity; fluorescence; Polypyridyl; ruthenium

Triton X-114 fractionated subcellular proteome ofleptospira interrogansshows selective enrichment of pathogenic and outer membrane proteins in the detergent fraction - Thoduvayil, Sikha; Dhandapani, Gunasekaran; Brahma, Rahul; Devasahayam Arokia Balaya, Rex; Mangalaparthi, Kiran K.; Patel, Krishna; Kumar, Manish; Tennyson, Jebasingh; Satheeshkumar, P. K.; Kulkarni, Mahesh J.; Pinto, Sneha M.; Prasad, T. S. Keshava; et al. (Proteomics, 2020)
The Triton X-114-based solubilization and temperature-dependent phase separation of proteins is used for subcellular fractionation where, aqueous, detergent, and pellet fractions represents cytoplasmic, outer membrane (OM), and inner membrane proteins, respectively. Mass spectrometry-based proteomic analysis of Triton X-114 fractions of proteomic analysis ofLeptospira interrogansidentified 2957 unique proteins distributed across the fractions. The results are compared with bioinformatics predictions on their subcellular localization and pathogenic nature. Analysis of the distribution of proteins across the Triton X-114 fractions with the predicted characteristics is performed based on ``number'' of unique type of proteins, and ``quantity'' which represents the amount of unique protein. The highest number of predicted outer membrane proteins (OMPs) and pathogenic proteins are found in aqueous and pellet fractions, whereas detergent fraction representing the OM has the highest quantity of OMPs and pathogenic proteins though lower in number than the aqueous and pellet fractions. This leaves the possibility of an upsurge in pathogenic proteins and OMPs on the OM under pathogenic conditions suggesting their potential use to combat leptospirosis. Further, the Triton X-114 subcellular fractions are more correlated to enrichment of pathogenic proteins predicted by MP3 software than predicted localization.
Keywords: intensity-based absolute quantification; Leptospira; outer membrane protein; subcellular localization; Triton X-114

Uncovering the origin of enhanced field emission properties of rGO-MnO(2)heterostructures: a synergistic experimental and computational investigation - Rondiya, Sachin R.; Karbhal, Indrapal; Jadhav, Chandradip D.; Nasane, Mamta P.; Davies, Thomas E.; Shelke, V. Manjusha; Jadkar, Sandesh R.; Chavan, Padmakar G.; Dzade, Nelson Y. (RSC Advances, 2020)
The unique structural merits of heterostructured nanomaterials including the electronic interaction, interfacial bonding and synergistic effects make them attractive for fabricating highly efficient optoelectronic devices. Herein, we report the synthesis of MnO(2)nanorods and a rGO/MnO(2)nano-heterostructure using low-cost hydrothermal and modified Hummers' methods, respectively. Detailed characterization and confirmation of the structural and morphological properties are doneviaX-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM) and Transmission Electron Microscopy (TEM). Compared to the isolated MnO(2)nanorods, the rGO/MnO(2)nano-heterostructure exhibits impressive field emission (FE) performance in terms of the low turn-on field of 1.4 V mu m(-1)for an emission current density of 10 mu A cm(-2)and a high current density of 600 mu A cm(-2)at a relatively very low applied electric field of 3.1 V mu m(-1). The isolated MnO(2)nanorods display a high turn-on field of 7.1 for an emission current density of 10 mu A cm(-2)and a low current density of 221 mu A cm(-2)at an applied field of 8.1 V mu m(-1). Besides the superior FE characteristics of the rGO/MnO(2)nano-heterostructure, the emission current remains quite stable over the continuous 2 h period of measurement. The improvement of the FE characteristics of the rGO/MnO(2)nano-heterostructure can be ascribed to the nanometric features and the lower work function (6.01 and 6.12 eV for the rGO with 8% and 16% oxygen content) compared to the isolated alpha-MnO2(100) surface (phi= 7.22 eV) as predicted from complementary first-principles electronic structure calculations based on density functional theory (DFT) methods. These results suggest that an appropriate coupling of rGO with MnO(2)nanorods would have a synergistic effect of lowering the electronic work function, resulting in a beneficial tuning of the FE characteristics.

Understanding alloy structure and composition in sinter-resistant AgPd@SiO2 encapsulated catalysts and their effect on catalytic properties (vol 41, pg 14652, 2017) - Mondal, Sourik; Rajesh, Thattarathody; Dhar, Basab B.; Snellman, Markus; Li, Junjie; Deepak, Francis Leonard; Devi, R. Nandini (New Journal of Chemistry, 2020)

Understanding the influence of alumina supported ruthenium catalysts synthesis and reaction parameters on the hydrodeoxygenation of lignin derived monomers - Singh, Dheerendra; Dhepe, Paresh L. (Molecular Catalysis, 2020)
Up-gradation of lignin derived monomers to value-added and fuel grade products is important to make overall bio-refinery process economical. Although, few studies are devoted on this work yet, systematic study on commercially viable (low loading of metal, recyclable catalyst, mild conditions, high selectivities etc.) is scarce and typically done under harsh conditions. Herein, we report, the methodical effect of support (SiO2, Al2O3 (acidic, basic and neutral), SiO2-Al2O3) on the hydrodeoxygenation (HDO) of lignin derived various monomers, guaiacol, veretrol, eugenol, phenol using very low loading (0.5 wt%) Ru catalyst. Very high yield (82%) of cyclohexanol from guaiacol could be achieved in presence of cyclohexane as a solvent and Ru/Al2O3-Acidic catalyst at 225 degrees C and under 1 MPa H-2 pressure. The detailed study on the effect of solvent, stability and adsorption of reactant & products etc. is done and it was observed that products are more prone to adsorb and undergo further reactions. The complete characterization of fresh and spent catalysts revealed that lower catalyst reduction temperature and presence of Ru in partially higher oxidation state proved by XPS, helps in enhancing the cyclohexanol formation. Subsequently, role of Ru particle size and support on the activity was also investigated.
Keywords: Cyclohexanol; Hydrodeoxygenation; lignin; reaction pathway; supported metal catalyst

Understanding unfolding and refolding of the antibody fragment (Fab). I. In-vitro study - Gani, Kayanat; Bhambure, Rahul; Deulgaonkar, Prashant; Mehta, Deepa; Kamble, Manoj (Biochemical Engineering Journal, 2020)
In-vitro protein refolding is a major rate-limiting step in the large scale production of antibody fragments expressed using a microbial source like E. coli. This investigation is focused on understanding the in-vitro unfolding and refolding of the multi-domain protein involving inter-domain disulfide linkage, like antibody fragment (Fab). Solubilization behavior of the inclusion bodies and unfolding events of Fab fragment (Biosimilar rHu Ranibizumab) were studied using nano-differential scanning fluorimetry (nano-DSF). Fab unfolding behavior was studied by fitting experimental data with the two-state and three-state thermodynamic model. Based on the Fab unfolding understanding, a two-stage design of experiment (DoE) strategy was used for the optimization of the in-vitro refolding condition of a Fab fragment. Refolding yield of 56.03 +/- 1.15 % was achieved using the optimized oxidative refolding conditions maintained by appropriate dilution factor and redox reagent ratio. Refolding kinetics of the rHu Ranibizumab was analyzed using a three-parameter kinetic model showing rate constant k(1) :7.05e(-6) l/mg.min, k(2) :0.57 l/mg.min, and k(3) :310.19 l/mg.min. Based on observed refolding kinetics, it was concluded that the Fab refolding follows a three-state mechanism with the refolding intermediate/(s) formation from light and heavy chain of the Fab fragment as an overall rate-limiting step. The method described here is a useful tool to identify high-yield scalable refolding conditions for multi-domain proteins involving inter-domain disulfide bonds.
Keywords: Antibody fragment; In-vitro refolding; Refolding kinetics; rHu Ranibizumab; Two-state and Three-state models

Unprecedented isomerism-activity relation in molecular electrocatalysis - Kottaichamy, Alagar Raja; Begum, Shabbah; Nazrulla, Mohammed Azeezulla; Dargily, Neethu Christudas; Devendrachari, Mruthyunjayachari Chattanahalli; Bhat, Zahid Manzoor; Thimmappa, Ravikumar; Kotresh, Harish Makri Nimbegondi; Vinod, Chathakudath Prabhakaran; Thotiyl, Musthafa Ottakam (Journal of Physical Chemistry Letters, 2020)
The role of electrocatalysts in energy storage/conversion, biomedical and environmental sectors, green chemistry, and much more has generated enormous interest in comprehending their structure-activity relations. While targeting the surface-to-volume ratio, exposing reactive crystal planes and interfacial modifications are time-tested considerations for activating metallic catalysts; it is primarily by substitution in molecular electrocatalysts. This account draws the distinction between a substituent's chemical identity and isomerism, when regioisomerism of the -NO2 substituent is conferred at the ``alpha'' and ``beta'' positions on the macrocycle of cobalt phthalocyanines. Spectroscopic analysis and theoretical calculations establish that the beta isomer accumulates catalytically active intermediates via a cumulative influence of inductive and resonance effects. However, the field effect in the alpha isomer restricts this activation due to a vanishing resonance effect. The demonstration of the distinct role of isomerism in substituted molecular electrocatalysts for reactions ranging from energy conversion to biosensing highlights that isomerism of the substituents makes an independent contribution to electrocatalysis over its chemical identity.

Untargeted metabolomics reveals alterations in metabolites of lipid metabolism and immune pathways in the serum of rats after long-term oral administration of Amalaki rasayana - Kumar, Vikas; Kumar, A. Aneesh; Joseph, Vinod; Dan, Vipin Mohan; Jaleel, Abdul; Kumar, T. R. Santhosh; Kartha, Chandrasekharan C. (Molecular and Cellular Biochemistry, 2020)
Amalaki rasayana, a traditional preparation, is widely used by Ayurvedic physicians for the treatment of inflammatory conditions, cardiovascular diseases, and cancer. Metabolic alterations induced by Amalaki rasayana intervention are unknown. We investigated the modulations in serum metabolomic profiles in Wistar rats following long-term oral administration of Amalaki rasayana. Global metabolic profiling was performed of the serum of rats administered with either Amalaki rasayana (AR) or ghee + honey (GH) for 18 months and control animals which were left untreated. Amalaki rasayana components were confirmed from AR extract using HR-LCMS analysis. Significant reductions in prostaglandin J2, 11-dehydrothromboxane B2, and higher levels of reduced glutathione and glycitein metabolites were observed in the serum of AR administered rats compared to the control groups. Eleven different metabolites classified as phospholipids, glycerophospholipids, glucoside derivatives, organic acids, and glycosphingolipid were exclusively observed in the AR administered rats. Pathway analysis suggests that altered metabolites in AR administered rats are those associated with different biochemical pathways of arachidonic acid metabolism, fatty acid metabolism, leukotriene metabolism, G-protein mediated events, phospholipid metabolism, and the immune system. Targeted metabolomics confirmed the presence of gallic acid, ellagic acid, and arachidonic acid components in the AR extract. The known activities of these components can be correlated with the altered metabolic profile following long-term AR administration. AR also activates IGF1R-Akt-Foxo3 signaling axis in heart tissues of rats administered with AR. Our study identifies AR components that induce alterations in lipid metabolism and immune pathways in animals which consume AR for an extended period.
Keywords: Amalaki rasayana; Ayurvedic medicines; Leukotriene metabolism; Lipid metabolism; Metabolic profiling

Variations in activity of Ru/TiO(2 )and Ru/Al2O3 catalysts for CO2 hydrogenation: an investigation by in-situ infrared spectroscopy studies - Dongapure, Pavan; Bagchi, Sayan; Mayadevi, S.; Devi, R. Nandini (Molecular Catalysis, 2020)
CO2 hydrogenation to methane, an important reaction strategically and also for value adding to CO2, is investigated on two different catalysts, Ru supported on alumina as well as titania to understand better low temperature activity of Ru/TiO2 catalyst. In-situ infrared studies are carried out in three different steps, viz., (i) CO2 adsorption on fully reduced catalyst (ii) reaction of these adsorbed species with gaseous H-2 and (iii) under co-feed of CO2 and H-2, at different temperatures. On Ru/Al2O3 catalyst, CO2 reacts with hydroxyls on the support surface to form carbonate and adsorbs reductively on metal as CO. Further reduction to formate and methyl species occurs on reaction with H. Small concentration of the reactive intermediate formyl forms only at high temperatures. Whereas, bare TiO2 itself seems capable of reductive adsorption of CO2 as formate indicating enhanced reducibility of titania based catalyst. Formyl groups are observed at low temperatures in Ru/TiO2 in step (ii), which further forms methyl and gaseous methane at much lower temperatures when compared to alumina catalyst. Highly reactive CO species loosely bound to metal-support interface observed at high temperatures, which is not present on Ru/Al2O3 catalyst also makes this catalyst superior. In comparison, linearly bound CO seen in alumina catalyst is not as reactive.
Keywords: CO2 hydrogenation; In-situ infra red spectroscopy; Ru/Al2O3; Ru/TiO2

Wavelength dependent luminescence decay kinetics in `quantum-confined' g-C(3)N(4)nanosheets exhibiting high photocatalytic efficiency upon plasmonic coupling - Mondal, Sanjit; Sahoo, Lipipuspa; Vaishnav, Yuvraj; Mishra, Samita; Roy, Raj Sekhar; Vinod, C. P.; De, Arijit K.; Gautam, Ujjal K. (Journal of Materials Chemistry A, 2020)
Serendipitous observations offer newer insights into materials properties. Here we describe g-C(3)N(4)nanosheets exhibiting remarkably blue-shifted photoluminescence within the 390-580 nm range centred at 425 nm which matches more closely with its `quantum-dots', and yet is excitation-wavelength independent. Moreover, surprisingly, the luminescence decay becomes increasingly slow at higher emission wavelengths, by up to 10 times. The nanosheets absorb only a fraction of visible-light. To improve this, when we designed a nanocomposite of g-C(3)N(4)and Au nanoparticles (NPs), it retained the PL characteristics and also exhibited excellent light-harvesting and photocatalytic efficiency for benzylamine (BA) oxidation. The surface plasmon resonance of the Au NPs is responsible for the high visible-light response and assisting the reaction by the `hot-electron' injection mechanism, while an uncharacteristic, pronounced co-catalytic effect by them further improves the efficiency. The conversion is 98% with >99% selectivity over 1.5 h of natural sunlight and open-air, probably the highest efficiency for BA photo-oxidation reactions. Even though such a dual role by plasmonic NPs has remained unscrutinized, we argue that the charge-transfer processes for the `hot-carrier' injection and co-catalytic events are well-separated in time due to a much slower photon incident frequency on a catalyst particle, enabling both to occur simultaneously in the same particle.

[1,3]-Claisen rearrangement via removable functional group mediated radical stabilization - Alam, Md Nirshad; Dash, Soumya Ranjan; Mukherjee, Anirban; Pandole, Satish; Marelli, Udaya Kiran; Vanka, Kumar; Maity, Pradip (Organic Letters, 2021)
A thermal O-to-C [1,3]-rearrangement of alpha-hydroxy acid derived enol ethers was achieved under mild conditions. The 2-aminothiophenol protection of carboxylic acids facilitates formation of the [1,3] precursor and its thermal rearrangement via stabilization of a radical intermediate. Experimental and theoretical evidence for dissociative radical pair formation, its captodative stability via aminothiophenol, and a unique solvent effect are presented. The aminothiophenol was deprotected from rearrangement products as well as after derivatization to useful synthons.

Acid mediated sulfonylation of para-quinone methides with tosylmethyl isocyanides for the synthesis of diarylmethyl sulfones - Kumar, Pawan; Kale, Someshwar B.; Gonnade, Rajesh G.; Das, Utpal (ChemistrySelect, 2021)
An efficient, hydrochloric acid promoted reaction for the synthesis of diarylmethyl sulfones has been developed via unprecedented 1, 6-conjugate addition reaction of tosylmethyl isocyanide (TosMIC) with para-quinone methides.This catalyst free reaction provides various diarylmethyl sulfones in good to excellent yields in an operationally simple method under metal free conditions. Further transformations of the productsare also demonstrated.
Keywords: 1; 6-Conjugate addition; aromatization; Diarylmethylsulfone; para-Quinonemethide; TosMIC

Advances in solid catalysts for selective hydrogenolysis of glycerol to 1,3-propanediol - Bhowmik, Susmita; Darbha, Srinivas (Catalysis Reviews-Science and Engineering, 2021)
Glycerol is one of the top 12 platform chemicals obtained from biomass. Its surplus availability as a by-product of biodiesel, fat-splitting and soap manufacturing industries and affordable price lends significant opportunity for its valorization, using solid catalysts, into propanediols (PDOs), particularly to 1,3-propanediol (1,3-PDO), by selective hydrogenolysis. 1,3-PDO is an important chemical with wide applications including that as a precursor in polymers manufacturing. However, the synthesis of 1,3-PDO by selective cleavage of the secondary C-O bond of glycerol in the presence of hydrogen (instead of the primary C-O bond yielding 1,2-PDO) is highly challenging. Of late, supported Pt and Ir catalysts in combination with a reducible oxide (WO(x)or ReOx) were found selective for 1,3-PDO formation. Support, metals composition and additives (co-added metals) affect the performance of these catalysts. Detailed investigations revealed that metal dispersion, electronic connectivity between metal and metal oxide/support, hydrogen activation/spillover and Bronsted acidity are some parameters that influence the activity and selectivity of these bi-functional, metal-metal oxide catalysts. This review summarizes the latest advances in these solid catalysts for selective hydrogenolysis of glycerol to 1,3-PDO, a monomer for advanced polymers.
Keywords: 1; 3-Propanediol; bifunctional metal-metal oxide catalyst; biomass valorization; Glycerol; Hydrogenolysis

Alpha-Linolenic acid inhibits Tau aggregation and modulates Tau conformation - Desale, Smita Eknath; Dubey, Tushar; Chinnathambi, Subashchandrabose (International Journal of Biological Macromolecules, 2021)
Alzheimer's disease is characterized by important patho-proteins, which being composed of Amyloid-beta, plaques and intracellular neurofibrillary tangles of Tau. Intrinsically disordered protein tau has several interacting partners, which are necessary for its normal functioning. Tau has been shown to interact with various proteins, nucleic acid, and lipids. alpha-Linolenic acid (ALA) a plant-based omega-3 fatty acid has been studied for its role as neuroprotective and beneficial fatty add in the brain. In this study, we are focusing on the ability of ALA to induce spontaneous assembly in tau protein. ALA inhibited the Tau aggregation as indicated by reduced ThS fluorescence kinetics, which indicates no aggregation of Tau. Similarly, SDS-PAGE analysis supported that ALA exposure inhibited the aggregation as no higher-order tau species were observed. Along with its ability to impede the aggregation of Tau, ALA also maintains a native random coiled structure, which was estimated by CD spectroscopy. Finally, TEM analysis showed that the formation of Tau fibrils was found to be discouraged by ALA. Hence, conclusion of the study suggested that ALA profoundly inhibited aggregation of Tau and maintained it's the random-coil structure. (C) 2020 Elsevier B.V. All rights reserved.
Keywords: alpha-linolenic acid; Alzheimer's disease; Free fatty adds; Tau conformation; Tau fibrillization

Alpha-Linolenic acid modulates phagocytosis and endosomal pathways of extracellular Tau in microglia - Desale, Smita Eknath; Chinnathambi, Subashchandrabose (Cell Adhesion & Migration, 2021)
Microglia, the resident immune cells, were found to be activated to inflammatory phenotype in Alzheimer's disease (AD). The extracellular burden of amyloid-beta plaques and Tau seed fabricate the activation of microglia. The seeding effect of extracellular Tau species is an emerging aspect to study about Tauopathies in AD. Tau seeds enhance the propagation of disease along with its contribution to microglia-mediated inflammation. The excessive neuroinflammation cumulatively hampers phagocytic function of microglia reducing the clearance of extracellular protein aggregates. Omega-3 fatty acids, especially docosahexaenoic acid and eicosapentaenoic acid, are recognized to induce anti-inflammatory phenotype of microglia. In addition to increased cytokine production, omega-3 fatty acids enhance phagocytic receptors expression in microglia. In this study, we have observed the phagocytosis of extracellular Tau in the presence of alpha-linolenic acid (ALA). The increased phagocytosis of extracellular Tau monomer and aggregates have been observed upon ALA exposure to microglia cells. After internalization, the degradation status of Tau has been studied with early and late endosomal markers Rab5 and Rab7. Further, the lysosome-mediated degradation of internalized Tau was studied with LAMP-2A, a lysosome marker. The enhanced migratory ability in the presence of ALA could be beneficial for microglia to access the target and clear it. The increased migration of microglia was found to induce the microtubule-organizing center repolarization. The data indicate that the dietary fatty acids ALA could significantly enhance phagocytosis and intracellular degradation of internalized Tau. Our results suggest that microglia could be influenced to reduce extracellular Tau seed with dietary fatty acids.
Keywords: alpha-linolenic acid; endosomal markers; Fatty acids; MTOC repolarization; Phagocytosis; Tauopathy

Antimicrobial and antioxidant potential of a standardized ayurvedic formulation explains its clinical efficacy as gargles in post-radiotherapy oral cancer patients - Chavan, Sandeep; Bhuvad, Sushama; Kumbhlakar, Bhagyashri; Auti, Jyoti; Walunj, Tanhaji; Pathak, Shridevi; Tanpure, Rahul; Gujar, Shweta; Shinde, Jagdish; Kulkarni, Arvind; Gupta, Vidya; Deshmukh, Vineeta; et al. (Journal of Herbal Medicine, 2021)
Introduction: Exploring the antioxidant and antimicrobial potential of a standardized proprietary poly-herbal powder and evaluating its clinical efficacy as an Ayurvedic gargle (Gandush) for reducing oral microbial load and side effects of radiotherapy in oral cavity cancer patients was the aim of this pilot study. Methods: Formulation (Gandush Churna) comprising Terminalia chebula Retz., Terminalia bellirica (Gaertn.) Roxb., Phyllanthus emblica L. and Curcuma longa L. and its decoction (Gandush Kwath) were standardized. In-vitro antioxidant potential and antimicrobial activity against selective bacterial and fungal strains were studied. Oral cavity cancer patients who had undergone radiotherapy were enrolled. The decoction was prepared by soaking Gandush Churna in water, boiling and reducing by 50 %; and was used for gargling, twice a day, for 7 days. Total microbial count and identification of microbiota in the oral cavity as well as symptoms graded as per Common Terminology Criteria for Adverse Events, were noted before and after the treatment. Change in microbial load and shift in symptom gradations were analyzed. Results: A monograph with physicochemical, chromatography, safety and stability parameters was developed. The decoction possessed good in-vitro antioxidant and antimicrobial activities. Gargling therapy significantly reduced bacterial load while mildly controlled the fungal infection in oral cavity cancer patients. It significantly reduced the severity of symptoms viz. stomatitis and local pain, with considerably decreased xerostomia and dysphagia. Conclusions: Intervention of gargle therapy using poly-herbal formulation may serve as an effective complementary treatment to improve oral hygiene and reduce side effects of radiotherapy in oral cancer patients.
Keywords: Anti-microbial; Antioxidant; Gandush; Gargle therapy; Oral cavity cancers; Radiotherapy side effects

Antiviral drugs prioritization for COVID-19 management based on rational selection - Joshi, Rakesh S.; Giri, Ashok P.; Kulkarni, Mahesh J.; Gupta, Mahesh; Verma, Savita; Chaudhry, Dhruva; Deshmukh, Narendra; Chugh, Anita (Current Science, 2021)
The SARS-CoV-2 infection has resulted in COVID-19 pandemic worldwide. It has infected around 0.1 billion individuals and caused 2 million fatalities across the globe till mid-January 2021. Drug repurposing has been utilized as the most preferred therapeutic intervention for COVID-19 mitigation due to its necessity and feasibility. To prioritize therapeutic regime against COVID-19, we used 61 antiviral drugs and their combinations. Selected molecules were subjected to virtual screening against: (i) human angiotensin-converting enzyme 2 receptor binding domain (hACE-2) which serves as an anchor for virus attachment and entry, (ii) SARS-CoV-2 RNA dependent RNA polymerase (RdRp) responsible for viral RNA replication, and (iii) SARS-CoV-2 main protease (M-Pro) needed for viral polyprotein slab proteolytic processing. Based on docking score, pharmacodynamic and pharmacokinetic parameters, combinations of Daclatasvir, Elbasvir, Indinavir, Ledipasvir, Paritaprevir and Rilpivirine were analysed further. Our analysis suggested Sofosbuvir in combination with Ledipasvir and Daclatasvir as potential therapeutic agents for SARS-CoV-2. The combined score suggests that these combinations have superior anti-SARS-CoV-2 potential than Remdesivir and other investigational drugs. The present work provides a rationale-based approach to select drugs with possible anti-SARS-CoV-2 activity for further clinical evaluation.
Keywords: Drug repurposing; hACE-2; main protease; RNA dependent RNA polymerase; SARS-CoV-2

Architecture of NaFe(MoO4)2 as a novel anode material for rechargeable lithium and sodium ion batteries - Tamboli, Asiya M.; Tamboli, Mohaseen S.; Praveen, C. S.; Dwivedi, Pravin Kumari; Karbhal, Indrapal; Gosavi, Suresh W.; Shelke, V, Manjusha; Kale, Bharat B. (Applied Surface Science, 2021)
In recent decades, particular focus has been given to enhance the capacity of LIBs and SIBs either by developing new materials or by modifying existing materials. Hence, we have demonstrated a new anode material i.e. sodium iron molybdate [NaFe(MoO4)2] for both LIBs and SIBs. NaFe(MoO4)2 has been successfully synthesized by solid-state combustion technique and tested as a promising new anode material for both LIBs and SIBs. A detailed analysis of the crystal structure has been performed using DFT calculations. NaFe(MoO4)2 crystallizes in the monoclinic phase with the space group C2/c (#15). FESEM also shows highly crystalline monoclinic shaped crystals of micron size. When evaluated as an anode material for LIBs, NaFe(MoO4)2 electrode exhibited electrochemical capacity of 920 mAhg- 1 in the second cycle at the current density of 50 mAg-1. Though capacity decreases on further cycling, the coulombic efficiency was maintained at 99% for 50 cycles. Significantly, a high discharge capacity of 100 mAhg- 1 was maintained at a very high rate of 1 Ag-1. On the other hand, we have also tested NaFe(MoO4)2 for SIBs which shows excellent reversible specific capacity i.e. 100 mAhg- 1 at the current density of 100 mAg-1 even after 500 cycles. This novel system has shown good stability for LIBs and SIBs which is hitherto unattempted.
Keywords: Electrochemical study; lithium-ion battery; Morphology; NaFe(MoO4)2; Sodium-ion battery

Aspergillus derived mycotoxins in food and the environment: prevalence, detection, and toxicity - Navale, Vishwambar; Vamkudoth, Koteswara Rao; Ajmera, Shanthipriya; Dhuri, Vaibhavi (Toxicology Reports, 2021)
<em style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">Aspergillus<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;"> species are the paramount ubiquitous fungi that contaminate various food substrates and produce biochemicals known as mycotoxins. Aflatoxins (AFTs), ochratoxin A (OTA), patulin (PAT), citrinin (CIT), aflatrem (AT), secalonic acids (SA), cyclopiazonic acid (CPA), terrein (TR), sterigmatocystin (ST) and gliotoxin (GT), and other toxins produced by species of <em style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">Aspergillus<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;"> plays a major role in food and human health. Mycotoxins exhibited wide range of toxicity to the humans and animal models even at nanomolar (nM) concentration. Consumption of detrimental mycotoxins adulterated foodstuffs affects human and animal health even trace amounts. Bioaerosols consisting of spores and hyphal fragments are active elicitors of bronchial irritation and allergy, and challenging to the public health. <em style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">Aspergillus<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;"> is the furthermost predominant environmental contaminant unswervingly defile lives with a 40–90 % mortality risk in patients with conceded immunity. Genomics, proteomics, transcriptomics, and metabolomics approaches useful for mycotoxins’ detection which are expensive. Antibody based detection of toxins chemotypes may result in cross-reactivity and uncertainty. Aptamers (APT) are single stranded DNA (ssDNA/RNA), are specifically binds to the target molecules can be generated by systematic evolution of ligands through exponential enrichment (SELEX). APT are fast, sensitive, simple, in-expensive, and field-deployable rapid point of care (POC) detection of toxins, and a better alternative to antibodies.

Bibliometric analysis of emerging technologies in the field of computer science helping in ovarian cancer research - Kothari, Dr. Sonali; Gupta, Anvita; Agrawal, Muskaan; Jaggi, Kajal; Goswami, Adhiraj; Kotecha, Ketan; Dr, Karthikeyan; Khedkar, Vijayhsri (Library Philosophy and Practice, 2021)
This study is carried out to provide an analysis of the literature available at the intersection of ovarian cancer and computing. A comprehensive search was conducted using Scopus database for English-language peer-reviewed articles. The study administers chronological, domain clustering and text analysis of the articles under consideration to provide high-level concept map composed of specific words and the connections between them.

Bibliometric analysis of named entity recognition for chemoinformatics and biomedical information extraction of ovarian cancer - Khedkar, Vijayhsri; Fernandes, Charlotte; desai, Devshi; Shinde, Mansi; Dr, Chavan,; Dr, Tidke,; Dr, Karthikeyan (Library Philosophy and Practice, 2021)
With the massive amount of data that has been generated in the form of unstructured text documents, Biomedical Named Entity Recognition (BioNER) is becoming increasingly important in the field of biomedical research. Since currently there does not exist any automatic archiving of the obtained results, a lot of this information remains hidden in the textual details and is not easily accessible for further analysis. Hence, text mining methods and natural language processing techniques are used for the extraction of information from such publications.Named entity recognition, is a subtask that comes under information extraction that focuses on finding and categorizing specific entities in text. In this paper, bibliometric analysis of named entity recognition of ovarian cancer is carried out using information about publications from Scopus. The most productive journals, countries and authors are determined. The most frequently cited article and its citation history has been described. Also bibliometric maps based on citation network among countries are constructed. This study can assist people in the medical field to get a comprehensive understanding of the study of BioNER. It can also be utilized for reference works, for the research and application of the BioNER visualization methods.

Bioglycerol (C3) upgrading to 2,3-butanediol (C4) by cell-free extracts of Enterobacter aerogenes NCIM 2695 - Parate, Roopa; Borgave, Mrunal; Dharne, Mahesh; Rode, Chandrashekhar (Journal of Chemical Technology and Biotechnology, 2021)
BACKGROUND Production of biobased chemicals from renewable resources is a green starring approach that serves as a substitute to petroleum derivatives. Bioglycerol, with its growing production as a co-product of biodiesel, is an attractive low-cost feedstock for the synthesis of platform chemicals by microbial fermentation. 2,3-butanediol (2,3-BDO) is amongst the top biorefinery platform chemicals that can be produced by glycerol fermentation. RESULTS The `Circular Economy' concept is demonstrated by converting the by-product bioglycerol using a cell-free extract of Enterobacter aerogenes NCIM 2695 (National Collection of Industrial Microorganisms, NCIM), yielding 22 g L-1 2,3-BDO, in 96 h, 98% atom economy and 0.4 g/g E factor. The cell-free bioglycerol conversion to 2,3-BDO was proved using a modified procedure for determining glycerol dehydrogenase enzyme assay by protein analysis and it was also shown to be cell-bounded. CONCLUSION Our study offers an effective utilization of the leftover material (i.e. cell-free extract) that biocatalysed C3 to C4 diol, which adds value to the overall economics of the process using only crude glycerol (C3) itself as a fermentative medium.
Keywords: 2; 3-Butanediol; atom economy; circular economy; E factor; Glycerol; glycerol dehydrogenase

Biological process of lysine-tRNA charging is therapeutically targetable in liver cancer - Zhang, Ruyi; Noordam, Lisanne; Ou, Xumin; Ma, Buyun; Li, Yunlong; Das, Pronay; Shi, Shaojun; Liu, Jiaye; Wang, Ling; Li, Pengfei; Verstegen, Monique M. A.; Reddy, D. Srinivasa; et al. (Liver International, 2021)
Background & Aims Mature transfer RNAs (tRNA) charged with amino acids decode mRNA to synthesize proteins. Dysregulation of translational machineries has a fundamental impact on cancer biology. This study aims to map the tRNAome landscape in liver cancer patients and to explore potential therapeutic targets at the interface of charging amino acid with tRNA. Methods Resected tumour and paired tumour-free (TFL) tissues from hepatocellular carcinoma (HCC) patients (n = 69), and healthy liver tissues from organ transplant donors (n = 21), HCC cell lines, and cholangiocarcinoma (CC) patient-derived tumour organoids were used. Results The expression levels of different mature tRNAs were highly correlated and closely clustered within individual tissues, suggesting that different members of the tRNAome function cooperatively in protein translation. Interestingly, high expression of tRNA-Lys-CUU in HCC tumours was associated with more tumour recurrence (HR 1.1;P = .022) and worse patient survival (HR 1.1;P = .0037). The expression of Lysyl-tRNA Synthetase (KARS), the enzyme catalysing the charge of lysine to tRNA-Lys-CUU, was significantly upregulated in HCC tumour tissues compared to tumour-free liver tissues. In HCC cell lines, lysine deprivation, KARS knockdown or treatment with the KARS inhibitor cladosporin effectively inhibited overall cell growth, single cell-based colony formation and cell migration. This was mechanistically mediated by cell cycling arrest and induction of apoptosis. Finally, these inhibitory effects were confirmed in 3D cultured patient-derived CC organoids. Conclusions The biological process of charging tRNA-Lys-CUU with lysine sustains liver cancer cell growth and migration, and is clinically relevant in HCC patients. This process can be therapeutically targeted and represents an unexplored territory for developing novel treatment strategies against liver cancer.
Keywords: Cladosporin; liver cancer; lysine; Lysyl-tRNA Synthetase; tRNA-Lys-CUU; tRNAome

Boolean model for melanogenesis - Dnyane, Pooja; Gadgil, Chetan (Physical Biology, 2021)
Melanogenesis is a highly regulated process through which the pigment melanin is produced in skin cells. Irregularities in the molecular events that govern the process of skin pigmentation can cause disorders like vitiligo. In order to understand the biology of disease progression, it is important to have an in depth understanding of intracellular events. Mathematical models provide an integrated view of intracellular signalling. There are very few models to date that incorporate intracellular processes relevant to melanogenesis and only one to our knowledge that simulates the dynamics of response to varying levels of input. Here, we report the formulation of the largest Boolean model (265 nodes) for melanogenesis to date. The model was built on the basis of a detailed interaction network graph published by Raghunath et al. Through additional manual curation of the reported interactions, we converted the graph into a set of Boolean rules, following the procedure of the first Boolean model (62 nodes) for melanogenesis published by Lee et al. Simulations show that the predicted response to varying UV levels for most of the nodes is similar to the predictions of the existing model. The greater complexity allows investigation of the sensitivity of melanin to additional nodes. We carried out perturbation analysis of the network through node deletion and constitutive activation to identify sensitivity of outcomes, and compared the nodes identified as sensitive to previous reports.
Keywords: Boolean model; melanogenesis; Signal transduction

Can we identify the salt-cocrystal continuum state using XPS? - Tothadi, Srinu; Shaikh, Tabrez Rafique; Gupta, Sharad; Dandela, Rambabu; Vinod, Chathakudath P.; Nangia, Ashwini K. (Crystal Growth & Design, 2021)
X-ray photoelectron spectroscopy (XPS) is used to understand the nature of acid-base crystalline solids, to know whether the product is a salt (proton transfer, O-center dot center dot center dot H-N+) or a cocrystal (neutral adduct, O-H center dot center dot center dot N). The present study was carried out to explore if intermediate states of proton transfer from COOH to nitrogen (the proton resides between hydrogen bonded to O and N, O center dot center dot center dot H center dot center dot center dot N, quasi state) can be differentiated from a salt (complete proton transfer, N+-H center dot center dot center dot center dot O-) and cocrystal (no proton transfer, O-H center dot center dot center dot N) using N 1s XPS spectroscopy. The intermediate states of proton transfer arise when the pK(a) difference between the acid and the conjugate base is between -1 and 4, -1 < Delta pK(a) < 4, a situation common with COOH and pyridine functional groups present in drug molecules and pharmaceutically acceptable coformers. Complexes of pyridine N bases with aromatic COOH molecules in nine salts/cocrystals were cocrystallized, and their N 1s core binding energies in XPS spectra were measured. The proton state was analyzed by single-crystal X-ray diffraction for confirmation. Three new complexes were crystallized and analyzed by XPS spectra (without knowledge of their X-ray structures), to assess the predictive ability of XPS spectra in differentiating salt-cocrystal intermediate states against the extremities. The XPS results were subsequently confirmed by single-crystal X-ray data. Complexes of 3,5-dinitrobenzoic acid and isonicotinamide in 1:1 and 1:2 ratios exist as a salt and a salt-cocrystal continuum, respectively, as shown by the N 1s core binding energies. The proton states of the crystalline solids by XPS are in good agreement with the corresponding crystal structures. Other complexes, such as those of 3,5-dinitrobenzoic acid with 1,2-bis(4-pyridyl)ethylene, exhibit a salt-cocrystal continuum, maleic acids with 1,2-bis(4-pyridyl)ethylene and acridine are salts, 2-hydroxybenzoic acid and acridine is a salt, and the complex of 3,5-dinitrobenzoic acid and 3-hydroxypyridine is a salt and salt-cocrystal continuum, while fumaric acids with 1,2-bis(4-pyridyl)ethylene and acridine are cocrystals. Furthermore, three new acidbase complexes of 3,5-dinitrobenzoic acid with phenazine, 4-hydroxypyridine, and 4-cyanopyridine were studied initially by XPS and then confirmed by X-ray diffraction. In summary, since the N 1s binding energies cluster in a narrow range as cocrystals (398.7-398.9 eV) and salts (400.1-401.1 eV), it is clearly possible to differentiate between cocrystals and salts, but the saltcocrystal continuum values in XPS spectra are clustered in an intermediate range of cocrystals and salts but overlap with those of cocrystal or salt binding energies.

Combating multi-drug resistant malaria parasite by inhibiting falcipain-2 and heme-polymerization: Artemisinin-peptidyl vinyl phosphonate hybrid molecules as new antimalarials - Aratikatla, Eswar K.; Kalamuddin, Md; Rana, Kalpeshkumar C.; Datta, Gaurav; Asad, Mohd; Sundararaman, Srividhya; Malhotra, Pawan; Mohmmed, Asif; Bhattacharya, Asish K. (European Journal of Medicinal Chemistry, 2021)
<span style="color: rgb(33, 33, 33); font-family: BlinkMacSystemFont, -apple-system, "Segoe UI", Roboto, Oxygen, Ubuntu, Cantarell, "Fira Sans", "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">Artemisinin-based combination therapies (ACTs) have been able to reduce the clinical and pathological malaria cases in endemic areas around the globe. However, recent reports have shown a progressive decline in malaria parasite clearance in South-east Asia after ACT treatment, thus envisaging a need for new artemisinin (ART) derivatives and combinations. To address the emergence of drug resistance to current antimalarials, here we report the synthesis of artemisinin-peptidyl vinyl phosphonate hybrid molecules that show superior efficacy than artemisinin alone against chloroquine-resistant as well as multidrug-resistant Plasmodium falciparum strains with EC<span style="box-sizing: inherit; font-size: 12px; line-height: 0; position: relative; bottom: -0.25em; color: rgb(33, 33, 33); font-family: BlinkMacSystemFont, -apple-system, "Segoe UI", Roboto, Oxygen, Ubuntu, Cantarell, "Fira Sans", "Droid Sans", "Helvetica Neue", sans-serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">50<span style="color: rgb(33, 33, 33); font-family: BlinkMacSystemFont, -apple-system, "Segoe UI", Roboto, Oxygen, Ubuntu, Cantarell, "Fira Sans", "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;"> in pico-molar ranges. Further, the compounds effectively inhibited the survival of ring-stage parasite for laboratory-adapted artemisinin-resistant parasite lines as compared to artemisinin. These hybrid molecules showed complete parasite clearance in vivo using P. berghei mouse malaria model in comparison to artemisinin alone. Studies on the mode of action of hybrid molecules suggested that these artemisinin-peptidyl vinyl phosphonate hybrid molecules possessed dual activities: inhibited falcipain-2 (FP-2) activity, a P. falciparum cysteine protease involved in hemoglobin degradation, and also blocked the hemozoin formation in the food-vacuole, a step earlier shown to be blocked by artemisinin. Since these hybrid molecules blocked multiple steps of a pathway and showed synergistic efficacies, we believe that these lead compounds can be developed as effective antimalarials to prevent the spread of resistance to current antimalarials.

Conserved RNA binding activity of phosphatidyl inositol 5-phosphate 4-kinase (PIP4K2A) - Behari, Jatin; Borkar, Pranita; Vindu, Arya; Dandewad, Vishal; Upadrasta, Sindhuri; Shanmugam, Dhanasekaran; Seshadri, Vasudevan (Frontiers in Molecular Biosciences, 2021)
Plasmodium falciparum is a causative agent for malaria and has a complex life cycle in human and mosquito hosts. During its life cycle, the malarial parasite Plasmodium goes through different asexual and sexual stages, in humans and mosquitoes. Expression of stage-specific proteins is important for successful completion of its life cycle and requires tight gene regulation. In the case of Plasmodium, due to relative paucity of the transcription factors, it is postulated that posttranscriptional regulation plays an important role in stage-specific gene expression. Translation repression of specific set of mRNA has been reported in gametocyte stages of the parasite. A conserved element present in the 3 ` UTR of some of these transcripts was identified. Phosphatidylinositol 5-phosphate 4-kinase (PIP4K2A) was identified as the protein that associates with these RNA. We now show that the RNA binding activity of PIP4K2A is independent of its kinase activity. We also observe that PIP4K2A is imported into the parasite from the host on Plasmodium berghei and Toxoplasma gondii. The RNA binding activity of PIP4K2A seems to be conserved across species from Drosophila and C. elegans to humans, suggesting that the RNA binding activity of PIP4K may be important, and there may be host transcripts that may be regulated by PIP4K2A. These results identify a novel RNA binding role for PIP4K2A that may not only play a role in Plasmodium propagation but may also function in regulating gene expression in multicellular organisms.
Keywords: malaria; posttranscriptional gene regulation; RNA-protein interaction; translation regulation

Construction of beta-cyclodextrin linked glycidyl methacrylate polymers for stereoselective separation of chiral drug - Wale, Apparav; Mulani, Khudbudin; Deshpande, Supriya; Rajan, C. R.; Ponrathnam, Surendra (Journal of Polymer Research, 2021)
In this present study, a series of cross-linked porous polymers based on Glycidyl Methacrylate (GMA) were synthesized by suspension polymerization using cyclohexanol and hexanol as pore generating solvents. beta-cyclodextrin (beta-CD) was covalently bonded to the polymers by using Hexamethylene Diisocyanate (HMDI) and Sebacoyl Chloride (SC) as spacer arms. The effects of matrix properties such as pore volume, type of crosslinker, and spacer on the loading of beta-cyclodextrin were investigated. The stereoselective binding of enantiomers of the anti-depressant drug citalopram was studied using beta-cyclodextrin loaded polymers under batch adsorption mode. The capacity factor and selectivity of isomers were investigated also. This study reveals that these beta-cyclodextrin bonded Glycidyl Methacrylate (GMA) polymers are potentially suitable for chromatographic separation of citalopram.
Keywords: beta-cyclodextrin; Citalopram; Glycidyl Methacrylate (GMA) beads; HPLC etc; Stereoslelctivity

Continuous citrate-capped gold nanoparticle synthesis in a two-phase flow reactor - Damilos, Spyridon; Alissandratos, Ioannis; Panariello, Luca; Radhakrishnan, Anand N. P.; Cao, Enhong; Wu, Gaowei; Besenhard, Maximilian O.; Kulkarni, Amol A.; Makatsoris, Charalampos; Gavriilidis, Asterios (Journal of Flow Chemistry, 2021)
A continuous manufacturing platform was developed for the synthesis of aqueous colloidal 10-20 nm gold nanoparticles (Au NPs) in a flow reactor using chloroauric acid, sodium citrate and citric acid at 95 degrees C and 2.3 bar(a) pressure. The use of a twophase flow system - using heptane as the continuous phase - prevented fouling on the reactor walls, while improving the residence time distribution. Continuous syntheses for up to 2 h demonstrated its potential application for continuous manufacturing, while live quality control was established using online UV-Vis photospectrometry that monitored the particle size and process yield. The synthesis was stable and reproducible over time for gold precursor concentration above 0.23 mM (after mixing), resulting in average particle size between 12 and 15 nm. A hydrophobic membrane separator provided successful separation of the aqueous and organic phases and collection of colloidal Au NPs in flow. Process yield increased at higher inlet flow rates (from 70% to almost 100 %), due to lower residence time of the colloidal solution in the separator resulting in less fouling in the PTFE membrane. This study addresses the challenges for the translation of the synthesis from batch to flow and provides tools for the development of a continuous manufacturing platform for gold nanoparticles.
Keywords: Continuous manufacturing; Nanomaterials; Online analysis; phase separation; segmented flow

Controlling draw resonance during extrusion film casting of nanoclay filled linear low-density polyethylene: an experimental study and numerical linear stability analysis - Rokade, Dhammaraj; Chougale, Sanket; Patil, Prashant; Bhattacharjee, Tanushree; Gawande, Dnyaneshwar; Pol, Harshawardhan; Dhadwal, Renu (Journal of Plastic Film & Sheeting, 2021)
Commercially important extrusion film casting (EFC) processes for manufacturing plastic films or sheets are hampered by several instabilities that severely limits their productivity. In this research we focussed on one important instability: the draw resonance that occurs during the EFC process mainly under extensional flow conditions. Draw resonance is the sustained periodic oscillations in the film dimensions, notably film width and thickness, when the process operates beyond a critical draw ratio (CDR). In this research our goal was to reduce this draw resonance instability by incorporating well dispersed nanoclay fillers in a base polymeric resin (such as a linear low density polyethylene - LLDPE) to determine how these nanocomposite (NC) formulations can prevent or reduce the draw resonance defect. EFC experiments were conducted on the base resin and on the NC formulations under non-isothermal conditions to determine the onset of the draw resonance experimentally. Conventional linear stability analysis was performed to determine the onset of the draw resonance defect numerically. Numerical predictions for the onset of draw resonance were in qualitative agreement with our experimental data. Our results showed that incorporating appropriate nanoclay concentrations in a base polymeric resin indeed enhanced the EFC process stability for those polymer formulations and thus can have important economic implications for processors.
Keywords: Draw resonance; extensional strain hardening; Extrusion; Film; hydrodynamic interactions; Nanoclay; Nanocomposites; Polyethylene; Rheology; stability

Convenient and mild protocol for preparation of α –trimethylsilyloxyphosphonates using sulfamic acid and their oxidation to α – ketophosphonates in the presence of N-bromosuccinimide - Mitragotri, Satish; Kulkarni, Makarand; Desai, Uday; Wadagaonkar, Prakash (Arkivoc, 2021)
A convenient and mild protocol was developed for the trimethylsilylation of α-hydroxyphosphonates using hexamethyldisilazane as the silylating agent in the presence of sulfamic acid (SA) as a heterogeneous solid acid catalyst in dichloromethane as the reaction medium. The utility of SA as the catalyst for deprotection of α-trimethylsilyloxyphosphonates to parent α-hydroxyphosphonates by making a switch to a protic solvent such as methanol was also demonstrated. Furthermore, the oxidation of α–trimethylsilyloxyphosphonates to corresponding α–ketophosphonates was achieved in excellent yields employing N-bromosuccinimide in the presence of catalytic quantity of AIBN.

Copolymers of bipyridinium and metal (Zn & Ni) porphyrin derivatives; theoretical insights and electrochemical activity towards CO2 - Kochrekar, Sachin; Kalekar, Ajit; Mehta, Shweta; Damlin, Pia; Salomaki, Mikko; Granroth, Sari; Meltola, Niko; Joshi, Kavita; Kvarnstrom, Carita (RSC Advances, 2021)
This study reports the electropolymerization of novel keto functionalized octaethyl metal porphyrins (Zn2+ and Ni2+) in the presence of 4,4 `-bipyridine (4,4 `-bpy) as a bridging nucleophile. The polymer films were characterized by electrochemical, spectroscopic (UV-Vis, XPS, FT-IR and Raman spectroscopy) and imaging (AFM and SEM) techniques. The absorption and electronic spectra confirm the presence of both porphyrin and 4,4 `-bipyridine units in the film. The surface morphology reveals homogeneous film deposition with average roughness values of approx. 8 nm. The theoretical studies performed offered insights into the interplay of different metal centres (Zn2+ and Ni2+) and the keto functionality of the porphyrin unit in the formation of copolymer films. The electrochemical interaction of polymer films with CO2 suggests a reversible trap and release of CO2 with low energy barriers for both the polymers.

Crack-free conjugated PbS quantum dot-hole transport layers for solar cells - Sharma, Ashish; Dambhare, V. Neha; Bera, Jayanta; Sahu, Satyajit; Rath, Arup K. (ACS Applied Nano Materials, 2021)
Colloidal quantum dots (QDs) benefit from solution-phase processing and band-gap tuning for their application in solar cell development. Today's QD solar cells rely on solid-state ligand exchange (SLE) to replace bulky oleic acid (OA) ligands with small 1,2-ethanedithiol (EDT) ligands to develop a conducting hole transport layer (HTL). High volume contraction in EDT conjugated QD films, however, leads to crack and porosity in the HTL, which is a major cause of concern for the device reproducibility and large-area solar cell development. We show that partial removal of the OA ligands in the solution phase reduces the volume contraction in solid films, thereby allowing the growth of crack-free QD films in the SLE process. The cleaning of QDs by repeated precipitation and redispersion using a protic methanol (MeOH) solvent helps with partial removal of the OA ligands, but it is detrimental to the electronic properties of QDs. We develop a one-step solution-phase partial ligand-exchange process using ammonium salts, which enable partial replacement of the OA ligands and passivation of the QD surface. Introduction of the facile partial ligand-exchange process eliminates the need for tedious and wasteful multiple cleaning steps with MeOH, while improving the photophysical properties of QDs. The advancement in QD processing helps to build crack-free, smooth, and conjugated QD films for their deployment as HTLs in solar cell development. Partial ligand exchange with NH4SCN leads to a 1.5 times increase in p doping and mobility over multiple MeOH-cleaned PbS QD films. HTLs developed using NH4SCN QDs show an improved photovoltaic performance to attain a 10.5% power conversion efficiency. Improvement in the depletion width and hole collection efficiency leads to a superior photovoltaic performance, as confirmed from experimental studies and one-dimensional solar cell capacitance simulation.
Keywords: Efficiency; ligand; polydispersity; quantum dot; solar cells; thin film

Deciphering the role of temperature in Li+ co-dopant occupancy in BaYF5:Yb3+,Er3+ up-converting nanocrystals and its structure-property relationship - Devi, Suman; Luwang, Meitram Niraj (Journal of Chemical Physics, 2021)
Precision engineering of defects in luminescent nanoscale crystalline materials with lesser controls to design is an area of interest in engineering materials with desired properties. Li+ co-doped BaYF5 nanocrystals were engineered, and temperature as controls for determining the co-dopant occupancies in the host lattice is studied. An observed enhancement in the up-conversion photoluminescence results from the co-dopant occupancy at Ba2+ sites via substitution through the hot injection method, whereas for samples prepared using co-precipitation, photoluminescence quenching was observed, which can be correlated with the Li+ occupancy at the interstitial site near Er3+ and also due to the incorporation of OH-. The crystal lattice deformation as a result of doping and the mechanism for the observed enhancement/quenching of luminescence are studied using x-ray diffraction, x-ray photoelectron spectroscopy, and energy transfer mechanism. Cytotoxicity assay and photoluminescence studies of the synthesized nanocrystals confirm that the material is biocompatible.

Design, synthesis, and structural analysis of cladosporin-based inhibitors of malaria parasites - Babbar, Palak; Das, Pronay; Manickam, Yogavel; Mankad, Yash; Yadav, Swati; Parvez, Suhel; Sharma, Amit; Reddy, Srinivasa (ACS Infectious Diseases, 2021)
Here we have described a systematic structure activity relationship (SAR) of a set of compounds inspired from cladosporin, a tool compound that targets parasite (Plasmodium falciparum) lysyl tRNA synthetase (KRS). Four sets of analogues, synthesized based on point changes in the chemical scaffold of cladosporin and other logical modifications and hybridizations, were assessed using high throughput enzymatic and parasitic assays along with in vitro pharmacokinetics. Co-crystallization of the most potent compound in our series (CL-2) with PfKRS revealed its structural basis of enzymatic binding and potency. Further, we report that CL-2 has performed better than cladosporin in terms of metabolic stability. It thus represents a new lead for further optimization toward the development of antimalarial drugs. Collectively, along with a lead compound, the series offers insights on how even the slightest chemical modification might play an important role in enhancing or decreasing the potency of a chemical scaffold.

Direct oxidation of cyclohexane to adipic acid by a WFeCoO(OH) catalyst: role of bronsted acidity and oxygen vacancies - Vernekar, Dnyanesh; Dayyan, Mohammad; Ratha, Satyajit; Rode, V, Chandrashekhar; Haider, M. Ali; Khan, Tuhin Suvra; Jagadeesan, Dinesh (ACS Catalysis, 2021)
This work reports the catalytic activity of the trimetallic mixed-metal oxyhydroxide WFeCoO(OH) for the direct oxidation of cyclohexane to adipic acid (AA) without the use of concentrated HNO3. WFeCoO(OH) displayed a 40% conversion of cyclohexane and a 67% selectivity to AA under relatively milder conditions of temperature (90 degrees C) and pressure (1 atm). Experimental evidence confirmed the presence of acidic, basic, and redox sites on WFeCoO(OH). The detailed investigation revealed that doping W in the Co-FeO(OH) matrix increased the amount of surface lattice oxygen (OS-L) and caused a significant surge in acidity (5.1 mmol/g). The calculated deprotonation energy of WFeCoO(OH) was 1434 kJ/mol, and the trend in acidity was WCoO(OH) < WFeCoO(OH) < FeCoO(OH) similar to CoO(OH). Energy calculations showed that WFeCoO(OH) had a high propensity to generate oxygen vacancies by the loss of either a water molecule or an oxygen atom (-132.2 or -140.9 kJ/mol, respectively). Basicity was generated due to the presence of conjugate pairs of the surface hydroxyl groups. The combined action of the trifunctional acidic, basic, and redox-active metal centers along with the oxygen vacancies was responsible for the enhanced catalytic performance.
Keywords: Adipic Acid; deprotonation energy; metal oxyhydroxides; multifunctional catalysts; oxygen vacancies

Disordered but efficient: understanding the role of structure and composition of the Co-Pt alloy on the electrocatalytic methanol oxidation reaction - Dalavi, Shankar B.; Agarwal, Sheena; Deshpande, Pooja; Joshi, Kavita; Bhagavatula L. V. Prasad (Journal of Physical Chemistry C, 2021)
A systematic investigation of the electrocatalytic Methanol Oxidation Reaction (MOR) was carried out using a model Co:Pt alloy system with different compositions and structural arrangements of the Co and Pt atoms. The structural variations with the same alloy composition included those with disordered arrangement of Co and Pt atoms in a face-centered cubic (fcc) lattice and ordered arrangements in face-centered tetragonal (fct) lattices. Our investigations clearly show that structures with disordered arrangements with Co:Pt atomic ratios near to 1:1 display better electrocatalytic efficiencies even when compared to pure Pt. These experimental findings were then rationalized by means of Density Functional Theory (DFT) calculations. Electronic level signatures in terms of charge transfer and relative shift in the peaks of the d band for surface metal atoms are proposed to be the reasons for the superior catalytic activity of a particular composition over the others. An increase in the number of inequivalent sites for methanol adsorption in disordered systems appears to result in better catalytic performance in comparison with ordered systems.

Diverse reactivity of carbenes and silylenes towards fluoropyridines - Kundu, Gargi; Ajithkumar, V. S.; Bisai, Milan Kumar; Tothadi, Srinu; Das, Tamal; Vanka, Kumar; Sen, Sakya S. (Chemical Communications, 2021)
The reaction of IDipp with C5F5N led to functionalization of all three carbon atoms of the imidazole ring with HF2- as the counter-anion (1). Reactivity with 2,3,5,6-tetrafluoropyridine gives only C-F bond activation leaving C-H bonds intact (5b). The reaction of SIDipp with C5F5N in the presence of BF3 afforded the ring cleavage product (3). Analogous reactions with silylene led to oxidative addition at the Si(II) center.

Dual-catalyst engineered porous organic framework for visible-light triggered, metal-free and aerobic sp(3) C-H activation in highly synergistic and recyclable fashion - Kumar, Gaurav; Dash, Soumya Ranjan; Neogi, Subhadip (Journal of Catalysis, 2021)
Photoredox and organo-catalysis denote powerful construction tools for new classes of carbon-carbon bonds, where incisive amalgamation of both the approaches over a single, recyclable platform can bring about synergic and eco-friendly reactions under mild conditions. Aiming at enamine-based photoredox catalysis for atom-economic and metal-free sp(3 )C-H activation, an amide-based two-dimensional (2D) porous organic framework (POF) is devised. The pendent -NH2 groups are judiciously anchored with two catalytic stations viz. Rose Bengal and L-proline, through stepwise variation of solid phase peptide synthesis. The dual-catalyst engineered POF represents a fully organic material that synergistically performs visible-light triggered oxidative Mannich reaction to produce biorelevant heterocycle beta-amino ketone in excellent yield at room temperature, using oxygen as clean and selective oxidant. Importantly, activity of this bi-functionalized catalyst compares favorably well to individual homogeneous counterparts. The covalently modified framework demonstrates economic viability via gram-scale synthesis besides admirable reusability, and proves to be effective for nineteen varieties of substrates. The photocatalytic path is detailed from efficient energy transfer from host polymer to substrate in light of experimental and theoretical studies, which provides proof-of-concept to the photo-organo combined mechanism. The material benefits heterogenising two homogeneous catalysts, besides excluding additional steps of conventional Mannich reactions, and offers a step-forward to smart and green cross-dehydrogenative coupling reactions. (C) 2020 Elsevier Inc. All rights reserved.
Keywords: Atom-economy; C-H activation; Dual-catalyst engineering; Metal-free reaction; Photo-organo catalysis; Porous organic framework

Easy and practical approach to access multifunctional cylcopentadiene- and cyclopentene-spirooxindoles via [3+2] annulation - Warghude, Prakash K.; Sabale, Abhijeet S.; Dixit, Ruchi; Vanka, Kumar; Bhat, Ramakrishna G. (Organic & Biomolecular Chemistry, 2021)
A highly regioselective [3 + 2] annulation of Morita-Baylis-Hillman (MBH) carbonates of isatin with aurone/thioaurone is developed. Spiroheterocycles such as spirooxindole cyclopentadiene and spirooxindole fused hydroxy cyclopentene derivatives are constructed in one pot by exploring the reactivity of Lewis bases. Combined experimental and density functional theory (DFT) calculations offered an insight into the reaction mechanism.

Effect of Mn2+ substitution into the hst lattice of ZnO via sol-gel route for boosting the dye-sensitized solar cells performance - Kumbhar, Deepak; Delekar, Sagar; Kumbhar, Sarita; Dhodamani, Ananta; Harale, Namdev; Nalawade, Rekha; Nalawade, Avinash (Chemical Papers, 2021)
In this study, Mn2+ ion is doped in ZnO lattice framework at 1, 3 and 5 wt % by a simple and low-cost sol-gel route to attain improved optoelectronic response. The structural investigation by XRD and Raman analysis explores the formation of hexagonal wurtzite framework with variations in lattice parameters comprising peak intensities favors the Mn doping. The extent of doping was supported by EDS analysis, while XPS confirms doping in + 2 chemical state. The optical investigation by UV-visible and PL provides prominent peaks that also specify peak shifting in order of doping level, while the significant hexagon-shaped nanoparticle (NP) formation was deduced in SEM and TEM micrographs. These proficient ZnO NPs have been deposited on fluorine-doped tin oxide (FTO) conducting glass plate by doctor-blade technique to get photoanodes. The electrical performance of these photoanodes especially photocurrent generation was investigated under standard AM 1.5 one sun illuminations. The highest photoconversion efficiency was attained for 3% Mn-doped ZnO photoanode after xanthene-based organic dye sensitization with output efficiency (eta%) of 0.25% higher than 0.03% of bare ZnO. The comparable ionic radii with exactly half-filled 3d orbital simply overlap with the ZnO valence bond responsible for enhanced overall structural and optical properties that beneficial for DSSCs performance.
Keywords: gel; Mixed dye; Mn-doped ZnO; Photoelectrochemical cell; Sol&#8211

Effect of Mn2+ substitution into the hst lattice of ZnO via sol-gel route for boosting the dye-sensitized solar cells performance (Apr, 10.1007/s11696-021-01615-w, 2021) - Kumbhar, Deepak; Delekar, Sagar; Kumbhar, Sarita; Dhodamani, Ananta; Harale, Namdev; Nalawade, Rekha; Nalawade, Avinash (Chemical Papers, 2021)

Efficient catalytic transfer hydrogenation-hydrodeoxygenation of lignin derived monomers: investigating catalyst properties-activity correlation - Singh, Dheerendra; Dhepe, Paresh L. (Catalysis Communications, 2021)
Reduction of O/C ratio of lignin derived monomers via hydrodeoxygenation (HDO) pathway is conventionally furnished using molecular hydrogen under severe conditions. Nonetheless, due to a prerequisite to accomplish HDO through commercially attractive methodology we report, HDO reactions of various phenolic compounds via catalytic transfer hydrogenation (CTH) pathway using very low loading of Ru (0.5 wt%) on neutral and acidic Al2O3 under nitrogen atmosphere. With guaiacol as a substrate, 74% cyclohexanol yield at 225 degrees C in the presence of IPA is realized. Bi-functionality of metal state, acidity of support and nature of alcohol are perceived to be responsible for the variation in activity.
Keywords: Catalytic transfer hydrogenation (CTH); Cyclohexanol; Hydrodeoxygenation; lignin; Supported metal catalysts

Efficient electrochemical oxygen reduction to hydrogen peroxide by transition metal-doped silicate Sr0.7Na0.3SiO3-delta - Thundiyil, Shibin; Kurungot, Sreekumar; Devi, R. Nandini (ACS Applied Materials & Interfaces, 2021)
Electrochemical oxygen reduction in a selective two-electron pathway is an efficient method for onsite production of H2O2. State of the art noble metal-based catalysts will be prohibitive for widespread applications, and hence earth-abundant oxide-based systems are most desired. Here we report transition metal (Mn, Fe, Ni, Cu)-doped silicates, Sr0.7Na0.3SiO3-delta, as potential electrocatalysts for oxygen reduction to H2O2 in alkaline conditions. These novel compounds are isostructural with the parent Sr0.7Na0.3SiO3-delta and crystallize in monoclinic structure with corner-shared SiO4 groups forming cyclic trimers. The presence of Na stabilizes O vacancies created on doping, and the transition metal ions provide catalytically active sites. Electrochemical parameters estimated from Tafel and Koutechy-Levich plots suggest a two-electron transfer mechanism, indicating peroxide formation. This is confirmed by the rotating ring disc electrode method, and peroxide selectivity and Faradaic efficiency are calculated to be in the range of 65-82% and 50-68%, respectively, in a potential window 0.3 to 0.6 V (vs RHE). Of all the dopants, Ni imparts the maximum selectivity and efficiency as well as highest rate of formation of H2O2 at 1.65 mu mol s(-1).
Keywords: H2O2; mixed metal oxide; ORR; silicate

Eichhornia crassipes mediated bioinspired synthesis of crystalline nano silver as an integrated medicinal material: a waste to value approach - Moudgil, Aliesha; Deval, Animesh S.; Dharne, Mahesh S.; Sarkar, Dhiman M.; Choudhari, Amit S.; Chaudhari, Bhushan P. (Journal of Cluster Science, 2021)
The present study deals with the synthesis of silver nanoparticles from Eichhornia crassipes. Dynamic light scattering (DLS), Transmission electron microscopy (TEM), UV-Vis spectroscopy, Fourier Transform Infrared (FTIR) spectroscopy and X-ray diffraction (XRD) were performed for nanoparticle characterization. The aqueous plant extract of Eichhornia crassipes was phytochemically analyzed for phenol, flavonoid, reducing sugar content, alkaloids, saponins and carotenoids. The synthesized particles after optimization of important parameters have an average diameter of 12.48 +/- 3.43 nm with a spherical morphology and zeta potential of - 31.53 mV. At 100 mu g/ml of nanoparticle concentration, the antioxidant activity of 93.6% was observed. MIC (Minimum inhibitory concentration) values exhibiting the antimicrobial attributes reported an estimated value of 7.8 mu g/ml for gram-negative and higher values of 31.25 and 250 mu g/ml for gram-positive bacteria. The antibiofilm assay showed 86.89% and 74.7% of the reduction in violacein synthesis and biofilm inhibition respectively at 15 mu g/ml nanoparticle concentration. The anticancer assay reported the IC50 (Inhibitory concentration) values of 13.32, 14.71 and 19.91 mu g/ml for HeLa, HCT 116 and L6 cell lines respectively. Thus the study establishes a significant integrative treatment to combat secondary infections in cancer patients. Graphic
Keywords: antibacterial activity; Antibiofilm activity; Anticancer activity; Antioxidant activity; Eichhornia crassipes; silver nanoparticles

Electrocatalytic nitrogen reduction directed through the p-band center of boron on BSAC@Mo2C - Maibam, Ashakiran; Krishnamurty, Sailaja; Dar, Manzoor Ahmad (Materials Advances, 2021)
Greener modes of ammonia synthesis via the electrocatalytic route have been investigated on pristine and defective Mo2C based monolayers anchored with metal-free boron atom catalysts. Boron single atom catalysts (SACs) on the defective Mo2C monolayer has been found to activate N2 strongly with an adsorption energy of −1.92 eV and reduce it to NH3 efficiently with a significantly low overpotential of 0.41 eV. The exothermic adsorption of N2 and low overpotential for the nitrogen reduction reduction (NRR) appertain to the p-band center of the boron atom catalyst and charge transfer between the adsorbed N2 and the catalyst, respectively. This work brings forth the correlation between electron occupancy on the boron center and NRR catalytic efficiency on a metal-free SACs@Mo2C monolayer couple, thereby serving as a lead in designing metal free electrocatalysts for the NRR.

Elucidating the effect of solid base on the hydrogenation of C5 and C6 sugars over Pt–Sn bimetallic catalyst at room temperature - Tathod, Anup P.; Dhepe, Paresh L. (Carbohydrate Research, 2021)
<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">Conversion of sugars into <a class="topic-link" href="https://www.sciencedirect.com/topics/biochemistry-genetics-and-molecular-biology/sugar-alcohols" style="background-color: transparent; text-decoration-line: underline; text-decoration-thickness: 1px; text-decoration-color: rgb(46, 46, 46); color: rgb(46, 46, 46); word-break: break-word; text-underline-offset: 1px;" title="Learn more about sugar alcohols from ScienceDirect's AI-generated Topic Pages">sugar alcohols at room temperature with exceedingly high yields are achieved over Pt–Sn/γ-Al<span style="font-size: 13.5px; line-height: 0; position: relative; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">2<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">O<span style="font-size: 13.5px; line-height: 0; position: relative; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">3<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;"> catalyst in the presence of calcined <a class="topic-link" href="https://www.sciencedirect.com/topics/biochemistry-genetics-and-molecular-biology/hydrotalcite" style="background-color: transparent; text-decoration-line: underline; text-decoration-thickness: 1px; text-decoration-color: rgb(46, 46, 46); color: rgb(46, 46, 46); word-break: break-word; text-underline-offset: 1px;" title="Learn more about hydrotalcite from ScienceDirect's AI-generated Topic Pages">hydrotalcite. pH of the reaction mixture significantly affects the conversion and selectivity for sugar alcohols. Selection of a suitable base is the key to achieve optimum yields. Various solid bases in combination with Pt–Sn/γ-Al<span style="font-size: 13.5px; line-height: 0; position: relative; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">2<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">O<span style="font-size: 13.5px; line-height: 0; position: relative; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">3<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;"> catalysts were evaluated for hydrogenation of sugars. Amongst all combinations, the mixture (1:1 <em style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">wt/wt<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">) of Pt–Sn/γ-Al<span style="font-size: 13.5px; line-height: 0; position: relative; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">2<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">O<span style="font-size: 13.5px; line-height: 0; position: relative; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">3<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;"> and calcined hydrotalcite showed the best results. Hydrotalcite helps to make the pH of reaction mixture alkaline at which sugar molecules undergo ring opening. The sugar molecule in open chain form has <a class="topic-link" href="https://www.sciencedirect.com/topics/chemistry/carbonyl-group" style="background-color: transparent; text-decoration-line: underline; text-decoration-thickness: 1px; text-decoration-color: rgb(46, 46, 46); color: rgb(46, 46, 46); word-break: break-word; text-underline-offset: 1px;" title="Learn more about carbonyl group from ScienceDirect's AI-generated Topic Pages">carbonyl group which can be polarized by Sn in Pt–Sn/γ-Al<span style="font-size: 13.5px; line-height: 0; position: relative; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">2<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">O<span style="font-size: 13.5px; line-height: 0; position: relative; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">3<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;"> and Pt facilitates the hydrogenation. In the current work, effect of both; solid base and Sn as a promoter has been studied to improve the yields of sugar alcohols from various C5 and C6 sugars at very mild reaction conditions.
Keywords: Bimetallic catalyst; Hydrogenation; Hydrotalcites; Sugar; Sugar alcohols

Energy and life cycle impact assessment for xylitol production from corncob - Dasgupta, Diptarka; Sidana, Arushdeep; Ghosh, Prasenjit; Sharma, Tripti; Singh, Jasvinder; Prabhune, Asmita; More, Snehal; Bhaskar, Thallada; Ghosh, Debashish (Journal of Cleaner Production, 2021)
The conversion of biobased feedstocks into energy and value-added chemicals is one main approach to address the current global challenge for waste mitigation through the biorefinery mode. Corncob biomass which is one of the most abundant agricultural residue in India with a high hemicellulose content, can serve as a potential low-cost raw material for food-grade xylitol production. The present study demonstrates a process for xylitol production from corncob biomass with detailed energy and life cycle analysis for viability assessment. The major highlight of the process is the use of microbial fermentation, where biomass-derived D-xylose is converted to xylitol with high selectivity. Overall, 0.502 kg of xylitol crystals could be produced from 3.5 kg of corncob biomass. Simulation analysis revealed that the evaporators are the primary consumers of energy, and the process of heat integration can significantly reduce the energy requirements of the overall process. Environmental impacts of the system evaluated showed emission results of 8.68 kg CO2 equivalent and revealed that marine aquatic and freshwater eco-toxicity are the only possible contributors to the environment. The results suggest that the process would have favourable energy balances, which can be used in pilot plant and heat exchanger network design and operation for xylitol production scale up to 500 L. (C) 2020 Elsevier Ltd. All rights reserved.
Keywords: biomass valorization; Life cycle impact assessment; simulation; xylitol

Engineering microstructure of LiFe(MoO4)(2) as an advanced anode material for rechargeable lithium-ion battery - Tamboli, Asiya M.; Tamboli, Mohaseen S.; Dwivedi, Pravin Kumari; Praveen, C. S.; Karbhal, Indrapal; Shelke, V, Manjusha; Kim, Bomyung; Park, Chinho; Kale, Bharat B. (Journal of Materials Science-Materials In Electronics, 2021)
Graphite is considered as an ideal anode material for lithium-ion battery (LIB) due to its high stability, good conductivity and wide source of availability. However, the low energy density and theoretical capacity of graphite cannot meet the needs of high performance anode materials. To circumvent this issue, alternative materials have been sought for many years now. Herein, we report the synthesis of highly crystalline lithium iron molybdate LiFe(MoO4)(2) by combustion method and evaluated its performance as an anode material for lithium-ion batteries. Triclinic LiFe(MoO4)(2) crystals having particle size 2-5 mu m with good crystallinity were obtained. The material shows long cycle life and high rate performance than commercial graphite and exhibits first reversible discharge capacity of 931.6 mAh/g at a current density of 100 mA/g which is three times higher than commercial graphite. The high specific capacity together with the outstanding rate and cycle performance makes LiFe(MoO4)(2) a promising anode material for LIB. A detailed analysis on the crystal structure and electronic properties of LiFe(MoO4)(2) is presented based on DFT studies to complement the experimental observations.

Enhanced photocatalytic properties of a chemically modified blue phosphorene - Maibam, Ashakiran; Das, Sawan Kumar; Samal, Pragnya Paramita; Krishnamurty, Sailaja (RSC Advances, 2021)
It is high time to placate the peak demand for an efficient, economic and green fuel in the form of H-2 through photocatalytic water splitting. Several low dimensional materials have been explored for their photocatalytic properties on account of their surface to volume ratio. The present study illustrates the excellent photocatalytic potential of a two-dimensional material, viz. a chemically tempered blue-phosphorene sheet, with single atom thickness and high carrier mobility. Metal-free element, sulphur, is explored as a dopant in a 32-atom blue-phosphorene sheet. The dopant is inserted at three locations viz. central, edge and central edge positions with varying concentrations from 3.125% to 18.75% (corresponding to n = 1 to 6 sulphur atoms within a 32-atom blue-phosphorene sheet, P32-nSn). The cohesive energy studies predict the higher stability of even number S doped sheets as compared to their odd counterparts. Photocatalytic activity is studied in terms of band gap and band alignment for different concentrations of the former. Studies reveal that edge doping demonstrates better water molecule activation independent of S atom concentration. The edge doped systems not only provide the chemical activity to activate water, but also show feasible HER overpotentials of 1.24-1.29 eV at neutral medium. Finally, this work opens up a driving lead of non-corrosive catalysts for water molecule splitting.

Enhanced photoelectrochemical cell performance of Co doped ZnO nanoparticles sensitized by affordable mixed dyes as sensitizer - Kumbhar, Deepak; Kumbhar, Sarita; Dhodamani, Anant; Delekar, Sagar; Harale, Namdev; Nalawade, Rekha; Nalawade, Avinash (Inorganic and Nano-Metal Chemistry, 2021)
In the present investigation, a simple sol-gel approach has been employed for the synthesis of hexagonal wurtzite ZnO nanoparticles (NPs). X-ray diffraction (XRD) rietveld study and Raman analysis reveal the mislaid of the mixed phases of ZnO NPs after doping. The scanning electron micrographs and transmission electron microscopy confirm the formation of hexagonal disk-shaped NPs. FTIR, PL, EDX, XPS validate optical and stoichiometric concentration of Co in ZnO lattice. UV-visible DRS study shows absorption edge with humps to the red region of the spectrum with increasing the absorption strength and shortening of band gap as the content of Co (II) increases. Finally, the prepared samples were coated on the surface of cleaned FTO substrate through a simple doctor blade technique and sensitized with prepared dye. The ZnO photoanode shows 0.036% of efficiency (eta%) while the photoanodes of Co doped samples expose the enhanced efficiencies of 0.29%, 0.389%, 0.089%.
Keywords: Co doped ZnO; mixed dyes as sensitizer; Photoelectrochemical cell; sol-gel

Evidence of an nN(amide) → π*Ar interaction in N-Alkyl-N,N′-diacylhydrazines - Deka, Jugal Kishore Rai; Sahariah, Biswajit; Sakpal, Sushil S.; Bar, Arun Kumar; Bagchi, Sayan; Sarma, Bani Kanta (Organic letters, 2021)
1,2-Dibenzoyl-1-tert-butylhydrazine (RH-5849) and related N-alkyl-N,N′-diacylhydrazines are environmentally benign insect growth regulators. Herein, we show that an unusual n<span style="outline: none; font-size: 12.75px; line-height: 0; position: relative; bottom: -0.25em; font-family: Georgia, serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; background-color: rgb(244, 244, 244);">N(amide) → π*<span style="outline: none; font-size: 12.75px; line-height: 0; position: relative; bottom: -0.25em; font-family: Georgia, serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; background-color: rgb(244, 244, 244);">Ar interaction mediated by a hydrazide amide nitrogen atom plays a crucial role in stabilizing their biologically active trans–cis (t–c) rotameric conformations. We provide NMR and IR spectroscopic evidence for the presence of these interactions, which is also supported by X-ray crystallographic and computational studies.

Excimer to exciplex transition through realization of donor-acceptor interactions in luminescent solvent-free liquids - Wakchaure, Vivek Chandrakant; Goudappagouda; Das, Tamal; Ravindranathan, Sapna; Babu, Sukumaran Santhosh (Nanoscale, 2021)
Luminescent solvent-free organic liquids are known for their enhanced quantum yield, color tunability, and availability of a matrix for other dopants to generate hybrid luminescent materials with improved features for newer applications. Herein, we report a donor-acceptor based luminescent ``exciplex liquid'' by utilizing the slightly different electron affinity of the acceptor molecules. A red-shifted broad exciplex emission exhibited by the donor-acceptor pair even at a lower concentration of the acceptor (0.001 equiv.) indicates high efficiency in the solvent-free state. A detailed NMR study revealed weak intermolecular interactions between the donor and acceptor in the solvent-free matrix that stabilizes the exciplex liquid. The failure of structurally similar solid counterparts to form an exciplex confirms the advantage of the available supportive liquid matrix. Besides, the luminescent exciplex liquid is found efficient in sensing application, which is unachievable by either the individual liquids or their solid counterparts. Here, a transition of a donor-acceptor pair from a solid to solvent-free liquid results in a new hybrid liquid that can be an alternative for solid sensor materials.

Expression, purification and crystallization of Asrij, A novel scaffold transmembrane protein - Motiwala, Zenia; Darne, Priti; Prabhune, Asmita; Inamdar, Maneesha S.; Kulkarni, Kiran (Journal of Membrane Biology, 2021)
Asrij/OCIAD1 is a scaffold transmembrane protein belonging to the Ovarian Carcinoma Immunoreactive Antigen Domain containing protein family. In Drosophila and mouse models, Asrij localizes at the endosomal and mitochondrial membrane and is shown to regulate the stemness of hematopoietic stem cells. Interaction of Asrij with ADP Ribosylation Factor 1 (Arf1) is shown to be crucial for hematopoietic niche function and prohemocyte maintenance. Here, we report the heterologous expression, standardization of detergents and purification methodologies for crystallization of Asrij/OCIAD1. To probe the activity of bacterially expressed Asrij, we developed a protein complementation assay and conclusively show that Asrij and Arf1 physically interact. Further, we find that sophorolipids improve the solubility and monodispersibility of Asrij. Hence, we propose that sophorolipids could be novel additives for stabilization of membrane proteins. To our knowledge, this is the first study detailing methodology for the production and crystallization of a heterologously expressed scaffold membrane protein and will be widely applicable to understand membrane protein structure and function. Graphic
Keywords: Asrij/OCIAD1; Membrane protein crystallography; sophorolipids

Fabrication of bacterial nanocellulose/polyethyleneimine (PEI-BC) based cationic adsorbent for efficient removal of anionic dyes - Thorat, Meghana N.; Jagtap, Ashish; Dastager, Syed G. (Journal of Polymer Research, 2021)
A bacterial cellulose (BC) based adsorbent was prepared by using polyethyleneimine (PEI) using epichlorohydrin as a cross-linker. The physicochemical characterization of the of the developed adsorbent was carried out using FTIR, BET analysis and SEM, respectively. The dye removal efficiency of the adsorbent was assessed towards two anionic model dyes viz. congo red (CR) and reactive red 120(RR). The kinetic data for the removal of both the anionic dyes were fitted better using pseudo-second-order model. Langmuir model describes well the process of adsorption with predicted maximum adsorption capacity (q(max)) 515.46 and 300.3 mg L-1 for CR (at pH 6.0) and RR (at pH 3.0) respectively. The adsorption-desorption study showed that PEI-BC adsorbent is effective with more than 90% dye removal efficiency even after four cycles. Furthermore, the bactericidal activity of the adsorbent was analysed using Escherichia coli and Staphylococcus aureus and adsorbent showed good inhibition against both test organisms. The study reveals that PEI-BC adsorbent can be a good candidate for water remediation purpose bearing multifunctional behaviour.
Keywords: adsorbent; Anionic dyes; Bacterial cellulose; Bactericidal; Polyethyleneimine

Facile access to functional polyacrylates with dual stimuli response and tunable surface hydrophobicity - Mohammad, Sk Arif; Dolui, Subrata; Kumar, Devendra; Mane, Shivshankar R.; Banerjee, Sanjib (Polymer Chemistry, 2021)
Magnetically separable and reusable Ni-Co alloy nanoparticles were employed to achieve ambient temperature reversible deactivation radical polymerization (RDRP) of methyl acrylate (MA), for the first time, yielding well-defined PMA (at least up to 124 500 g mol(-1)) with a low dispersity (D <= 1.20). The controlled polymerization character of RDRP of MA was confirmed from the linear semilogarithmic plot exhibiting pseudo first order kinetics, a linear increase of the molecular weight of the polymer with monomer conversion maintaining low D and the synthesis of PMAs of varying molecular weights from 2200 to 124 500 g mol(-1) with low D. In addition, linear PMA-Br was used as a macroinitiator for the synthesis of several well-defined PMA-b-poly(M) block copolymers (where ``M'' stands for (2-dimethylamino)ethyl methacrylate (DMAEMA), tert-butyl methylacrylate (TBMA) and 2,2,3,3,4,4,5,5-octafluoropentyl acrylate (OFPA)), with acceptable Ds (<= 1.24), demonstrating the high chain-end fidelity of the macroinitiator. The synthesized PMA-b-PDMAEMA demonstrated dual pH- and thermo-responsive properties. Upon hydrolysis, the synthesized PMA-b-PTBMA leads to the formation of unprecedented carboxylic acid-functionalized PMA derivatives. PMA-b-POFPA copolymers with varying OFPA mol% in the copolymer led to polymers with tunable surface hydrophobicity, as revealed by the water contact angle measurements.

Flexible energy harvester from an organic ferroelectric ammonium salt - Gupta, Rishabh; Sahoo, Supriya; Deswal, Swati; Kothavade, Premkumar; Dixit, Prashant; Zareba, Jan K.; Shanmuganathan, Kadhiravan; Boomishankar, Ramamoorthy (Chemistry-An Asian Journal, 2021)
Organic ferroelectrics due to their low cost, easy preparation, light weight, high flexibility and phase stability are gaining tremendous attention in the field of portable electronics. In this work, we report the synthesis, structure and ferroelectric behavior of a two-component ammonium salt 2, containing a bulky [Bn(4-BrBn)NMe2](+) (Bn=benzyl and 4-BrBn=4-bromobenzyl) cation and tetrahedral (BF4)(-) anion. The structural analysis revealed the presence of rich non-classical C-H...F and C-H...Br interactions in this molecule that were quantified by Hirshfeld surface analysis. The polarization (P) vs. electric field (E) hysteresis loop measurements on 2 gave a remnant polarization (P-r) of 14.4 mu C cm(-2) at room temperature. Flexible polymer composites with various (5, 10, 15 and 20) weight percentages (wt%) of 2 in thermoplastic polyurethane (TPU) were prepared and tested for mechanical energy harvesting applications. A notable peak-to-peak output voltage of 20 V, maximum current density of 1.1 mu A cm(-2) and power density of 21.1 mu W cm(-2) were recorded for the 15 wt% 2-TPU composite device. Furthermore, the voltage output generated from this device was utilized to rapidly charge a 100 mu F capacitor, with stored energies and measured charges of 156 mu J and 121.6 mu C, respectively.
Keywords: Dielectric; energy harvesting; ferroelectricity; organic composites; piezoelectric

Functional metagenomic landscape of polluted river reveals potential genes involved in degradation of xenobiotic pollutants - Yadav, Rakeshkumar; Rajput, Vinay; Dharne, Mahesh (Environmental Research, 2021)
Rapid industrialization contributes substantially to xenobiotic pollutants in rivers. As a result, most of the rivers traversing urban settlements are in significantly deteriorated conditions. These pollutants are recalcitrant, requiring robust catabolic machinery for their complete transformation into bioavailable and non-toxic byproducts. Microbes are versatile dwellers that could adapt to such contaminants by using them as a source of nutrients during growth. However, efficient bioremediation requires an in-depth knowledge of microbial diversity and their metabolism related genes in the polluted niches. We employed MinION shotgun sequencing, to comprehend the biodegradation related genes and their function potential operating in the polluted urban riverine system of Western India. A vast number of catabolic genes were detected for the xenobiotic pollutants such as Benzoate, Nitrotoluene, Aminobenzoate, Drug metabolism, and Polycyclic Aromatic Hydrocarbons. Aerobic, and anaerobic catabolism genes, were mapped for their ability of degradation of xenobiotics. Interestingly, catabolism profiles of multiple aromatic compounds culminated into the Benzoate degradation pathway, suggesting it as a plausible central pathway for the autochthonous bacterial communities. Further mapping with RemeDB database, predicted plastic and dye degrading enzymes. Moreover, the diversity indices for the pollutant degrading enzymes suggested little variations (R-2 value of 18%) between the city and non-city (outskirts of city limits) riverine stretch indicating the impact of industrialization in the outskirts of the city stretch as well. Altogether, this study would serve as a preliminary baseline for future explorations concerning river cleaning programs and also exploiting such microbes for bioremediation applications.
Keywords: Benzoate; Bioremediation; MinION; Riverine system; Xenobiotics

Glycerol-triazole conjugated rhodamine as colorimetric and fluorimetric sensor for Cu2+ - Verma, Abhishek; Gahlyan, Parveen; Bawa, Rashim; Dash, Soumya Ranjan; Prasad, Ashok K.; Kumar, Rakesh (ChemistrySelect, 2021)
{A glycerol-triazole tethered rhodamine based colorimetric and fluorimetric sensor 3 `,6 `-bis(diethylamino)-2-(((1-(1,3-dihydroxypropan-2-yl)-1H-1,2,3-triazol-4 -yl)methylene)aminospiro [isoindoline-1,9 `-xanthen]-3-one (L1) is designed and synthesized for the selective recognition of Cu2+ ion. The sensor L1 allows naked eye detection of Cu2+ ion with a fast response (<1 min). Among the various metal ions tested, the sensor L1 shows selective binding with Cu2+ through turn-on fluorescence mechanism. The sensor shows 1 : 2 binding stoichiometry with binding constant
Keywords: Cu2+ Sensor; DFT; Glycerol; Rhodamine B; Triazole

Gold-catalysed nitroalkyne cycloisomerization - synthetic utility - Dhote, Pawan S.; Halnor, Swapnil V.; Ramana, Chepuri V. (Chemical Record, 2021)
The gold-catalysed intramolecular redox cyclization of o-alkynylnitrobenzens documented by Professors Naoki Asao and Yoshinori Yamamoto is an important discovery that has opened two complementary research domains. Advancing this cyclization with other metals as well as developing new methods around the products that result from this reaction is one aspect that has seen growing interest. On the other hand, the idea of generating alpha-oxo gold carbenes via oxygen transfer to alkynes has established another important aspect in gold-catalysis. In this account, we will be dealing with the first aspect, which revolves around the internal redox cyclization of nitroalkynes (trivially called as nitroalkyne cycloisomerization), focusing mainly on the gold-complexes and the synthetic methods developed around it from our group and from other groups, and also providing the details of similar transformations documented with other metals so that the complementary reactivity/diversity of these transformations could be appreciated.
Keywords: alpha-Oxo Gold Carbene; Anthranil; Gold-catalysis; Internal Redox Cyclization; Isatogen

Gold-catalyzed complementary nitroalkyne internal redox process: a DFT study - Vipin Raj, K.; Dhote, Pawan S. S.; Vanka, Kumar; Ramana, Chepuri V. V. (Frontiers in Chemistry, 2021)
Gold-catalysis, in this century, is one of the most emerging and promising new areas of research in organic synthesis. During the last two decades, a wide range of distinct synthetic methodologies have been unveiled employing homogeneous gold catalysis and aptly applied in the synthesis of numerous natural products and biologically active molecules. Among these, the reactions involving alpha-oxo gold carbene/alpha-imino gold carbene intermediates are of contemporary interest, in view of their synthetic potential and also due to the need to understand the bonding involved in these complexes. In this manuscript, we document the theoretical investigations on the regio-selectivity dependence of substitution on the gold-catalyzed cycloisomerization of o-nitroarylalkyne derivatives. We have also studied the relative stabilities of alpha-oxo gold carbene intermediates.
Keywords: alpha-Oxo Gold Carbene; cycloisomerization; DFT calculation; Gold-catalysis; internal redox

Herbicidal bio-assay of isocladosporin enantiomers and determination of its plausible absolute configuration - Mankad, Yash; Das, Pronay; Pathan, Ejaj; Deshpande, V. M.; Reddy, D. Srinivasa (Journal of Antibiotics, 2021)
A fungal metabolite, isocladosporin was isolated from natural fungus, Cladosporium cladosporioides in the mid of 90s. Due to the lack of optical rotation of isolated natural product sample, the absolute configuration of the natural product remained undetermined for more than two decades. Herein, we demonstrated an SAR study of enantiomers of isocladosporin in herbicidal bio-assay against wheat coleoptile. Using this study as a comparative tool we further proposed the plausible absolute configuration of natural isocladosporin for the first time. The assigned configuration was also supported through biogenetic precursors.

Heterogeneous nucleation in citrate synthesis of AgNPs: effect of mixing and solvation dynamics - Deshpande, J. B.; Chakrabarty, S.; Kulkarni, A. A. (Chemical Engineering Journal, 2021)
<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">The heterogeneity issues in silver nanoparticle nucleation (Lee-Meisel route) have been investigated. The final polydispersity and sphericity of the nanoparticles in the Lee-Meisel scheme are shown to depend upon the early time dynamics of silver-citrate complexation. The formation of macromolecular intermediary complexes in the early stages of the reaction is visualized based on online DLS data, TEM analysis, and the mass balances of silver and citrate ions. The reversible complexation between citrate ions and silver citrate is shown to be the limiting step that governs the directional growth of the nanoparticles. The dynamics of the complexation of citrate are seen to form a very rapid step and intense mixing was required for the complexation to happen uniformly across the reaction. This specific observation is also confirmed from the MD simulations. Thus, to get particles of high sphericity, irrespective of the reaction concentration, temperature, or reactor geometry, the mixing time should be <4 s and <em style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">Da<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;"> ~ 0.1. Optimal mixing conditions for isotropic growth are suggested based on the reaction kinetics and are also demonstrated with experimental evidence.

High efficiency lithium storage in 3D composite foam of Co3O4 nanoparticles integrated carbon nanohorns - Dwivedi, Pravin K.; Parte, Golu; Thripuranthaka, M.; Shelke, Manjusha V. (Materials Science and Engineering B-Advanced Functional Solid-State Materials, 2021)
A well-designed 3 dimensional (3D) nanocomposite foam of Co3O4 nanoparticles and functionalized carbon nano horns (CNH) is prepared by feasible wet chemistry followed by lyophilization. This 3D nanocomposite foam is evaluated electrochemically as anode material for lithium-ion battery (LIB). 3D hierarchical mesoporous hybrid of functionalized carbon nano horn-Co3O4 (CCO) shows excellent lithium storage properties with long cycle life due to high surface area, good conductivity, 3D interconnected mesoporous structure, mechanical and chemical stability and shortened diffusion path length for Li+ ions during lithiation-delithiation. The Co3O4 nanoparticles incorporated into interconnected CNH foam effectively increases the number of active sites of CCO nanocomposite and consequently increase in the reversible specific capacity and coulombic efficiency. Different compositions of CNH foam with Co3O4 nanoparticles are prepared, among which the CCO 1:1 foam displays reversible capacity of 797 mAhg1 at current density of 0.1 Ag-1 along with excellent rate performance. High specific capacity of around 702 mAhg(-1) is obtained even at the current density of 5 Ag-1.
Keywords: 3D CCO foam; carbon nanohorns; Excellent rate capability; Li ion diffusion coefficient; Long Cycle life

Highly efficient and extremely simple protocol for the oxidation α-hydroxyphosphonates to α-ketophosphonates using Dess-Martin periodinane - Kupwade, Ravindra; Mitragotri, Satish D.; Kulkarni, Makarand A.; Desai, Uday V.; Wadagaonkar, Prakash P. (ARKIVOC, 2021)

Hydrogenolysis of glycerol in an aqueous medium over Pt/WO3/zirconium phosphate catalysts studied by H-1 NMR spectroscopy - Bhowmik, Susmita; Enjamuri, Nagasuresh; Darbha, Srinivas (New Journal of Chemistry, 2021)
Bifunctional Pt/WO3/zirconium phosphate catalyzes the liquid-phase hydrogenolysis of glycerol in an aqueous medium. H-1 NMR spectroscopy (solvent suppression pulse program) is employed to monitor this reaction. Propanediols (1,3 + 1,2-PDO) formed as the major product along with propanols (1- and 2-POs) as the minor product. A synergistic enhancement in glycerol conversion and selectivity to 1,3-PDO was observed when both Pt and WO3 were present in the catalyst. A volcano-shape variation of catalytic activity with W content was observed. A catalyst with 8 wt% W and 1 wt% Pt exhibited the highest selective hydrogenolysis performance (glycerol conversion = 92.3% and total PDOs selectivity = 45.9% and 1,3-PDO selectivity = 20.8% at 200 degrees C). Dispersed Pt in contact with polytungstate-type WO3 species was found to be the active catalytic site. H-1 NMR spectroscopy is demonstrated as an attractive technique to quantify the products of a glycerol hydrogenolysis reaction.

Hydrophilic 3D interconnected network of bacterial nanocellulose/black titania photothermal foams as an efficient interfacial solar evaporator - Nabeela, Kallayi; Thorat, Meghana; Sumina, N. B.; Ramachandran, Animesh M.; Thomas, Reny Thankam; Preethikumar, Gopika; Mohamed, A. Peer; Asok, Adersh; Dastager, Syed Gulam; Pillai, Saju (ACS Applied Bio Materials, 2021)
The design and development of scalable, efficient photothermal evaporator systems that reduce microplastic pollution are highly desirable. Herein, a sustainable bacterial nanocellulose (BNC)-based self-floating bilayer photothermal foam (PTF<span style="outline: none; font-size: 12.75px; line-height: 0; position: relative; bottom: -0.25em; font-family: Georgia, serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; background-color: rgb(244, 244, 244);">b) is designed that eases the effective confinement of solar light for efficient freshwater production via interfacial heating. The sandwich nanoarchitectured porous bilayer solar evaporator consists of a top solar-harvesting blackbody layer composed of broad-spectrum active black titania (BT) nanoparticles embedded in the BNC matrix and a thick bottom layer of pristine BNC for agile thermal management, the efficient wicking of bulk water, and staying afloat. A decisive advantage of the BNC network is that it enables the fabrication of a lightweight photothermal foam with reduced thermal conductivity and high wet strength. Additionally, the hydrophilic three-dimensional (3D) interconnected porous network of BNC contributes to the fast evaporation of water under ambient solar conditions with reduced vaporization enthalpy by virtue of intermediated water generated via a BNC–water interaction. The fabricated PTF<span style="outline: none; font-size: 12.75px; line-height: 0; position: relative; bottom: -0.25em; font-family: Georgia, serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; background-color: rgb(244, 244, 244);">b is found to yield a water evaporation efficiency of 84.3% (under 1054 W m<span style="outline: none; font-size: 12.75px; line-height: 0; position: relative; top: -0.5em; font-family: Georgia, serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; background-color: rgb(244, 244, 244);">–2) with 4 wt % BT loading. Furthermore, scalable PTF<span style="outline: none; font-size: 12.75px; line-height: 0; position: relative; bottom: -0.25em; font-family: Georgia, serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; background-color: rgb(244, 244, 244);">b realized a water production rate of 1.26 L m<span style="outline: none; font-size: 12.75px; line-height: 0; position: relative; top: -0.5em; font-family: Georgia, serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; background-color: rgb(244, 244, 244);">–2 h<span style="outline: none; font-size: 12.75px; line-height: 0; position: relative; top: -0.5em; font-family: Georgia, serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; background-color: rgb(244, 244, 244);">–1 under real-time conditions. The developed eco-friendly BNC-supported BT foams could be used in applications such as solar desalination, contaminated water purification, extraction of water from moisture, etc., and thus could address one of the major present-day global concerns of drinking water scarcity.

Imidazole/4,4 `-azopyridine bridging binuclear Ru(II) complexes: design, synthesis, bimolecular interactions and cytotoxicity against HeLa cell line - Khanvilkar, Priyanka; Dash, Soumya R.; Pulipaka, Ramadevi; Shirsath, Kavita; Devkar, Ranjitsinh; Chakraborty, Debjani (Journal of the Iranian Chemical Society, 2021)
Binuclear Ru(II)-arene complexes [(eta(6)-pcym)(Flq)Ru(mu-im/mu-azpy)Ru(Flq)(eta(6)-p-cym)]Cl (C1-C8) (cym = cymene; Flq = fluoroquinolones; im = imidazole; azpy = 4,4 ` azo pyridine) have been synthesized and characterized by elemental analysis, molar conductivity and various spectral techniques (ESI-MS, IR, UV-Vis and H-1-NMR). The geometry of the complexes was optimized by DFT calculations, which revealed a pseudo-octahedral coordination around each metal centre. Binding of the synthesized complexes with CT-DNA and BSA was studied spectroscopically, and it has been established that the presence of two hydrophobic planar arene moieties enhances the binding efficacies of the binuclear complexes to the macromolecules, compared to their mononuclear analogues. The results of competitive binding between C1-C8 and ethidium bromide (EB) towards DNA have shown that the complexes are able to displace EB from DNA-EB adduct and interact with DNA via intercalation. The complexes display cytotoxicity against the HeLa human cervical cancer cell lines with IC50 values in the range of 30.1-120.9 mu M.
Keywords: Binuclear ruthenium (II) complexes; BSA binding interactions; DFT calculations; DNA; Fluoroquinolones (FQs); HeLa human cervical carcinoma

Influence of domestication on specialized metabolic pathways in fruit crops - Dar, M. Saleem; Dholakia, Bhushan B.; Kulkarni, Abhijeet P.; Oak, Pranjali S.; Shanmugam, Dhanasekaran; Gupta, Vidya S.; Giri, Ashok P. (Planta, 2021)
Main conclusionDuring the process of plant domestication, the selection and traditional breeding for desired characters such as flavor, juiciness and nutritional value of fruits, probably have resulted in gain or loss of specialized metabolites contributing to these traits. Their appearance in fruits is likely due to the acquisition of novel and specialized metabolic pathways and their regulation, driven by systematic molecular evolutionary events facilitated by traditional breeding.AbstractPlants change their armory of specialized metabolism to adapt and survive in diverse ecosystems. This may occur through molecular evolutionary events, such as single nucleotide polymorphism, gene duplication and transposition, leading to convergent or divergent evolution of biosynthetic pathways producing such specialized metabolites. Breeding and selection for improved specific and desired traits (fruit size, color, taste, flavor, etc.) in fruit crops through conventional breeding approaches may further alter content and profile of specialized metabolites. Biosynthetic routes of these metabolites have been studied in various plants. Here, we explore the influence of plant domestication and breeding processes on the selection of biosynthetic pathways of favorable specialized metabolites in fruit crops. An orderly clustered arrangement of genes associated with their production is observed in many fruit crops. We further analyzed selection-based acquisition of specialized metabolic pathways comparing first the metabolic profiles and genes involved in their biosynthesis, followed by the genomic organization of such genes between wild and domesticated horticultural crops. Domestication of crop plants favored the acquisition and retention of metabolic pathways that enhanced the fruit value while eliminated those which produced toxic or unfavorable metabolites. Interestingly, unintentional reorganization of complex metabolic pathways by selection and traditional breeding processes has endowed us with flavorful, juicy and nutritionally rich fruits.
Keywords: Aroma; Domestication; Flavour; Fruit crops; Gene cluster; Specialized metabolites; Taste

Influence of sodium caseinate, maltodextrin, pectin and their Maillard conjugate on the stability, in vitro release, anti-oxidant property and cell viability of eugenol-olive oil nanoemulsions - Nagaraju, Pramod G.; Sindhu, P.; Dubey, Tushar; Chinnathambi, Subashchandrabose; Priyadarshini, Poornima; Rao, Pooja J. (International Journal of Biological Macromolecules, 2021)
<span style="color: rgb(33, 33, 33); font-family: BlinkMacSystemFont, -apple-system, "Segoe UI", Roboto, Oxygen, Ubuntu, Cantarell, "Fira Sans", "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">The influence of protein (sodium caseinate-SC), polysaccharide (maltodextrin-MD; pectin-PC) and their Maillard conjugates (sodium caseinate maltodextrin conjugate-SCMDC; sodium caseinate pectin conjugate-SCPCC) were studied on the physico-chemical and biological properties of eugenol nanoemulsions/powder. The chemical composition was optimized using Taguchi design. The particles size of eugenol nanoemulsions with SC, MD, PC, SCMDC and SCPCC were 104.6, 323.5, 1872, 181.7, and 454.4 nm, respectively while their zeta potentials were -31.2, -28.5, -21.4, -40.1 and -25.1 mV, respectively. Turbidity studies revealed higher stability of nanoemulsion prepared with Maillard conjugate (SCMDC) compared to protein or polysaccharides alone. The dispersion of SCMDC eugenol nanoparticles in buffer was prepared to study its stability at different pH (3.0, 5.0, and 7.0) and temperature (4°, 37°, 60 °C) range. In-vitro enzymatic release study showed 31 and 74% release of eugenol after 6 h at pH 2.4 and 7.4, respectively. In vitro antioxidant capacity of SCMDC encapsulated eugenol was higher than native eugenol, as demonstrated by free radical scavenging assays. In comparison to native eugenol, E:SCMDC eugenol showed reduced toxicity. These findings suggested that nanoencapsulated eugenol (E:SCMDC) have a huge potential in nutraceutical and therapeutic applications.

Insights from a pan India Sero-epidemiological survey (Phenome-India Cohort) for SARS-CoV2 - Naushin, Salwa; Sardana, Viren; Ujjainiya, Rajat; Bhatheja, Nitin; Kutum, Rintu; Bhaskar, Akash Kumar; Pradhan, Shalini; Prakash, Satyartha; Khan, Raju; Rawat, Birendra Singh; Tallapaka, Karthik Bharadwaj; Anumalla, Mahesh; et al. (eLife, 2021)
To understand the spread of SARS-CoV2, in August and September 2020, the Council of Scientific and Industrial Research (India) conducted a serosurvey across its constituent laboratories and centers across India. Of 10,427 volunteers, 1058 (10.14%) tested positive for SARS-CoV2 anti-nucleocapsid (anti-NC) antibodies, 95% of which had surrogate neutralization activity. Three-fourth of these recalled no symptoms. Repeat serology tests at 3 (n = 607) and 6 (n = 175) months showed stable anti-NC antibodies but declining neutralization activity. Local seropositivity was higher in densely populated cities and was inversely correlated with a 30-day change in regional test positivity rates (TPRs). Regional seropositivity above 10% was associated with declining TPR. Personal factors associated with higher odds of seropositivity were high-exposure work (odds ratio, 95% confidence interval, p value: 2.23, 1.92-2.59, <0.0001), use of public transport (1.79, 1.43-2.24, <0.0001), not smoking (1.52, 1.16-1.99, 0.0257), non-vegetarian diet (1.67, 1.41-1.99, <0.0001), and B blood group (1.36, 1.15-1.61, 0.001).

Insights into chemical reactions at the beginning of the universe: from HeH+ to H-3 (+) - Dash, Soumya Ranjan; Das, Tamal; Vanka, Kumar (Frontiers in Chemistry, 2021)
At the dawn of the Universe, the ions of the light elements produced in the Big Bang nucleosynthesis recombined with each other. In our present study, we have tried to mimic the conditions in the early Universe to show how the recombination process would have led to the formation of the first ever formed diatomic species of the Universe: HeH+, as well as the subsequent processes that would have led to the formation of the simplest triatomic species: H-3 (+). We have also studied some special cases: higher positive charge with fewer number of hydrogen atoms in a dense atmosphere, and the formation of unusual and interesting linear, dicationic He chains beginning from light elements He and H in a positively charged atmosphere. For all the simulations, the ab initio nanoreactor (AINR) dynamics method has been employed.
Keywords: ab initio molecular dynamics; ab initio nanoreactor; Density functional theory; origin of molecules in the universe; the earliest lewis acid

Insights into the nature of self-extinguishing external donors for ziegler-natta catalysis: a combined experimental and DFT study - Vipin Raj, K.; Kumawat, Jugal; Dhamaniya, Sunil; Subaramanian, Murugan; Balaraman, Ekambaram; Kumar Gupta, Virendra; Vanka, Kumar; Grubbs, Robert H. (ChemCatChem, 2021)
Developing donors for Ziegler-Natta (ZN) catalysis to control the polymerization reaction and produce polymers with desirable properties has always been challenging due to the multi-component nature of the catalytic systems. Here, we have developed a new synthetic protocol for making two external donors, D-1 (2,2,2-trifluoroethyl myristate) and D-2 (2,2,2-trifluoroethyl palmitate) that show self-extinguishing properties, followed by a systematic DFT study to understand this peculiar property of these donors. D-1 and D-2 can undergo parallel reactions with aluminum and titanium species present in the system to produce ketones and aldehydes, which are poisons for ZN catalytic systems, thus explaining their self-extinguishing nature. The non-covalent interaction between the long alkyl chain of the donors with the surface plays a vital role in determining the donors ` self-extinguishing nature. There is a significant thermodynamic preference for the binding of the donor with the longer alkyl chain at the titanium center. The current work, therefore, provides interesting insights into how self-extinguishing donors function in ZN catalytic systems.
Keywords: DFT; donors; non-covalent interactions; self-extinguishing; Ziegler-Natta catalysis

Intermolecular interception of alpha-oxo gold carbenes of nitroalkyne cycloisomerization with 1, 2-benzo[d]isoxazole: synthesis of functionalized quinazoline 1-oxides - Dhote, Pawan S.; Pund, Kishor A.; Ramana, V, Chepuri (Journal of Organic Chemistry, 2021)
The known nitrogen-transfer reagent 1,2-benzo[d]isoxazole has been used to trap the postulated a-oxo gold carbene intermediate involved in the [Au]-catalyzed internal redox process of 2-alkynylnitrobenzenes. This process led us to develop a general convergent method for the synthesis of highly functionalized quinazoline 1-oxides.

Interrupting the [Au]-catalyzed nitroalkyne cycloisomerization: trapping the putative alpha-oxo gold carbene with benzo[c]isoxazole - Dhote, Pawan S.; Ramana, V, Chepuri (Organic Letters, 2021)
The [Au]-catalyzed nitroalkyne cycloisomerization of 2-alkynylnitrobenzenes leading to anthranils has been interrupted by possible trapping of the postulated intermediate alpha-oxo gold carbene with an external nucleophile such as benzo[c]isoxazole (anthranil). At the outset, this provides a simple synthesis of highly functionalized 3-acyl-(2-formylphenyl)-2H-indazoles with the sequential C-O, C-N, and N-N bond formations. This provides indirect support for the existence of alpha-oxo gold carbenes in the [Au]-catalyzed internal redox processes of nitroalkynes.

Intramolecularly double-donor-stabilized stannylene and its coordination towards Ag(I) and Au(I) centers - Chibde, Purva; Raut, Ravindra K.; Kumar, Vikas; Deb, Rahul; Gonnade, Rajesh; Majumdar, Moumita (Chemistry-An Asian Journal, 2021)
The intramolecularly double-donor-stabilized stannylene 1 has been synthesized from the salt-metathesis reaction between two equivalents of lithium pyridine ene-amide L1 and SnCl2. Compound 1 exhibits dipolar behavior when reacted with B(C6F5)(3) leading to the zwitterionic compound 2. The reaction of 1 with one equivalent and 0.5 equivalent of AgOTf (OTf=trifluoromethane sulfonate) result in the formation of a stannylene-AgOTf complex 3 and a homoleptic distannylene-silver ionic complex 4, respectively. Analogous to complex 4, the gold(I) complex 5 has been synthesized from the reaction between two equivalents of 1 and 0.5 equivalent of AuCl.SMe2/Me3SiOTf. Complex 5 is the first example of homoleptic stannylene-Au(I) ionic complex among the very scarce reports on stannylene-gold(I) coordination complexes. All compounds have been structurally characterized using single crystal X-ray crystallography. Solution-state characterization have been performed using multinuclear NMR techniques. Detailed DFT calculations on the optimized geometries 1 o, 3 o-5 o reveal the change in sp- hybridization on the pyramidal Sn(II) center upon metal coordination and their bonding overlaps.
Keywords: coordination; gold cation; hybridization; intramolecular donor; stannylene

Kinetics of 1-decene hydroformylation in an aqueous biphasic medium using a water-soluble Rh-sulfoxantphos catalyst in the presence of a cosolvent - Pagar, Nitin S.; Deshpande, Raj M. (International Journal of Chemical Kinetics, 2021)
The kinetics of hydroformylation of 1-decene has been studied in an aqueous biphasic medium using a water-soluble Rh-sulfoxantphos catalyst in the presence of N-methyl pyrrolidone as a cosolvent at 383-403 K. The rate was found to be first order, with concentrations of catalyst and olefin and partial order, with concentrations of hydrogen in the liquid phase. The plot of rate versus excess ligand and CO concentrations passed through maxima, indicating negative order dependence at higher concentrations. These trends have been interpreted based on the established hydroformylation mechanism. High selectivity towards the linear aldehyde was maintained (n: iso ratio > 30). An empirical rate equation has been proposed which was found to be in good agreement with the observed rate data within the experimental error. The activation energy was evaluated to be 74.76 kJ/mol.
Keywords: 1‐ aqueous‐ biphasic; cosolvent; decene; Hydroformylation; kinetics; rh‐ sulfoxantphos

Laser cladding of PAC 718, tribaloy T-700 and METCO 41 C hard facing powders on AISI SS 304L substrate - More, S. R.; Bhatt, D. V.; Menghani, J.; Paul, C. P.; Desale, G. R. (Materials Science, 2021)
The present investigation aims to deposit the three different hard facing powder (Triboloy T-700 and PAC 718, and TETCO 41 C) on SS 304L using laser cladding technique. The single and overlapped clad track was deposited using 2 kW laser power system. The optimized laser process parameters and 50% overlap clad track was used to deposit a large surface area. The optimum laser process parameters were finalised using single clad structure study. The cross-sections of the clad layers were used to obtain the microstructure and micro-hardness from different regions namely, clad layer, diffusion layer, and substrate. Throughout the study, the laser power was kept constant i.e. 1.2 kW. For single clad deposition, the scanning speed and powder feed rate varied from 0.3 to 0.5 m/min and 4 to 9 g/min, respectively. T-700 and PAC 718 shows uniform developing micro-structure while METCO 41 C shows the development of mixed dendritic and cellular type microstructure. The Triboloy shows the maximum surface hardness of 534 Hv, 321 Hv for PAC 718, and 294 Hv for METCO 41 C.

L-Histidine-derived smart antifouling biohybrid with multistimuli responsivity - Mohammad, Sk Arif; Dolui, Subrata; Kumar, Devendra; Mane, Shivshankar R.; Banerjee, Sanjib (Biomacromolecules, 2021)
A novel dual pH/thermoresponsive amphiphilic poly(histidine methacrylamide)-block-hydroxyl-terminated polybutadiene-block-poly(histidine methacrylamide) (PHisMAM-b-PB-b-PHisMAM) triblock copolymer biohybrid, composed of hydrophobic PB and ampholytic PHisMAM segments, is developed via direct switching from living anionic polymerization to recyclable nanoparticle catalyst-mediated reversible-deactivation radical polymerization (RDRP). The transformation involved in situ postpolymerization modification of living polybutadiene-based carbanionic species, end-capped with ethylene oxide, into dihydroxyl-terminated polybutadiene and a subsequent reaction with 2-bromo-2-methylpropionyl bromide resulting in a telechelic ATRP macroinitiator (Br-PB-Br). Br-PB-Br was used to mediate RDRP of an L-histidine-derived monomer, HisMAM, yielding a series of PHisMAM-b-PB-b-PHisMAM triblock copolymers. The copolymer's stimuli response was assessed against pH and temperature changes. The copolymer is capable of switching among its zwitterionic, anionic, and cationic forms and exhibited unique antifouling properties in its zwitterionic form. These novel triblock copolymers are expected to be show promising potential in biomedical applications.

Lithium compound catalyzed deoxygenative hydroboration of primary, secondary and tertiary amides - Bisai, Milan Kumar; Gour, Kritika; Das, Tamal; Vanka, Kumar; Sen, Sakya S. (Dalton Transactions, 2021)
A selective and efficient route for the deoxygenative reduction of primary to tertiary amides to corresponding amines has been achieved with pinacolborane (HBpin) using simple and readily accessible 2,6-di-tert-butyl phenolate lithium center dot THF (1a) as a catalyst. Both experimental and DFT studies provide mechanistic insight.

Lithium silicate nanosheets with excellent capture capacity and kinetics with unprecedented stability for high-temperature CO2 capture - Belgamwar, Rajesh; Maity, Ayan; Das, Tisita; Chakraborty, Sudip; Vinod, Chathakudath P.; Polshettiwar, Vivek (Chemical Science, 2021)
An excessive amount of CO2 is the leading cause of climate change, and hence, its reduction in the Earth's atmosphere is critical to stop further degradation of the environment. Although a large body of work has been carried out for post-combustion low-temperature CO2 capture, there are very few high temperature pre-combustion CO2 capture processes. Lithium silicate (Li4SiO4), one of the best known high-temperature CO2 capture sorbents, has two main challenges, moderate capture kinetics and poor sorbent stability. In this work, we have designed and synthesized lithium silicate nanosheets (LSNs), which showed high CO2 capture capacity (35.3 wt% CO2 capture using 60% CO2 feed gas, close to the theoretical value) with ultra-fast kinetics and enhanced stability at 650 degrees C. Due to the nanosheet morphology of the LSNs, they provided a good external surface for CO2 adsorption at every Li-site, yielding excellent CO2 capture capacity. The nanosheet morphology of the LSNs allowed efficient CO2 diffusion to ensure reaction with the entire sheet as well as providing extremely fast CO2 capture kinetics (0.22 g g(-1) min(-1)). Conventional lithium silicates are known to rapidly lose their capture capacity and kinetics within the first few cycles due to thick carbonate shell formation and also due to the sintering of sorbent particles; however, the LSNs were stable for at least 200 cycles without any loss in their capture capacity or kinetics. The LSNs neither formed a carbonate shell nor underwent sintering, allowing efficient adsorption-desorption cycling. We also proposed a new mechanism, a mixed-phase model, to explain the unique CO2 capture behavior of the LSNs, using detailed (i) kinetics experiments for both adsorption and desorption steps, (ii) in situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy measurements, (iii) depth-profiling X-ray photoelectron spectroscopy (XPS) of the sorbent after CO2 capture and (iv) theoretical investigation through systematic electronic structure calculations within the framework of density functional theory (DFT) formalism.

Lowering the C-H bond activation barrier of methane by means of SAC@Cu(111): periodic DFT investigations - Bhati, Meema; Dhumal, Jignesh; Joshi, Kavita (New Journal of Chemistry, 2021)
Methane has long captured the world's attention for being the simplest yet one of the most notorious hydrocarbons. Exploring its potential to be converted into value-added products has raised compelling interest. In the present work, we have studied the efficiency of single-atom catalysts (SACs) for methane activation employing density functional theory (DFT). The climbing image-nudged elastic band (CI-NEB) method is used in tandem with the improved dimer (ID) method to determine the minimum energy pathway for the first C-H bond dissociation of methane. Our study reported that the transition-metal doped Cu(111) surfaces enhance the adsorption, activate the C-H bond, and reduce the activation barrier for first C-H bond cleavage of methane. The results suggest Ru-/Co-/Rh-doped Cu(111) as promising candidates for methane activation with a minimal activation barrier and a less endothermic reaction. For these SACs, the calculated activation barriers for the first C-H bond cleavage are 0.17 eV, 0.24 eV, and 0.26 eV respectively, which is substantially lower than 1.13 eV, the activation barrier for Cu(111).

Lsi2: A black box in plant silicon transport - Coskun, Devrim; Deshmukh, Rupesh; Shivaraj, S. M.; Isenring, Paul; Belanger, Richard R. (Plant and Soil, 2021)
Background Silicon (Si) is widely considered a non-essential but beneficial element for higher plants, providing broad protection against various environmental stresses (both biotic and abiotic), particularly in species that can readily absorb the element. Two plasma-membrane proteins are known to coordinate the radial transport of Si (in the form of Si(OH)(4)) from soil to xylem within roots: the influx channel Lsi1 and the efflux transporter Lsi2. From a structural and mechanistic perspective, much more is known about Lsi1 (a member of the NIP-III subgroup of the Major Intrinsic Proteins) compared to Lsi2 (a putative Si(OH)(4)/H+ antiporter, with some homology to bacterial anion transporters). Scope Here, we critically review the current state of understanding regarding the physiological role and molecular characteristics of Lsi2. We demonstrate that the structure-function relationship of Lsi2 is largely uncharted and that the standing transport model requires much better supportive evidence. We also provide (to our knowledge) the most current and extensive phylogenetic analysis of Lsi2 from all fully sequenced higher-plant genomes. We end by suggesting research directions and hypotheses to elucidate the properties of Lsi2. Conclusions Given that Lsi2 is proposed to mediate xylem Si loading and thus root-to-shoot translocation and biosilicification, it is imperative that the field of Si transport focus its efforts on a better understanding of this important topic. With this review, we aim to stimulate and advance research in the field of Si transport and thus better exploit Si to improve crop resilience and agricultural output.
Keywords: Efflux; Lsi2; Membrane transport; Root-to-shoot translocation; silicon; Xylem loading

Mechanical properties of anodic titanium dioxide nanostructures - Kulkarni, Mukta; Sepitka, Josef; Junkar, Ita; Bencina, Metka; Rawat, Niharika; Mazare, Anca; Rode, Chandrashekhar; Gokhale, Suresh; Schmuki, Patrik; Daniel, Matej; Iglic, Ales (Materiali in Tehnologije, 2021)
Highly ordered and uniform titanium dioxide (TiO2) nanotubes (NTs) with different morphologies (15 nm, 50 nm and 100 nm in diameter) were prepared by the electrochemical anodization of Ti substrates. The TiO2 NTs' surface properties were characterized by X-ray diffraction (XRD) spectroscopy, Raman spectroscopy, scanning electron microscopy (SEM) and atomic force microscopy (AFM). The elastic modulus (E) and the Vickers hardness (HV) of the Ti foil and of the different-morphology TiO2 NTs were evaluated with the nano-indentation technique. E and HV increase with the decreasing length/diameter of the NTs, meaning that NTs with smaller diameters are more resistant to mechanical wear. The elastic modulus of the TiO2 NTs with 15-nm and 50-nm diameters is similar to that of the human bone.
Keywords: Elastic modulus; mechanical properties; titanium dioxide (TiO2) nanotubes; Vickers hardness

Mechanistic investigations on the catalytic transfer hydrogenation of lignin-derived monomers over Ru catalysts: theoretical and kinetic studies - Khan, Tufeil Sartaj; Singh, Dheerendra; Samal, Pragnya Paramita; Krishnamurty, Sailaja; Dhepe, Paresh Laxmikant (ACS Sustainable Chemistry & Engineering, 2021)
The hydrodeoxygenation (HDO) reaction of oxygenated compounds such as lignin-derived phenolics is well studied using molecular H-2 as a hydrogen source, yet the use of high pressures discourages its use on an industrial scale. As an alternative, the catalytic transfer hydrogenation (CTH) pathway provides in situ hydrogenation species, which reduces the need for the high-pressure infrastructure required when molecular hydrogen is used. Nevertheless, this strategy is scantly studied, and in lieu with this, herein we report the kinetic and mechanistic investigations of the CTH strategy for the HDO of guaiacol, phenol, anisole veratrole, and eugenol to their respective products. For potential commercialization purposes, low loading of metal, milder reaction conditions, and high selectivity toward desired products with a high H/C ratio were considered while designing catalysts (0.5 wt % Ru on SiO2-Al2O3, SiO2, Al2O3-acidic, Al2O3-basic, and Al2O3-neutral) for these reactions. As high as 74% cyclohexanol yield from guaiacol was achieved at 225 degrees C in the presence of isopropyl alcohol (IPA) as the hydrogen source and over the Ru/Al2O3-acidic catalyst reduced at 150 degrees C. A detailed kinetic study is carried out to understand the interaction of the substrate and intermediates with the catalyst and the influence of reaction parameters on the product formation. It was observed that the cisisomer of 2-methoxycyclohexanol rapidly undergoes further conversion than the trans-isomer. The experimental observations are substantiated through density functional theory (DFT) studies on Ru(0001) and guaiacol molecule complexes. DFT studies indicate that the adsorption of the cis-isomer is more exothermic as compared to that of the trans counterpart, and the underlying electronic factors are elucidated using charge density difference and density of states plots.
Keywords: catalytic transfer hydrogenation; Cyclohexanol; DFT; Hydrodeoxygenation; kinetics; lignin monomers; Supported metal catalysts

Metabolic engineering and synthetic biology for isoprenoid production in Escherichia coli and Saccharomyces cerevisiae - Navale, Govinda R.; Dharne, Mahesh S.; Shinde, Sandip S. (Applied Microbiology and Biotechnology, 2021)
Isoprenoids, often called terpenoids, are the most abundant and highly diverse family of natural organic compounds. In plants, they play a distinct role in the form of photosynthetic pigments, hormones, electron carrier, structural components of membrane, and defence. Many isoprenoids have useful applications in the pharmaceutical, nutraceutical, and chemical industries. They are synthesized by various isoprenoid synthase enzymes by several consecutive steps. Recent advancement in metabolic engineering and synthetic biology has enabled the production of these isoprenoids in the heterologous host systems like Escherichia coli and Saccharomyces cerevisiae. Both heterologous systems have been engineered for large-scale production of value-added isoprenoids. This review article will provide the detailed description of various approaches used for engineering of methyl-d-erythritol-4-phosphate (MEP) and mevalonate (MVA) pathway for synthesizing isoprene units (C-5) and ultimate production of diverse isoprenoids. The review particularly highlighted the efforts taken for the production of C-5-C-20 isoprenoids by metabolic engineering techniques in E. coli and S. cerevisiae over a decade. The challenges and strategies are also discussed in detail for scale-up and engineering of isoprenoids in the heterologous host systems.
Keywords: Escherichia coli; Isoprenoids; Metabolic engineering; Saccharomyces cerevisiae; synthetic biology

Metagenomic analysis of a mega-city river network reveals microbial compositional heterogeneity among urban and peri-urban river stretch - Yadav, Rakeshkumar; Rajput, Vinay; Dharne, Mahesh (Science of the Total Environment, 2021)
The rivers in the megacities face a constant inflow of extremely polluted wastewaters from various sources, and their influence on the connected peri-urban river is still poorly understood. The riverine system in Pune consists of Rivers Mula, Ramnadi, Pawana, Mutha, and Mula-Mutha, traversing through the urban settlements of Pune before joining River Bhima in the peri-urban region. We used MinION-based metagenomic sequencing to generate a comprehensive understanding of the microbial diversity differ-ences between the urban and peri-urban zones, which has not been explored at the meta scale until date. The taxonomic analysis revealed significant enrichment of pollution indicators microbial taxa (Welsch's t-test, p < 0.05, Benjamini-Hochberg FDR test) such as Bacteriodetes, Firmicutes, Spirochaetes, Synergistetes, Euryarcheota in the urban waters as compared to peri-urban waters. Further, the peri-urban waters showed a significantly higher prevalence of ammonium oxidising archaeal groups such as Nitrososphaeraceae (Student's t-test p-value <0.05 with FDR correction), thereby probably suggesting the influence of agricultural runoffs. Besides, the microbial community diversity assessment also indicated the significant dissimilarity in the microbial community of urban and peri-urban waters. Overall, the analysis predicted 295 virulence genes mapping to 38 different path-ogenic bacteria in the riverine system. Moreover, the higher genome coverage (at least 60%) for priority patho-gens such as Pseudomonas, Klebsiella, Acinetobacter, Escherichia, Aeromonas in the sediment metagenome consolidates their dominance in this riverine system. To conclude, our investigation showed that the unre-strained anthropogenic and related activities could potentially contribute to the overall dismal conditions and in-fluence the connected riverine stretches on the outskirts of the city . (c) 2021 Elsevier B.V. All rights reserved.
Keywords: Industrialisation; Peri-urban; Riverine system; Urbanisation; Virulence factors

Metagenomic analysis reveals genetic insights on biogeochemical cycling, xenobiotic degradation, and stress resistance in mudflat microbiome - Mohapatra, Madhusmita; Yadav, Rakeshkumar; Rajput, Vinay; Dharne, Mahesh S.; Rastogi, Gurdeep (Journal of Environmental Management, 2021)
<span style="color: rgb(33, 33, 33); font-family: BlinkMacSystemFont, -apple-system, "Segoe UI", Roboto, Oxygen, Ubuntu, Cantarell, "Fira Sans", "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">Mudflats are highly productive coastal ecosystems that are dominated by halophytic vegetation. In this study, the mudflat sediment microbiome was investigated from Nalabana Island, located in a brackish water coastal wetland of India; Chilika, based on the MinION shotgun metagenomic analysis. Bacterial, archaeal, and fungal communities were mostly composed of Proteobacteria (38.3%), Actinobacteria (20.7%), Euryarchaeota (76.1%), Candidatus Bathyarchaeota (6.8%), Ascomycota (47.2%), and Basidiomycota (22.0%). Bacterial and archaeal community composition differed significantly between vegetated mudflat and un-vegetated bulk sediments. Carbon, nitrogen, sulfur metabolisms, oxidative phosphorylation, and xenobiotic biodegradation were the most common microbial functionalities in the mudflat metagenomes. Furthermore, genes involved in oxidative stresses, osmotolerance, secondary metabolite synthesis, and extracellular polymeric substance synthesis revealed adaptive mechanisms of the microbiome in mudflat habitat. Mudflat metagenome also revealed genes involved in the plant growth and development, suggesting that microbial communities could aid halophytic vegetation by providing tolerance to the abiotic stresses in a harsh mudflat environment. Canonical correspondence analysis and co-occurrence network revealed that both biotic (vegetation and microbial interactions) and abiotic factors played important role in shaping the mudflat microbiome composition. Among abiotic factors, pH accounted for the highest variance (20.10%) followed by available phosphorus (19.73%), total organic carbon (9.94%), salinity (8.28%), sediment texture (sand) (6.37%) and available nitrogen (5.53%) in the mudflat microbial communities. Overall, this first metagenomic study provided a comprehensive insight on the community structure, potential ecological interactions, and genetic potential of the mudflat microbiome in context to the cycling of organic matter, xenobiotic biodegradation, stress resistance, and in providing the ecological fitness to halophytes. These ecosystem services of the mudflat microbiome must be considered in the conservation and management plan of coastal wetlands. This study also advanced our understanding of fungal diversity which is understudied from the coastal lagoon ecosystems.

Metagenomic exploration reveals a differential patterning of antibiotic resistance genes in urban and peri-urban stretches of a riverine system - Rajput, Vinay; Yadav, Rakeshkumar; Dharne, Mahesh S. (Environmental Science and Pollution Research, 2021)
{Antimicrobial resistance in the riverine ecosystem of urban areas is an alarming concern worldwide, indicating the importance of molecular monitoring to understand their patterning in urban and peri-urban areas. In the present study, we evaluated the influence of urban rivers on the connected peri-urban rivers of a riverine system of India in the context of antibiotic resistance genes. The rivers traversing through urban (Mula, Mutha, Pawana, and Ramnadi) and peri-urban stretches (Bhima and Indrayani) form the riverine system of Pune district in Maharashtra, India. The MinION-based shotgun metagenomic analysis revealed the resistome against 26 classes of antibiotics, including the last line of antibiotics. In total, we observed 278 ARG subtypes conferring resistance against multiple drugs (40%), bacitracin (10%), aminoglycoside (7.5%), tetracycline (7%), and glycopeptide (5%). Further, the alpha diversity analysis suggested relatively higher ARG diversity in the urban stretches than peri-urban stretches of the riverine system. The NMDS (non-metric multidimensional scaling) analysis revealed significant differences with overlapping similarities (stress value = 0.14
Keywords: Antibiotic resistance; MinION; Peri-urban rivers; Urbanization

Microglial remodeling of actin network by Tau oligomers, via G protein-coupled purinergic receptor, P2Y12R-driven chemotaxis - Das, Rashmi; Chinnathambi, Subashchandrabose (Traffic, 2021)
Alzheimer's disease (AD) is associated with age-related neurodegeneration, synaptic deformation and chronic inflammation mediated by microglia and infiltrated macrophages in the brain. Tau oligomers can be released from damaged neurons via various mechanisms such as exosomes, neurotransmitter, membrane leakage etc. Microglia sense the extracellular Tau through several cell-surface receptors and mediate chemotaxis and phagocytosis. The purinergic receptor P2Y12R recently gained interest in neurodegeneration for neuro-glial communication and microglial chemotaxis towards the site of plaque deposition. To understand the effect of extracellular Tau oligomers in microglial migration, the P2Y12R-mediated actin remodeling, reorientation of tubulin network and rate of migration were studied in the presence of ATP. The extracellular Tau species directly interacted with P2Y12R and also induced this purinoceptor expression in microglia. Microglial P2Y12R colocalized with remodeled membrane-associated actin network as a component of migration in response to Tau oligomers. As an inducer of P2Y12R, ATP facilitated the localization of P2Y12R in lamellipodia and filopodia during accelerated microglial migration. The direct interaction of extracellular Tau oligomers with microglial P2Y12R would facilitate the signal transduction in both way, directional chemotaxis and receptor-mediated phagocytosis. These unprecedented findings emphasize that microglia can modulate the membrane-associated actin structure and incorporate P2Y12R to perceive the axis and rate of chemotaxis in Tauopathy.
Keywords: actin remodeling; Alzheimer' chemotaxis; microglia; migration; s disease; Tau Oligomers

Molecular insights of fungal endophyte co-inoculation with Trichoderma viride for the augmentation of forskolin biosynthesis in Coleus forskohlii - Mastan, Anthati; Rane, Digeshwar; Dastager, Syed G.; Babu, C. S. Vivek (Phytochemistry, 2021)
To understand the compatibility of three native endophytic fungi Phialemoniopsis cornearis (SF1), Macrophomina pseudophaseolina (SF2) and Fusarium redolens (RF1) with Trichoderma viride (TV1) on Coleus forskohlii in enhancing plant growth and forskolin content, field experiments were conducted. Co-inoculation of RF1+TV1 showed significant improvement in plant growth (52%), root biomass (67%), and in planter forskolin content (94%), followed by treatment with SF2+TV1 and SF1+TV1. qRT-PCR was carried out to quantify expression of five key forskolin biosynthetic pathway genes (CfTPS2, CfTPS3, CfTPS4, CfCYP76AH15, and CfACT1-8) in RF1+TV1 treated C. forskohlii plants. Elevated expression of CfTPS2, CfTPS4, CfCYP76AH15 and CfACT1-8 genes was observed with RF1+TV1 combination as compared to uninoculated C. forskohlii plants. Besides, RF1+TV1 treatment considerably reduced the severity of nematode infection of C. forskohlii plants under field conditions. Thus, congruent properties of F. redolens (RF1) were witnessed with co-inoculation of T. viride (TV1) under field conditions which resulted in enhanced forskolin content, root biomass, and reduced nematode infections in C. forskohlii. Overall, this approach could be an economical and sustainable step towards cultivation of commercially important medicinal plants.
Keywords: Co-inoculation; Coleus forskohlii; endophytes; Forskolin; Lamiaceae; Trichoderma viride

Mycology and mycotechnology on postal stamps - Ghormade, Vandana; Pathan, Ejaj; Jyoti, Jeevan; Vartak, Ajit; Deshpande, Mukund (Current Science, 2021)
Mycology, the study of fungal biology, and philately, the study of postage stamps, are rarely connected, as they are very different activities. However, philatelic mycology can raise awareness of the facets of fungi which contribute significantly to human welfare. Fungi are photogenic and exhibit physiological wonders such as luminescence. They are important in biotechnology for their secondary metabolites. So, stamps depicting fungi signal the recognition of problems and prospects of prosperity posed by fungi in nutrition and health, agriculture, engineering, industry and ecology. Many countries have issued thousands of stamps on fungi. India with a rich heritage of fungal diversity lags in this respect. This article hopes to inspire action by celebrating the beauty and significance of fungi in the art of philately.
Keywords: mycology; mycophilately; Mycotechnology; photogenic appeal; postal stamps

Nanoparticles of biotite mica as Krishna Vajra Abhraka Bhasma: synthesis and characterization - Wele, Asmita; Sourav, De; Dalvi, Madhuri; Devi, Nandini; Pandit, Vijaya (Journal of Ayurveda and Integrative Medicine, 2021)
<div id="abssec0010" style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;"><h3 class="u-h4 u-margin-m-top u-margin-xs-bottom" id="sectitle0015" style="color: rgb(80, 80, 80); margin-top: 24px !important; margin-bottom: 8px !important; font-weight: 400 !important; line-height: 1.4 !important; font-size: 1rem !important;">Background Bio-inorganic <a class="topic-link" href="https://www.sciencedirect.com/topics/medicine-and-dentistry/nanoparticle" style="background-color: transparent; text-decoration-line: underline; text-decoration-thickness: 1px; text-decoration-color: rgb(46, 46, 46); color: rgb(46, 46, 46); word-break: break-word; text-underline-offset: 1px;" title="Learn more about nanoparticles from ScienceDirect's AI-generated Topic Pages">nanoparticles or <a class="topic-link" href="https://www.sciencedirect.com/topics/medicine-and-dentistry/metal-nanoparticle" style="background-color: transparent; text-decoration-line: underline; text-decoration-thickness: 1px; text-decoration-color: rgb(46, 46, 46); color: rgb(46, 46, 46); word-break: break-word; text-underline-offset: 1px;" title="Learn more about metal nanoparticles from ScienceDirect's AI-generated Topic Pages">metal nanoparticles are used in medicine for diagnostic and treatment purposes. The <a class="topic-link" href="https://www.sciencedirect.com/topics/medicine-and-dentistry/nanomedicine" style="background-color: transparent; text-decoration-line: underline; text-decoration-thickness: 1px; text-decoration-color: rgb(46, 46, 46); color: rgb(46, 46, 46); word-break: break-word; text-underline-offset: 1px;" title="Learn more about nanomedicines from ScienceDirect's AI-generated Topic Pages">nanomedicines from traditional Ayurvedic system are termed as bhasma. Rasashastra, the branch of inorganic medicines of <a class="topic-link" href="https://www.sciencedirect.com/topics/medicine-and-dentistry/ayurveda" style="background-color: transparent; text-decoration-line: underline; text-decoration-thickness: 1px; text-decoration-color: rgb(46, 46, 46); color: rgb(46, 46, 46); word-break: break-word; text-underline-offset: 1px;" title="Learn more about Ayurveda from ScienceDirect's AI-generated Topic Pages">Ayurveda, has documented monographs of metal-mineral bhasmas as potent drugs. However there is lack of scientific analytical data of the end products. <div id="abssec0015" style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;"><h3 class="u-h4 u-margin-m-top u-margin-xs-bottom" id="sectitle0020" style="color: rgb(80, 80, 80); margin-top: 24px !important; margin-bottom: 8px !important; font-weight: 400 !important; line-height: 1.4 !important; font-size: 1rem !important;">Objectives Present study was aimed at finding out the morphological, structural, elemental and chemical composition of the Krishna vajra abhraka bhasma (KVB). <div id="abssec0020" style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;"><h3 class="u-h4 u-margin-m-top u-margin-xs-bottom" id="sectitle0025" style="color: rgb(80, 80, 80); margin-top: 24px !important; margin-bottom: 8px !important; font-weight: 400 !important; line-height: 1.4 !important; font-size: 1rem !important;">Materials and methods Bhasma of KVB (Biotite Mica) was prepared in our laboratory using biotite mica sheets befitting selection criteria and carrying out further processes with strict SOPs as per AFI. <div id="abssec0025" style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;"><h3 class="u-h4 u-margin-m-top u-margin-xs-bottom" id="sectitle0030" style="color: rgb(80, 80, 80); margin-top: 24px !important; margin-bottom: 8px !important; font-weight: 400 !important; line-height: 1.4 !important; font-size: 1rem !important;">Results The bhasma complied with the confirmatory tests from Rasashastra. The physical and physicochemical tests correlate with the results obtained by instrumental analytical methods. SEM revealed square shaped nanoparticles of mean size of 92.3 nm. EDAX showed presence of Si, Mg, O, Fe, Ca, Na, C, K and Al. XRD revealed the crystalline nature of bhasma with mixture of various individual oxides and spinel shape of the crystal. DLS showed that the nanoparticles are unimodal in nature. FTIR and NMR showed the organic functional groups obtained from cow milk and selected herbs, indicating unique bio-inorganic nature of the KVB.

Naphthalene dianhydride organic anode for a `rocking-chair' zinc-proton hybrid ion battery - Ghosh, Meena; Vijayakumar, Vidyanand; Kurian, Maria; Dilwale, Swati; Kurungot, Sreekumar (Dalton Transactions, 2021)
Rechargeable batteries consisting of a Zn metal anode and a suitable cathode coupled with a Zn2+ ion-conducting electrolyte are recently emerging as promising energy storage devices for stationary applications. However, the formation of high surface area Zn (HSAZ) architectures on the metallic Zn anode deteriorates their performance upon prolonged cycling. In this work, we demonstrate the application of 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA), an organic compound, as a replacement for the Zn-metal anode enabling the design of a `rocking-chair' zinc-proton hybrid ion battery. The NTCDA electrode material displays a multi-plateau redox behaviour, delivering a specific discharge capacity of 143 mA h g(-1) in the potential window of 1.4 V to 0.3 V vs. Zn|Zn2+. The detailed electrochemical characterization of NTCDA in various electrolytes (an aqueous solution of 1 M ZnOTF, an aqueous solution of 0.01 M H2SO4, and an organic electrolyte of 0.5 M ZnOTF/acetonitrile) reveals that the redox processes leading to charge storage involve a contribution from both H+ and Zn2+. The performance of NTCDA as an anode is further demonstrated by pairing it with a MnO2 cathode, and the resulting MnO2||NTCDA full-cell (zinc-proton hybrid ion battery) delivers a specific discharge capacity of 41 mA h g(total)(-1) (normalized with the total mass-loading of both anode and cathode active materials) with an average operating voltage of 0.80 V.

Neem derivatives inhibits tau aggregation - Nalini, Gorantla Vijay; Das, Rashmi; Mulani, Fayaj Alam; Thulasiram, Hirekodathakallu V.; Chinnathambi, Subashchandrabose (Journal of Alzheimer s Disease Reports, 2021)
Tau is a phosphoprotein with natively unfolded conformation that functions to stabilize microtubules in axons. Alzheimer's disease pathology triggers several modifications in tau, which causes it to lose its affinity towards microtubule, thus, leading to microtubule disassembly and loss of axonal integrity. This elicit accumulation of tau as paired helical filaments is followed by stable neurofibrillary tangles formation. A large number of small molecules have been isolated from Azadirachta indica with varied medicinal applications. The intermediate and final limonoids, nimbin and salannin respectively, isolated from Azadirachta indica, were screened against tau aggregation. ThS and ANS fluorescence assay showed the role of intermediate and final limonoids in preventing heparin induced cross-β sheet formation and also decreased hydrophobicity, which are characteristic nature of tau aggregation. Transmission electron microscopy studies revealed that limonoids restricted the aggregation of tau to fibrils; in turn, limonoids led to the formation of short and fragile aggregates. Both the limonoids were non-toxic to HEK293T cells thus, substantiating limonoids as a potential lead in overcoming Alzheimer's disease.

New 1,2,3-triazole-appended bis-pyrazoles: synthesis, bioevaluation, and molecular docking - Danne, Ashruba B.; Deshpande, V, Mukund; Sangshetti, Jaiprakash N.; Khedkar, Vijay M.; Shingate, Bapurao B. (ACS Omega, 2021)
The present work describes design of a small library of new 1,2,3-triazole-appended bis-pyrazoles by using a molecular hybridization approach, and the synthesized hybrids were evaluated for their antifungal activity against different fungal strains, namely, Candida albicans, Cryptococcus neoformans, Candida glabrata, Candida tropicalis, Aspergillus niger, and Aspergillus fumigatus. All the compounds exhibited broad-spectrum activity against the tested fungal strains with excellent minimum inhibitory concentration values. The molecular docking study against sterol 14 alpha-demethylase (CYP51) could provide valuable insights into the binding modes and affinity of these compounds. Furthermore, these compounds were also evaluated for their antioxidant activity, which also resulted in promising data.

NHC-catalyzed desymmetrization of N-aryl maleimides leading to the atroposelective synthesis of N-Aryl succinimides - Barik, Soumen; Shee, Sayan; Das, Soumik; Gonnade, Rajesh G.; Jindal, Garima; Mukherjee, Subrata; Biju, Akkattu T. (Angewandte Chemie-International Edition, 2021)
Although the construction of axially chiral C-C bonds leading to the atroposelective synthesis of biaryls and allied compounds are well-known, the related synthesis of compounds bearing axially chiral C-N bonds are relatively rare. Described herein is the N-heterocyclic carbene-catalyzed atroposelective synthesis of N-aryl succinimides having an axially chiral C-N bond via the desymmetrization of N-aryl maleimides. The NHC involved intermolecular Stetter-aldol cascade of dialdehydes with prochiral N-aryl maleimides followed by oxidation afforded N-aryl succinimides in good yields and ee values. Preliminary studies on rotation barrier for the C-N bond, the temperature dependence, and detailed DFT studies on mechanism are also provided.
Keywords: asymmetric catalysis; axial chirality; desymmetrization; N-heterocyclic carbenes; organocatalysis

One-dimensional multichannel g-C3N4.7 nanostructure realizing an efficient photocatalytic hydrogen evolution reaction and its theoretical investigations - Antil, Bindu; Kumar, Lakshya; Ranjan, Ravi; Shenoy, Sulakshana; Tarafder, Kartick; Gopinath, Chinnakonda S.; Deka, Sasanka (ACS Applied Energy Materials, 2021)
The emerging metal-free carbon nitride (C3N4) offers prominent possibilities for realizing the highly effective hydrogen evolution reaction (HER). However, its poor surface conductivity and insufficient catalytic sites hinder the HER performance. Herein, a one-dimensional vermicular rope-like graphitic carbon nitride nanostructure is demonstrated that consists of multichannel tubular pores and high nitrogen content, which is fabricated through a cost-effective approach having the final stoichiometry g-C3N4.7 for HER application. The present g-C3N4.7 is unique owing to the presence of abundant channels for the diffusion process, modulated surface chemistry with rich- electroactive sites from N-electron lone pairs, greatly reduced recombination rate of photoexcited exciton pairs, and a high donor concentration (4.26 x 10(17) cm(3)). The catalyst offers a visible-light-driven photocatalytic H-2 evolution rate as high as 4910 mu mol h(-1)g(-1) with an apparent quantum yield of 14.07% at band gap absorption (2.59 eV, 479 nm) under 7.68 mW cm(-2) illumination. The number of hydrogen gas molecules produced is 1.307 x 10(15) s(-1) cm(-2), which remained constant for a minimum of 18 h of repeated cycling in the HER without any degradation of the catalyst. In density functional theory calculations, a significant change in the band offset is observed due to N doping into the system in favor of electron catalysis. The theoretical band gap of a monolayer of g-C3N4.7 was enormously reduced because of the presence of additional densities of states from the doped N atom inside the band gap. These impurity or donor bands are formed inside the band gap region, which ultimately enhance the hydrogen ion reduction reaction enormously.
Keywords: carbon nitride; Density functional theory; hydrogen evolution reaction; nitrogen-rich; Photocatalyst

One-pot bioconversion of tomato waste into poly-gamma-glutamic acid (gamma-PGA) biopolymer by a novel biocatalyst - Nair, Pranav G.; Joseph, Emmanuel; Killi, Naresh; Konchada, Sravanya; Nisal, Anuya; Gundloori, Rathna Venkata Naga; Dharne, Mahesh S. (ACS Sustainable Chemistry & Engineering, 2021)
Landfilling of rotten tomatoes can lead to environmental instability and a huge economic loss to the producers. This letter reports an effective valorization of tomato waste into a promising biopolymer, i.e., poly-gamma-glutamic acid (gamma-PGA) by a novel biocatalyst Bacillus paralicheniformis NCIM 5769. The gamma-PGA is one of the most expensive biopolymers with multifarious applications in wound healing, drug delivery, and regenerative medicine fields. However, its adoption into various applications is finite due to its exorbitant production cost. Herein, rotten tomatoes (without additional nutrient supplementation) served as the chassis for the fermentative production of 40 g/L of highly pure gamma-PGA within 48 h at ambient temperature. Further, NMR, DSC, and TGA confirmed the purity of synthesized gamma-PGA identical to standard gamma-PGA. This process has potential in the commercialization of.-PGA by significantly reducing the production cost, followed by the effective utilization of tomato waste leading to United Nations Sustainable Development Goal 12 (i.e., ensure sustainable consumption and production patterns).
Keywords: Commercialization; Poly-gamma-glutamic acid; Rotten tomatoes; United Nations Sustainable Development Goals; Waste utilization