Synthesis and biological evaluation of 2,4,5-trisubstituted thiazoles as antituberculosis agents effective against drug-resistant tuberculosis - Karale, Uttam B.; Krishna, Vagolu Siva; Krishna, E. Vamshi; Choudhari, Amit S.; Shukla, Manjulika; Gaikwad, Vikas R.; Mahizhaveni, B.; Chopra, Sidharth; Misra, Sunil; Sarkar, Dhiman; Sriram, Dharmarajan; Dusthackeer, V. N. Azger; et al. (European Journal of Medicinal Chemistry, 2019)
The dormant and resistant form of Mycobacterium tuberculosis presents a challenge in developing new anti-tubercular drugs. Herein, we report the synthesis and evaluation of trisubstituted thiazoles as antituberculosis agents. The SAR study has identified a requirement of hydrophobic substituent at C2, ester functionality at C4, and various groups with hydrogen bond acceptor character at C5 of thiazole scaffold. This has led to the identification of 13h and 13p as lead compounds. These compounds inhibited the dormant Mycobacterium tuberculosis H37Ra strain and M. tuberculosis H37Rv selectively. Importantly, 13h and 13p were non-toxic to CHO cells. The 13p showed activity against multidrug-resistant tuberculosis isolates. (C) 2019 Elsevier Masson SAS. All rights reserved.

Synthesis, characterization, Hirshfeld surface, cytotoxicity, DNA damage and cell cycle arrest studies of N, N-diphenyl-N `-(biphenyl-4-carbonyl/4-chlorobenzoyl) thiocarbamides - Pandey, Sunil K.; Pratap, Seema; Rai, Sunil K.; Marverti, Gaetano; Kaur, Manpreet; Jasinski, Jerry P. (Journal of Molecular Structure, 2019)
The condensation reaction of biphenyl-4-carbonyl isothiocyanate/4-chlorobenzoyl isothiocyanate with diphenylamine yielded two new compounds; N-diphenyl-N'-(biphenyl-4-carbonyl) thiocarbamide (1) and N, N-diphenyl-N'-(4-chlorobenzoyl) thiocarbamide (2). Structure of the compounds were determined by analytical, spectroscopic (UV-Visible, FT-IR, H-1, & C-13 NMR), powder and single-crystal X-ray diffraction methods. Hirshfeld surface analysis and their associated two dimensional fingerprint plots of compounds were used as theoretical approach to assess driving force for crystal structure formation via the intermolecular interactions in their crystal lattices. The compounds were screened for their in vitro cytotoxicity activity against a panel of five human cancer cell lines namely; cervical (2008 and C13*) and ovarian carcinoma (A2780, A2780/CP and IGROV-1). Both the compounds exhibited promising activity against cervical and IGROV-1 cancer cells whereas for the other two cell lines appreciable activities were observed. The cell cycle arrest at G(0)/G(1) phase is supported by the DNA damage and apoptosis studies of the compounds against 2008, C13* and IGROV-1 cell lines. (C) 2019 Elsevier B.V. All rights reserved.
Keywords: DNA damage and cell cycle arrest; Hirshfeld surface analysis; In vitro cytotoxicity; Thiocarbamide; X-ray crystal structure

Synthesis of a 3D free standing crystalline NiSex matrix for electrochemical energy storage applications - Dinara, Syed Mukulika; Samantara, Aneeya K.; Das, Jiban K.; Behera, J. N.; Nayak, Saroj K.; Late, Dattatray J.; Rout, Chandra Sekhar (Dalton Transactions, 2019)
The electrochemical performance for energy storage of three-dimensional (3D) self-supported heterogeneous NiSex cubic-orthorhombic nanocrystals grown by a facile one-step chemical vapour deposition (CVD) approach on Ni foam substrates has been explored. NiSex shows a high specific capacitance of 1333 F g(-1) with ultra-high energy (105 W h kg(-1)) and power (54 kW kg(-1)) densities. Furthermore, by integrating the as-grown NiSex as the anode and reduced graphene oxide as the cathode, a hybrid super-capacitor (HSC) prototype with a coin cell configuration has been fabricated. The device shows better capacitance (40 F g(-1)) with high energy (22 W h kg(-1)) and power (5.8 kW kg(-1)) densities and robust cycling durability (similar to 88% capacitance retention after 10 000 repeated cycles). For practical reliability of the as-fabricated HSC, a red LED has been illuminated by connecting it with two charged coin cells. These outstanding performances of the HSC prove to be promising for applications in high energy storage systems.

Synthesis of biodiesel using the Mg/Al/Zn hydrotalcite/SBA-15 nanocomposite catalyst - Prabu, Marimuthu; Manikandan, Marimuthu; Kandasamy, Prabu; Kalaivani, P. R.; Rajendiran, Nagappan; Raja, Thirumalaiswamy (Acs Omega, 2019)
Biodiesel production is an enchanting and eccentric pathway for the reduction of use of fossil fuels and is procured from biologically available renewable sources such as oils and fats. A novel Mg/Al/Zn-based hydrotalcite/SBA-15 composite material having a high catalytic activity was developed and investigated for the transesterification of vegetable oil. The rationally developed composites were systematically characterized and assessed in the transesterification of soybean oil in the presence of methanol. The physicochemical evaluation of the nanocomposites demonstrated the influence of Zn in the textural characteristics, density of the basic sites, and successively the catalytic activity. The catalytic efficiency of the MAZ-x/SBA-15 composite could be linked with the basic site density determined by the temperature-programmed desorption of CO2. Among all the composites used, the MAZ-1/SBA-15 nanocomposite showed the highest activity for biodiesels, with a yield of around 90% under economical reaction conditions. The catalytic studies conferred that the fatty acid methyl ester yield is significantly influenced by various experimental conditions such as the catalyst molar ratio, reaction temperature, pressure, and contact time. It was also found that the incorporation of hydrotalcite into SBA-15 pore channels can enhance the catalyst efficiency and stability of the nanocomposite. Moreover, under mild reaction conditions, a remarkably stable catalytic performance was achieved for more than 200 h of time on stream with no catalyst deactivation.

Synthesis of chiral tetrahydrofuran building blocks from pantolactones: application in the synthesis of empagliflozin and amprenavir analogs - Athawale, Paresh R; Kumari, Neeta; Kashinath, K; Reddy, D. Srinivasa (Europen Journal of Organic Chemistry, 2019)
Chiral 4,4-dimethyl tetrahydrofuran (THF) derivatives were synthesized from commercially available D-(-)/ l-(+) pantolactones, which can serve as chiral building blocks in medicinal chemistry. In addition, two of the synthesized building blocks were utilized for the synthesis of new amprenavir (HIV protease inhibitor) and empagliflozin (anti-diabetic) analogs. The synthesized analogs may have beneficial effects in terms of pharmacokinetics and modulation of bioactivity.

Targeted phenotypic screening in plasmodium falciparum and toxoplasma gondii reveals novel modes of action of medicines for malaria venture malaria box molecules (vol 3, e00534-17, 2018) - Subramanian, Gowtham; Belekar, Meenakshi A.; Shukla, Anurag; Tong, Jie Xin; Sinha, Ameya; Chu, Trang T. T.; Kulkarni, Akshay S.; Preiser, Peter R.; Reddy, D. Srinivasa; Tan, Kevin S. W.; Shanmugam, Dhanasekaran; Chandramohanadas, Rajesh (MSphere, 2019)

Taxonomic insights into the phylogeny of Bacillus badius and proposal for its reclassification to the genus Pseudobacillus as Pseudobacillus badius comb. nov. and reclassification of Bacillus wudalianchiensis Liu et al. - Verma, Ashish; Pal, Yash; Ojha, Anup Kumar; Kumari, Munesh; Khatri, Indu; Rameshkumar, N.; Schumann, Peter; Dastager, Syed G.; Mayilraj, Shanmugam; Subramanian, Srikrishna; Krishnamurthi, Srinivasan (Systematic and Applied Microbiology, 2019)
The species Bacillus badius is one of the oldest members of the genus Bacillus isolated from faeces of children and was classified based on its ability to form endospores [8]. In 16S rRNA gene sequence and phylogenetic analysis, Bacillus badius DSM 23(T) shared low similarity (93.0%) and distant relationship with B. subtilis, the type species of the genus Bacillus indicating that it does not belong to this genus. Additional strains of the species, B. badius DSM 5610, DSM 30822 and B. encimensis SGD-V-25 (which has been recently reclassified as a member of this species) were included in the study to consider intraspecies diversity. Detailed molecular phylogenetic and comparative genome analysis clearly showed that the strains of B. badius were consistently retrieved outside the cluster of Bacillus sensu stricto and also distantly related to the genera Domibacillus and Quasibacillus. Further, the data from biochemical reactions (inability to ferment most carbohydrates), polar lipids profile (presence of diphosphatidylglycerol, phosphatidylglycerol, phosphatidylethanolamine and an aminophosphoglycolipid) and fatty acids supported the molecular analysis. Thus the four B. badius strains; DSM 23(T), DSM 5610, DSM 30822 and SGD-V-25 displayed sufficient demarcating phenotypic characteristics that warrant their classification as members of a novel genus and single species, for which the name Pseudobacillus badius gen. nov. comb. nov. is proposed with Pseudobacillus badius DSM 23(T) (= ATCC 14574(T)) as the type strain. Additionally, based on our findings from phenotypic, chemotaxonomic and genotypic parameters, Bacillus wudalianchiensis DSM 100757(T) was reclassified as Pseudobacillus wudalianchiensis comb. nov. (C) 2019 Elsevier GmbH. All rights reserved.
Keywords: 16S rRNA; Bacillus; Bacillus wudalianchiensis; Fatty acids; polar lipids; Pseudobacillus

Temperature-dependent phonon dynamics of supported and suspended monolayer tungsten diselenide - Carvalho, Thais C. V.; Araujo, Francisco D. V.; dos Santos, Clenilton Costa; Alencar, Luciana M. R.; Ribeiro-Soares, Jenaina; Late, Dattatray J.; Lobo, Anderson Oliveira; Souza Filho, Antonio Gomes; Alencar, Rafael S.; Viana, Bartolomeu C. (AIP Advances, 2019)
Two-dimensional materials exhibit great potential for high-performance electronics applications and the knowledge of their thermal properties is extremely necessary, since they are closely related to efficient heat dissipation and electron-phonon interactions. In this study we report the temperature-dependence of the out-of-plane A(1g) Raman mode of suspended and supported CVD-grown single-crystalline tungsten diselenide (WSe2) monolayer. The A(1g) phonon wavenumber is linearly red-shifted for temperature ranging from 98 to 513 K, with first-order temperature coefficients beta of -0.0044 and -0.0064 cm(-1)/K for suspended and supported monolayer WSe2, respectively. The higher beta module value for supported sample is attributed to the increase of the phonon anharmonicity due to the phonon scattering with the surface roughness of the substrate. Our analysis of the temperature-dependent phonon dynamics reveal the influence of the substrate on thermal properties of monolayer WSe2 and provide fundamental information for developing of atomically-thin 2D materials devices. (C) 2019 Author(s).

Tf2NH catalyzed 1,6-conjugate addition of 2-hydroxy-p-quinone methides with -functionalized ketones: access to 2,3,4,9-Tetrahydro-1H-xanthenones and 4H-Chromene Derivatives - Satbhaiya, Shruti; Khonde, Nilesh S.; Rathod, Jayant; Gonnade, Rajesh; Kumar, Pradeep (European Journal of Organic Chemistry, 2019)
A Bronsted acid catalyzed tandem 1,6-conjugate sequential cycloaddition reaction using 2-hydroxy-p-quinone methides and -functionalized ketones is reported. The method allows xanthenones and chromenes to be accessed in moderate to excellent yield with broad substrate scope, which could be further functionalized to give a versatile set of products.
Keywords: -Functionalized ketone; 1; 6-Conjugated addition; Bronsted acid; Chromenes; Xanthenones

Thiol and halometallate, mutually passivated quantum dot ink for photovoltaic application - Mandal, Debranjan; Goswami, Prasenjit N.; Rath, Arup K. (ACS Applied Materials & Interfaces, 2019)
Tunable-band-gap colloidal QDs are a potential building block to harvest the wide-energy solar spectrum. The solution-phase surface passivation with lead halide-based halometallate ligands has remarkably simplified the processing of quantum dots (QDs) and enabled the proficient use of materials for the development of solar cells. It is, however, shown that the hallometalate ligand passivated QD ink allows the formation of thick crystalline shell layer, which limits the carrier transport of the QD solids. Organic thiols have long been used to develop QD solar cells using the solid-state ligand exchange approach. However, their use is limited in solution-phase passivation due to poor dispersity of thiol-treated QDs in common solvents. In this report, a joint passivation strategy using thiol and halometallate ligand is developed to prepare the QD ink. The mutually passivated QDs show a 50% reduction in shell thickness, reduced trap density, and improved monodispersity in their solid films. These improvements lead to a 4 times increase in carrier mobility and doubling of the diffusion length, which enable the carrier extraction from a much thicker absorbing layer. The photovoltaic devices show a high efficiency of 10.3% and reduced hysteresis effect. The improvement in surface passivation leads to reduced oxygen doping and improved ambient stability of the solar cells.
Keywords: ligand; mobility; quantum dot; solar cell; surface passivation

Total synthesis of Met(10)-teixobactin - Gunjal, Vidya B.; Reddy, D. Srinivasa (Tetrahedron Letters, 2019)
The total synthesis of cyclic depsipeptide Met(10)-teixobactin in solution-phase is described. Teixobactin is a structurally and mechanistically novel antimicrobial peptidic natural product with very impressive activities against Gram-positive pathogens. It happens to possess an L-allo-enduracididine (End) residue as part of macrocyclic ring which is not readily accessible. In this report, we have used serine ligation strategy as the key step to prepare an analogue of teixobactin where End being replaced with a readily available amino acid methionine. (C) 2019 Elsevier Ltd. All rights reserved.
Keywords: antibiotic; Cyclic tetrapeptides; Serine ligation; Teixobactin

Unusual route to synthesize indolizines through a domino SN2/michael addition reaction between 2‐mercaptopyridine and nitroallylic acetates - Roy, S. (European Journal of Organic Chemistry, 2019)
A straightforward synthesis of indolizines has been demonstrated from the reaction of 2‐mercaptopyridine and nitroallylic acetates in the presence of a base. The products were obtained in good isolated yield under relatively mild reaction conditions. The mechanistic insight of the reaction has been revealed by performing some control experiments demonstrating that the reaction is initiated by a sequential SN2/Michael addition reaction followed by removal of the sulfur moiety.
Keywords: domino reactions; Michael addition; nitrogen heterocycles; nucleophilic substitution; synthetic methods

Valorization of oceanic waste biomass: a catalytic perspective - Lucas, Nishita; Athawale, Anjali A.; Rode, Chandrashekhar V. (Chemical Record, 2019)
Efficacious waste utilization is vital in context of sustainability. The past decade has witnessed attempts of usage of land biomass and wastes for various applications, contributing towards a sustainable society. Exploitation of the marine biomass, which does not compete with habitation and food production like land biomass has been largely unnoticed and therefore not being utilized judiciously. Researchers have mainly exploited these resources as functional materials having significant potential applications. However, a catalytic perspective for the valorisation of these polymers arising from oceanic waste widens their scope and ameliorates its use. The objective of the present review is to demonstrate the effectiveness of chitin/chitosan as a catalyst and as a feedstock for deriving important fuels and chemicals. It displays all the reactions heterogeneously catalyzed by them along with the strategic methodology. Their important catalytic organic transformations attempted so far, have also been discussed. The future perspectives are also presented which if inculcated would improve the value addition of the waste, paving a way for greener and imperishable world.

VSe2-reduced graphene oxide as efficient cathode material for field emission - Ratha, S. (Journal of Physics and Chemistry of Solids, 2019)
Field emission properties of pristine VSe2 and its hybrid with reduced graphene oxide (RGO) have been investigated in detail. Promising field emission performance were noted with lower values of turn-on and threshold fields of ∼1.3 V μm−1 and 2.12 V μm−1 respectively for the VSe2/RGO hybrid which is much more superior than that of pristine VSe2 emitter and other 2D materials. Density Functional Theory (DFT) simulations have also been performed to qualitatively support our experimental observations through demonstration of Density of States and computation of work function for pristine VSe2 and hybrid VSe2/RGO. The lowering of work function and appearance of additional states near Fermi level from carbon p orbital of RGO is responsible for superior field emission characteristics in hybrid VSe2/RGO compared to pristine VSe2 which supports our experimental observations. Our experimental data and theoretical insight from electronic structure simulations strongly infer that the synthesized hybrid VSe2/RGO has the potential to be tailored as efficient and high performance cathode material in field emission based devices.
Keywords: cathode material; Chalcogenide; Density functional theory; field emission; Vanadium diselenide; Work function

Water-promoted surface basicity in FeO(OH) for the synthesis of pseudoionones (PS) and their analogues - Vernekar, Dnyanesh; Sakate, Sachin S.; Rode, Chandrashekhar V.; Jagadeesan, Dinesh (Journal of Catalysis, 2019)
Use of Iron oxyhydroxide (gamma-FeO(OH)) as a robust catalyst for the synthesis of important intermediates like pseudoionones and their analogues through the C-C bond formation reactions like knoevenagel and aldol condensation is explored. These motifs are the building blocks for the construction of the sesquiterpenes as well as the diterpenes such as retinoic acid, Vitamin A etc. Iron oxyhydroxide (gamma-FeO(OH)) was synthesized and well characterized using XRD, FT-IR, TEM, XPS and adsorption studies to establish the catalytic activity. A thorough investigation on the nature of basic sites and the role of water as a promoter was explored based on dye adsorption, in situ methanol dissociation and CO2 adsorption studies. The catalyst also showed a wide range of substrate scope with active methylene groups involving various functional groups such as cyanides, esters and acetophenones along with its stability and reproducibility. (C) 2019 Elsevier Inc. All rights reserved.
Keywords: Bronsted basicity; Iron (III) oxyhydroxide; Knoevenagel condensation; Pseudoionones; Surface hydroxyl groups

Zebrafish acid ceramidase: expression in Pichia pastoris GS115and biochemical characterization - Rajput, Vijay B.; Karthikeyan, Muthukumarasamy; Ramasamy, Sureshkumar (International Journal of Biological Macromolecules, 2019)
Acid ceramidase (N-acylsphingosine deacylase EC 3.5.1.23; AC) catalyzes the hydrolysis of ceramide into sphingosine (SPH) and free fatty acid. Zebrafish acid ceramidase (AC) has 60% homology with the human AC). Mutations in the human AC gene asah1 are known to cause Farber disease and spinal muscular atrophy with progressive myoclonic epilepsy. Zebrafish AC was overexpressed in Pichia pastoris by inserting asah1b gene into the genome. The majority of the overexpressed enzyme was secreted into the culture medium and purified to apparent homogeneity by stepwise chromatography. The recombinant protein was glycosylated precursor, that further undergoes limited autoproteolytic processing into two subunits (alpha and beta) which are visible in SDS-PAGE. The zebrafish AC is heterodimer associated with an inter-subunit disulfide bond. SDS-PAGE estimated the mass of native enzyme to be approximately 50 kDa & size exclusion chromatography estimated the mass of the active enzyme as approximately 100 kDa, suggesting the formation of a dimer of heterodimers. The protein was secreted as a mixture of processed and unprocessed forms in the culture media. A preliminary characterization of purified zebrafish AC was done by an enzyme assay. The zebrafish AC expressed in Pichia pastoris would be used for further structural and functional analysis. (C) 2018 Elsevier B.V. All rights reserved.
Keywords: Autoproteolytic processing; Pichia pastoris; Zebrafish acid ceramidase

2,5-Diformylfuran—an oxidation product of 5-hydroxymethylfurfural - Shinde, Suhas Hanmant; Rode, Chandrashekhar Vasant (2,5-Diformylfuran—an oxidation product of 5-hydroxymethylfurfural, 2020)
In the current scenario of depleting fossil-derived resources, biomass is considered a potential feedstock for sustainable energy supply and production of alternative chemicals. Among them, 2,5-diformylfuran (DFF) is one of the most important chemicals having widespread potential applications. DFF is produced from bioderived resources through the catalytic oxidation process. In this chapter, catalytic routes for the production of DFF starting from biomass-derived furan derivatives and sugars (e.g., mono/polysaccharides) are discussed in detail. Comprehensive emphasis is given to the catalysts (e.g., homogeneous and heterogeneous) and enzymes used for the transformation of various bioderived sources into DFF. Moreover, a brief look has also been given at the transformations and applications of DFF.
Keywords: 2; 5-Diformylfuran; 5-Hydroxymethylfurfural Biomass; Catalysis Chemicals; Oxidation Sugars

6 alpha-Hydroxy-4[14], 10[15]-guainadien-8 beta, 12-olide induced cell cycle arrest via modulation of EMT and Wnt/beta-catenin pathway in HER-2 positive breast cancer cells - Javir, Gitanjali; Joshi, Kalpana; Khedkar, Vijay; Rojatkar, Supada (Journal of Steroid Biochemistry and Molecular Biology, 2020)
Cyathocline purpurea has potential biological activities and has been widely used in traditional Chinese and Ayurvedic medicine. The aim of the present study is to elucidate the anticancer effect of its 6 alpha-hydroxy-4[14], 10 [15]-guainadien-8 beta, 12-olide (SRCP1) against HER-2 positive subtype of breast carcinoma. Anticancer effect of SRCP1 was assessed by cell viability, senescence, apoptosis, cell cycle, DNA synthesis, and gene expression assays. The activity was further validated by the molecular docking study. SRCP1 inhibits human HER-2 positive breast cancer growth via inhibition of DNA synthesis in a dose-dependent manner. SRCP1 induces cell cycle arrest at G(2)/M phase, late apoptosis, and necrosis. Further, it induces senescence causing reduction in migration via down-regulation of EMT. A remarkable increase in the number of necrotic cells and Annexin-V staining revealed that exposure to SRCP1 triggers late apoptosis. Treatment with SRCP1 increased E-cadherin, p21, p53, ER-alpha expression and decreased beta-catenin, MMP-9, snaill, TNF-alpha expression. SRCP1 showed binding affinity towards an active site of the HER-2 receptor. Our results of molecular docking and biological assays demonstrated the potent anticancer activity of SRCP1 in MDA-MB-453 cells via multiple pathways including EMT, TNF-alpha, and Wnt/beta-catenin signaling.
Keywords: Anticancer; beta-Catenin; EMT; Guaianolide; HER-2 inhibitor

Amidinato germylene-zinc complexes: synthesis, bonding, and reactivity - Yadav, Sandeep; Kumar, Rohit; Raj, K. Vipin; Yadav, Prashant; Vanka, Kumar; Sen, Sakya S. (Chemistry-An Asian Journal, 2020)
Despite the explosive growth of germylene compounds as ligands in transition metal complexes, there is a modicum of precedence for the germylene zinc complexes. In this work, the synthesis and characterization of new germylene zinc complexes [PhC(NtBu)(2)Ge{N(SiMe3)(2)}-> ZnX2](2)(X= Br (2) and I (3)) supported by (benz)-amidinato germylene ligands are reported. The solid-state structures of2and3have been validated by single-crystal X-ray diffraction studies, which revealed the dimeric nature of the complexes, with distorted tetrahedral geometries around the Ge and Zn center. DFT calculations reveal that the Ge-Zn bonds in2and3are dative in nature. The reaction of2with elemental sulfur resulted in the first structurally characterized germathione stabilized ZnBr(2)complexes PhC(NtBu)(2)Ge(=S){N(SiMe3)(2)}-> ZnBr2(5). Therefore, the Ge=S in5is in-between Ge-S single and Ge=S double bond length, owing to the coordination of a sulfur lone pair of electrons to ZnBr2.
Keywords: DFT; Germathione; Germylene; X-ray Structure; zinc

Analysis and artificial neural network prediction of melting properties and ideal mole fraction solubility of cocrystals - Gamidi, Rama Krishna; Rasmuson, Ake C. (Crystal Growth & Design, 2020)
Different artificial neural network (ANN) models have been developed and examined for prediction of cocrystal properties based on pure component physical properties only. From the molecular weight, melting temperature, melting enthalpy, and melting entropy of the pure compounds, the corresponding melting properties of the cocrystals and the cocrystal ideal solubility have been successfully predicted. Notably, no information whatsoever about the cocrystals is needed, besides the identification of the two compounds from which the cocrystal is formed. In total, 30 cocrystal systems of 8 different model components, namely, theophylline, piracetam, gabapentin-lactam, tegafur, nicotinamide, salicylic acid, syringic acid, and 4,4'-bipyridine, with distinct coformers have been chosen as the model systems for the construction of ANN models. In all the cases, 70% of the data points have been used to train the model, and the rest were used to test the capability of the model (as a validation set) as selected through a random selection process. The training process was stopped with overall r(2) values above 0.986. In particular, the models capture how the coformer structure influences the targeted physical properties of cocrystals.

Antibacterial properties of glycosylated surfaces: variation of the glucosidal moiety and fatty acid conformation of grafted microbial glycolipids - Valotteau, Claire; Roelants, Sophie L. K. V.; Dhasaiyan, Prabhu; Zibek, Susanne; Guenther, Michael; Soetaert, Wim; Everaert, Bernd; Pradier, Claire-Marie; Babonneau, Florence; Baccile, Niki; Humblot, Vincent (Molecular Systems Design & Engineering, 2020)
Glycosylated surfaces can display antimicrobial properties. It has been shown that sophorolipids can be used to develop biocidal coatings against Gram-positive and Gram-negative bacteria, but with a limited efficiency so far. Therefore, it appears necessary to further investigate the surface antibacterial activity of a broader set of structurally related glycolipids. The present work explores the influence of the glucosidic moiety (gluco-, sophoro-, cellobio-) and the fatty acid backbone (saturated,cisortransmonounsaturated). We show that the fatty acid backbone plays an important role:cisderivative of sophorolipids (SL) grafted onto model gold surfaces has better biocidal properties than saturated (SL0) andtransmonounsaturated (SLt) molecules, which appear to be inefficient. The number of glucose units is also a key factor: a one-third decrease in antibacterial activity is observed when having one glucose unit (GL) compared to two (SL). Sugar acetylation (SLa) does not seem to have an impact on the biocidal properties of surfaces. These results are not limited to sophorolipids, with cellobioselipids (CL) leading to similar antibacterial observations.

Antimicrobial profiling of coral reef and sponge associated bacteria from southeast coast of India - Rajasabapathy, Raju; Ghadi, Sanjeev C.; Manikandan, Balakrishnan; Mohandass, Chellandi; Surendran, Akhila; Dastager, Syed G.; Meena, Ram M.; James, Rathinam Arthur (2020)
Culturable bacteria associated with marine sponges and coral mucus (collected from Gulf of Mannar and Palk Bay) were screened for their prospective antimicrobial compounds against 9 bacterial pathogens (Bacillus megaterium, B. cereus, Salmonella typhimurium, Staphylococcus aureus, Proteus vulgaris, Klebsillla pneumoniae, Escherichia coli, Pseudomonas aeruginosa and Acinetobacter baumannii) and a fungal pathogen (Candida albicans). Of the 263 bacterial isolates obtained during this study, 52 isolates displayed antimicrobial activity against one or more pathogens. 16S rRNA gene sequencing revealed that these 52 strains affiliated to 14 genera from three phyla Proteobacteria, Firmicutes and Actinobacteria. Sponge associated bacterial strains F-04, 1-23, 1-33 and G-03 inhibited the growth of all the bacterial pathogens tested in this study and significantly the former 2 strains inhibited the growth of fungal pathogen also. Majority of the potential strains (88.4% out of 52 strains) inhibited the growth of Bacillus cereus. Interestingly, an actinomycete strain F-04 (isolated from sponge Orina sagittaria) inhibited the growth of methicillin resistant Staphylococcus aureus. In total, 10 volatile organic compounds were determined from the ethyl acetate and hexane extract of the strain F-04 using GC-MS. Overall, marine bacteria isolated during this study demonstrate the potential for the development of broad spectrum antibiotics.
Keywords: Anti-MRSA; Antimicrobial activity; Bacterial diversity; Coral reef; Sponge

Apparent umpolung reactivity of indole through [Au]-catalysed cyclisation and lewis-acid-mediated allylation - Shinde, Mahesh H.; Ramana, Chepuri V. (Chemistry-A European Journal, 2020)
The sequential functionalization of indole C2 and C3 in an umpolung fashion was executed with a predesigned substrate and choice of reagents. The developed method comprises gold-catalysed alkynol cycloisomerisation/intramolecular addition of C2 of indole and subsequent BF3.OEt2-mediated regioselective C3 allylation, resulting in the synthesis of the functionalized indoloisoquinolinone scaffold. The reaction involves 5-endo-alkynol cycloisomerisation and the dearomative addition of indole C2 to the intermediate oxocarbenium cation, which results in two equilibrating fused and spiropentacyclic intermediates, which upon treatment with allyl silane in the presence of BF3.OEt2, undergo selective indole C3 allylation. Other nucleophiles, such as hydride, azide and indole, were also found to be compatible with this process.
Keywords: Allylation; cyclization; domino reactions; Gold; umpolung

Archeal Di-O-geranylgeranyl glyceryl phosphate synthase of a UbiA superfamily member provides insight into the multiple human diseases - Boral, Debjyoti; Rao, Vamkudoth Koteswara; Ramasamy, Sureshkumar (Protein and Peptide Letters, 2020)
One of the unique characteristic features of the domain archaea, are the lipids that form the hydrophobic core of their cell membrane. These membrane lipids are characterized by distinctive isoprenoid biochemistry and the building blocks are two core lipid structures, sn-2,3-diphytanyl glycerol diether (archaeol) and sn-2,3-dibiphytanyl diglycerol tetraether (caldarchaeol). Archaeol has two phytanyl chains (C-20 in a bilayer structure connected to the glycerol moiety by an ether bond. The enzyme involved in this bilayer formation is Di-O-Geranylgeranyl Glyceryl Phosphate Synthase (DGGGPS), which is a member of a very versatile superfamily of enzymes known as UbiA superfamily. Multiple sequence analysis of the typical members of the UbiA superfamily indicates that the majority of conserved residues are located around the central cavity of these enzymes. Interestingly few of these conserved residues in the human homologs are centrally implicated in several human diseases, on basis of the major mutations reported against these diseases in the earlier clinical studies. It remains to he investigated about the role of these conserved residues in the biochemistiy of these enzymes. The binding and active site of these enzymes found to be similar architecture but have different substrate affinities ranging from aromatic to linear compounds. So further investigation of UbiA superfamily may be translated to novel therapeutic and diagnostic application of these proteins in human disease management.
Keywords: Archeal lipids; biA superfamily; DGGGPS; genetic diseases; lipid synthesis; membrane protein

Assessing the impact of deviations in optimized multistep flow synthesis on the scale-up - Sharma, M. K.; Raval, J.; Ahn, Gwang-Noh; Kim, Dong-Pyo; Kulkarni, A. (Reaction Chemistry & Engineering, 2020)
This manuscript highlights the unavoidable connection between manual and self-optimized flow synthesis protocols for multistep flow synthesis and its scale-up. While briefly summarizing the state of the art in the self-optimization approach, a brief summary of industrially scaled-up processes is also given. We have used as a case study the flow synthesis of ivacaftor that is optimized at the laboratory scale and is subjected to specific deviations deliberately. The resulting effects are captured in terms of their effect on the scale-up approach. The analysis shows that small deviations in performance viz. conversion or selectivity at every reaction step would lead to significant deviation in the process and the overall capital investment. Translating ``laboratory synthesis'' into ``commercial scale manufacturing'' needs careful differentiation between an optimized reaction step and realizing a commercially feasible process. We have also highlighted the role of 3D printing in fabricating prototype and scalable flow systems.

Bio-surfactant: a green and environmentally benign reaction medium for ligand-free Pd-catalyzed Mizoroki-Heck cross-coupling reaction in water - Patil, Seema P.; Jadhav, Sanjay N.; Rode, Chandrashekhar V.; Shejwal, Rajendra V.; Kumbhar, Arjun S. (Transition Metal Chemistry, 2020)
A simple and efficient protocol for the ligand-free Mizoroki-Heck coupling reaction of various aryl bromides with different olefins has been reported by using in situ generated PdNPs of size 5-10 nm in aqueous solution of bio-surfactant. The bio-surfactant used in this study is a saponin extract of the seeds of pericarps (pods) of theAcacia concinnaplant. The in situ generated PdNPs have been characterized by various techniques such as HRTEM, EDS and XPS. The influence of various parameters such as the nature and amount of bases, the nature of Pd precatalysts as well as the effect of temperature has been investigated on Mizoroki-Heck coupling reaction. The generated PdNPs significantly coupled the various aryl bromides with different olefins in aqueous extract of the seeds of pericarps (pods) of theAcacia concinnaplant at 100 degrees C. [GRAPHICS] .

Boron nitride and oxide supported on dendritic fibrous nanosilica for catalytic oxidative dehydrogenation of propane - Belgamwar, Rajesh; Rankin, Andrew G. M.; Maity, Ayan; Mishra, Amit Kumar; Gomez, Jennifer S.; Trebosc, Julien; Vinod, Chathakudath P.; Lafon, Olivier; Polshettiwar, Vivek (ACS Sustainable Chemistry & Engineering, 2020)
In this work, we were able to significantly increase the activity of boron nitride (BN) catalysts used for the oxidative dehydrogenation (ODH) of propane by designing and synthesizing BN supported on dendritic fibrous nanosilica (DFNS). DFNS/BN showed a markedly increased catalytic efficiency, accompanied by exceptional stability and selectivity. Textural characterization, together with solid-state nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopic analyses, indicates the presence of a combination of unique fibrous morphology of DFNS and various boron sites connected to silica to be the reason for this increase in the catalytic performance. Notably, DFNS/B2O3 also showed catalytic activity, although with more moderate selectivity compared to that of DFNS/BN. Solid-state NMR spectra indicate that the higher selectivity of DFNS/BN might stem from a larger amount of hydrogen-bonded hydroxyl groups attached to B atoms. This study indicates that both boron nitride and oxide are active catalysts and by using high surface area support (DFNS), conversion from propane to propene as well as productivity of olefins was significantly increased.
Keywords: Electron microscopy; heterogeneous catalysis; Nanostructures; NMR spectroscopy; propane dehydrogenation; X-ray diffraction; X-ray photoelectron spectroscopy

Can half-a-monolayer of pt simulate activity like that of bulk pt? solar hydrogen activity demonstration with quasi-artificial leaf device - Bajpai, Himanshu; Patra, Kshirodra Kumar; Ranjan, Ravi; Nalajala, Naresh; Reddy, Kasala Prabhakar; Gopinath, Chinnakonda S. (ACS Applied Materials & Interfaces, 2020)
Pt is the best cocatalyst for hydrogen production. It is also well-known that the surface atomic layer is critical for catalysis. To minimize the Pt content as cocatalyst, herein we report on half-a-monolayer of Pt (0.5 theta(Pt)) decorated on earth-abundant Ni-Cu cocatalyst, which is integrated with a quasiartificial leaf (QuAL) device (TiO2/ZnS/CdS) and demonstrated for efficient solar hydrogen production. For the QuAL, TiO2 is sensitized with ZnS and CdS quantum dots by the SILAR method. The 0.5 theta(Pt)-decorated Ni-Cu shows an onset potential of 0.05 V vs reversible hydrogen electrode for the hydrogen evolution reaction, which is almost similar to that of commercial Pt/C. Photoactivity of the present QuAL device with either bulk Pt or 0.5 theta(Pt)-coated Ni-Cu cocatalyst is, surprisingly, equal. Our findings underscore that a fraction of a monolayer of Pt can enhance the activity of the cocatalyst, and it is worth exploring further for the high activity associated with atomic Pt and other noble metals.
Keywords: artificial leaf; nickel-copper; Photocatalysis; platinum; Solar hydrogen

Cascade dehydrative amination of glycerol to oxazoline (vol 8, pg 2954, 2018) - Pandya, R.; Mane, R.; Rode, C. V. (Catalysis Science & Technology, 2020)
Correction for `Cascade dehydrative amination of glycerol to oxazoline' by R. Pandyaet al.,Catal. Sci. Technol., 2018,8, 2954-2965, DOI: ;10.1039/C8CY00185E.

Catalyst-free regioselective [3+2] cycloadditions of alpha,beta-unsaturated N-arylnitrones with alkenes to access functionalized isoxazolidines: a DFT study - Ghosh, Arnab; Mane, Manoj V.; Rode, Haridas B.; Patil, Siddappa A.; Sridhar, Balasubramanian; Dateer, Ramesh B. (Chemistry-An Asian Journal, 2020)
The catalyst-free regioselective [3+2]-cycloaddition of alpha,beta-unsaturated N-arylnitrones with alkenes are developed. The series of synthetically important functionalized isoxazolidines are prepared in good to excellent yields by step economic pathway under ligand and transition-metal-free conditions. The regioselective cycloaddition pathway supported by control experiment and computational study.
Keywords: DFT study; isoxazolidines; metal and ligand free; nitrone cycloaddition; Regioselective

Catalytic reductive deoxygenation of esters to ethers driven by hydrosilane activation through non-covalent interactions with a fluorinated borate salt - Rysak, Vincent; Dixit, Ruchi; Trivelli, Xavier; Merle, Nicolas; Agbossou-Niedercorn, Francine; Vanka, Kumar; Michon, Christophe (Catalysis Science & Technology, 2020)
We report the catalytic and transition metal-free reductive deoxygenation of esters to ethers through the use of a hydrosilane and a fluorinated borate BArF salt as a catalyst. Experimental and theoretical studies support the role of noncovalent interactions between the fluorinated catalyst, the hydrosilane and the ester substrate in the reaction mechanism.

CD44, a predominant protein in methylglyoxal-induced secretome of muscle cells, is elevated in diabetic plasma - Bai, Shakuntala; Chaurasiya, Arvindkumar H.; Banarjee, Reema; Walke, Prachi B.; Rashid, Faraz; Unnikrishnan, Ambika G.; Kulkarni, Mahesh J. (ACS Omega, 2020)
Methylglyoxal (MG), a glycolytic intermediate and reactive dicarbonyl, is responsible for exacerbation of insulin resistance and diabetic complication. In this study, NIG-induced secretome of rat muscle cells was identified and relatively quantified by SWATH-MS. A total of 643 proteins were identified in MG induced' secretome, of which 82 proteins were upregulated and 99 proteins were downregulated by more than 1.3-fold in SWATH analysis. Further, secretory proteins from the dassical secretory pathway and nonclassical secretory pathway were identified using SignalP and SecretomeP, respectively. A total of 180 proteins were identified with SignalP, and 113 proteins were identified with SecretomeP. The differentially expressed proteins were functionallyannotated by KEGG pathway analysis using Cytoscape soft ware with plugin clusterMaker. The differentially expressed proteins were'sfound to he involved m various pathways like extracellular matrix (ECM) receptor interaction, leukocyte transendothelial migration, fluid shear tress and atherosclerosis, complement and coagulation cascades, and lysosomal pathway. Since the MG levels are high in diabetic conditions, the presence of MG-induced isecreted proteins was inspected `by profiling human plasma of healthy and diabetic subjects (n = 10 each). CD44, a predominant MG -induced secreted protein, was found to be elevated in the diabetic plasma and to have a role in the development of insulin resistance.

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

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

Cooperative acid-base sites of solid Ba-Zr mixed oxide catalyst for efficient isomerization of glucose to fructose in aqueous medium - Shaikh, Samrin S.; Patil, Chetana R.; Kondawar, Sharda E.; Rode, Chandrashekhar V. (ChemistrySelect, 2020)
Efficient and highly selective isomerization of glucose to fructose was achieved by using the inexpensive Ba-Zr mixed metal oxide catalyst. Catalyst was prepared by varying Ba-Zr ratios using co-precipitation method. Various phases formed, planes exposed, morphology, elemental composition and particle size, basic site density and strength, oxidation state of elements were well studied by using various characterization techniques. The XRD analysis clearly indicates the presence of Ba+2 and Zr+4 in the form of BaO, ZrO2 and BaZrO3 phases. The SEM and HR-TEM images indicate that, Ba-Zr (2 : 1) catalyst prepared showed uniform morphology with spherical and rod-shaped particles ranging from 300 to 600 nm. Under the optimized reaction conditions Ba-Zr (2 : 1) catalyst exhibited excellent results in terms of 57 % of glucose conversion with 89 % selective formation of glucose. The presence of both acidic as well as basic sites play vital roles in activating the substrate molecules to selectively yield fructose. Ba-Zr (2 : 1) catalyst showed excellent recyclability performance up to four recycles.
Keywords: Co-precipitation; fructose; glucose; isomerization; mixed metal oxide

Correlation between multifunctional properties of lead free Iron doped BCT perovskite ceramics - Redhu, Preeti; Punia, Rajesh; Hooda, Ashima; Malik, B. P.; Sharma, Geeta; Sharma, Preeti (Ceramics International, 2020)
Present study investigates the effect of Fe doping on structural, microstructural, dielectric, ferroelectric, piezoelectric and magnetic properties of Barium calcium titanate (BCT) ceramics synthesized by solid state reaction route. The polycrystalline tetragonal structure of prepared ceramics was confirmed from XRD study. Analysis done using Rietveld refinement reveals reduction in lattice parameters as well as unit cell volume on substitution of Fe3+ ions in BCT lattice. Occurrence of four distinct Raman bands viz. 297 cm(-1) -302 cm(-1), 473 cm(-1)-475 cm(-1), 516 cm(-1) -524 cm(-1) and 729 cm(-1) -733 cm(-1) in Raman spectroscopic studies confirms the tetragonal phase of prepared ceramic compositions which are in accordance with XRD study. The Scanning Electron Microscopy analysis revealed polyhedral shaped grains whose average grain size decreased with increase in Fe content (x) in BCT ceramics. A diffused frequency independent phase transition was observed in temperature dependent dielectric measurements. Dielectric properties improved significantly, with shifting of transition temperature, T c close to room temperature with Fe doping. These studiessuggest applications of these ceramics in the development of environment friendly dielectric materials meeting X7R MLCCs specifications. The ferroelectric and piezoelectric properties of these ceramic compositions were found to decrease with increase in Fe concentration. Feeble room temperature ferromagnetism was observed for composition x = 0.020.
Keywords: BCT; dielectric response; Fe doping; ferroelectric properties; Lead free ceramics; Magnetic measurements

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.

Destroying antimicrobial resistant bacteria (AMR) and difficult, opportunistic pathogen using cavitation and natural oils/plant extract - Mane, Maya B.; Bhandari, Vinay M.; Balapure, Kshama; Ranade, Vivek V. (Ultrasonics Sonochemistry, 2020)
The present study reports, for the first time, a new and techno-economic strategy for effective removal of antimicrobial resistant bacteria (AMR) and difficult, opportunistic pathogen using cavitation and natural oils/plant extract. A hybrid methodology using natural oils of known health benefits has been discussed in combination with conventional physico-chemical method of hydrodynamic cavitation that not only provides efficient and effective water disinfection, but also eliminates harmful effects of conventional methods such as formation of disinfection by-products apart from reducing cost of treatment. A proof-of concept is demonstrated by achieving exceptionally high rates for practically complete removal of antimicrobial resistant (AMR) and relatively less researched, gram-negative opportunistic pathogen, Pseudomonas aeruginosa and gram-positive methicillin resistant, Staphylococcus aureus using a natural oil-Peppermint oil and two different cavitating reactors employing vortex flow (vortex diode) and linear flow (orifice) for hydrodynamic cavitation. > 99% disinfection could be obtained, typically in less than 10 min, using vortex diode with operating pressure drop of 1 bar and low dose of 0.1% peppermint oil as an additive, depicting very high rates of disinfection. The rate of disinfection can be further increased by using simple aeration which can result in significant lowering of oil dose. The conventional device, orifice requires relatively higher pressure drop of 2 bar and comparatively more time (similar to 20 min) for disinfection. The cost of the disinfection was also found to be significantly lower compared to most conventional processes indicating techno-economic feasibility in employing the developed hybrid method of disinfection for effectively eliminating bacteria including AMR bacteria from water. The developed approach not only highlights importance of going back to nature for not just conventional water disinfection, but also for eliminating hazardous AMR bacteria and may also find utility in many other applications for the removal of antimicrobial bacteria.
Keywords: AMR bacteria; Cavitation; Disinfection; Oil; Water treatment

Development of multiple reaction monitoring assay for quantification of carnosine in human plasma - Pandya, Vaibhav Kumar; Sonwane, Babasaheb; Rathore, Rajeshwari; Unnikrishnan, A. G.; Kumaran, Sangaralingam; Kulkarni, Mahesh J. (RSC Advances, 2020)
Carnosine, a histidine containing dipeptide, exerts beneficial effects by scavenging reactive carbonyl compounds (RCCs) that are implicated in pathogenesis of diabetes. However, the reduced carnosine levels may aggravate the severity of diabetes. The precise quantification of carnosine levels may serve as an indicator of pathophysiological state of diabetes. Therefore, we have developed a highly sensitive targeted multiple reaction monitoring (MRM) method for quantification of carnosine in human plasma samples. Various mass spectrometry parameters such as ionization of precursor, fragment abundance and stability, collision energy, tube lens offset voltage were optimized to develop a sensitive and robust assay. Using the optimized MRM assay, the lower limit of detection (LOD) and limit of quantification (LOQ) for carnosine were found to be 0.4 nM and 1.0 nM respectively. Standard curves were constructed ranging from 1.0 nM to 15.0 mu M and the levels of carnosine in mice and human plasma were determined. Further, the MRM assay was extended to study carnosine hydrolyzing activity of human carnosinases, the serum carnosinase (CN1) and the cytosolic carnosinase (CN2). CN1 showed three folds higher activity than CN2. The MRM assay developed in this study is highly sensitive and can be used for basal plasma carnosine quantification, which can be developed as a novel marker for scavenging of RCCs in diabetes.

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.

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.

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.

Effect of physical properties of dispersed phase on the residence time distribution in straight capillaries - Raval, Joy; Suryawanshi, Nalinee B.; Kulkarni, Amol A. (Chemical Engineering Science, 2020)

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.

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

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

Engineering staphylococcal protein A for high-throughput affinity purification of monoclonal antibodies - Amritkar, Vinod; Adat, Satish; Tejwani, Vijay; Rathore, Anurag; Bhambure, Rahul (Biotechnology Advances, 2020)
Protein A chromatography is one of the most widely used purification steps in the manufacturing of the various classes of recombinant and non-recombinant antibodies. Due to the higher cost, lower binding capacity, and limited life cycle of Protein A ligand, this affinity-based purification step is often one of the most significant contributors to the cost of manufacturing of monoclonal antibody (mAb) products. In the last decade, there has been significant progress in improving the Protein A chromatography throughput by designing new engineered Staphylococcal Protein A (SPA) variants with higher dynamic binding capacity, considerable alkaline tolerance, and mild acidic elution pH. This review aims at summarizing the various protein engineering approaches used for improving the throughput of the Protein A-based affinity purification of various immunoglobulins. With biopharmaceutical producers operating under ever-increasing pressure towards reducing the cost of manufacturing, these advances in engineered protein A variants will help in processing larger cell culture volumes with high throughput and thereby significantly lower the cost of raw materials.
Keywords: Alkaline tolerance; Dynamic binding capacity; Elution pH; Monoclonal antibodies; Protein A

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.

Enhancing thermomechanical and chemical stability of polymer electrolyte membranes using polydopamine coated nanocellulose - Ram, Farsa; Velayutham, Parthiban; Sahu, Akhila Kumar; Lele, Ashish K.; Shanmuganathan, Kadhiravan (ACS Applied Energy Materials, 2020)
We report here an approach to enhance the chemical and thermomechanical stability of polymer electrolyte membranes without compromising proton conductivity. Multifunctional polydopamine coated nanocellulose (PNC) was prepared by oxidative polymerization of dopamine on nano cellulose fibers and subsequently incorporated in Nafion by solution blending. PNC had a very significant effect on the thermomechanical properties of Nafion showing up to 200% improvement in the storage modulus at 90 degrees C. The PNC network also enhanced the dimensional stability of Nafion under constant stress. The 3 wt % PNC composite membrane showed a drastic reduction in creep compliance of about 39.9% and 46.5% in J(max) at 30 degrees and 60 degrees C, respectively. Free radical scavenging properties of polydopamine also helped to significantly enhance the chemical stability of Nafion, which was ascertained by accelerated degradation tests conducted in Fenton's reagent at 70 degrees C over 40 days. F-19 CP MAS solid state NMR, FTIR, and tensile tests on the membranes show higher chemical stability of the 3 wt % PNC composite membrane. The proton conductivity of the 3 wt % PNC composite membrane at 90 degrees C and 100% RH (similar to 125 mS/cm) was slightly higher than the Nafion membrane (similar to 94 mS/cm) at similar conditions. The retention of proton conductivity even with lower water uptake could be ascribed to proton hopping through polydopamine coated nanocellulose. Performance of the composite membrane was also evaluated in a single stack fuel cell and found to be better than recast Nafion. The benefits derived by this approach are not restricted to Nafion alone and shall broadly apply to many other polymer membranes.
Keywords: cellulose nanofibers; chemical stability; dimensional stability; fuel cell; polydopamine; polymer electrolyte membrane

Enzymatic and non-enzymatic detoxification of reactive carbonyl compounds improves the oxidative stress tolerance in cucumber, tobacco and rice seedlings - Nareshkumar, Ambekar; Subbarao, Sindhu; Vennapusa, Amarnatha Reddy; Ashwin, Vargheese; Banarjee, Reema; Kulkarni, Mahesh J.; Ramu, Vemanna S.; Udayakumar, Makarla (Journal of Plant Growth Regulation, 2020)
Detoxification of reactive carbonyl compounds (RCC) is crucial to sustain cellular activity to improve plant growth and development. Seedling growth is highly affected by accumulation of RCC under stress. We report non-enzymatic, enzymatic mechanisms of detoxification of RCC in the cucumber, tobacco and rice seedling systems exposed to glucose, NaCl, methyl viologen (MV) induced oxidative stress. The cucumber seedlings exposed to carbonyl stress had higher levels of malondialdehyde (MDA), protein carbonyls (PCs) and advanced glycation end-product N-carboxymethyl-lysine (AGE-CML) that negatively affected the seedling growth. The overexpression of enzyme encoding aldo-keto reductase-1 (AKR1) in tobacco and rice showed detoxification of RCC, MDA and methylglyoxal (MG) with improved seedling growth under glucose, NaCl and MV-induced oxidative stress. Further, small molecules like acetylsalicylic acid (ASA), aminoguanidine (AG), carnosine (Car), curcumin (Cur) and pyridoxamine (PM) showed detoxification of RCC non-enzymatically and rescued the cucumber seedling growth from glucose, NaCl and MV-stress. In autotrophically grown rice seedlings these molecules substantially improved seedling growth under MV-induced oxidative stress. Seedlings treated with the small molecules sustained higher guaiacol peroxidase (GPX) enzyme activity signifying the role of small molecules in reducing carbonyl stress-induced protein inactivation and AGE-CML protein modifications. The results showed that besides enzymatic detoxification of RCC, the small molecules also could reduce cytotoxic effect of RCC under stress. The study demonstrates that small molecules are attractive compounds to improve the seedling growth under stress conditions.
Keywords: Oxidative stress; plant growth; Reactive carbonyl scavengers; Seed germination; small molecules

Epoxy functionalized polymer grafted magnetic nanoparticles by facile surface initiated polymerization for immobilization studies of Candida Antarctica lipase B - Afzal, Haq Asif; Ghorpade, Ravindra V.; Thorve, Asmita K.; Nagaraja, Sreeharsha; Al-Dhubiab, Bandar E.; Meravanige, Girish; Rasool, Sahibzada Tasleem; Roopashree, Teeka S. (Reactive & Functional Polymers, 2020)
Immobilization of Candida Antarctica lipase B (Cal-B) was done on the epoxy functionalized polymer (EFP) grafted magnetic nanoparticles (MNPs) via covalent attachment with the active epoxy groups. The EFP brushes were grafted on iron-oxide based MNPs by a facile surface-initiated atom transfer radical polymerization (ATRP) using activators generated by electron transfer (AGET) of glycidyl methacrylate (GMA). Each step of the surface modification, polymer grafting, and enzyme immobilization process on the polymer grafted MNPs was studied using Fourier transform infrared spectroscopy (FTIR). A thermogravimetric analysis (TGA) calculated the amount of engineered organic components, a transmission electron microscopy (TEM) visualized the core-shell formation of the MNPs, and a vibrating sample magnetometer (VSM) validated their magnetic properties at various modification stages. The lipase immobilization efficiency was described as a function of immobilization time, as well as, enzyme amount. The activity was characterized within a range of pH, temperature, kinetic parameters, resusability and storage stability, for both the free and immoblized Cal-B enzyme. The results of this study suggested that poly(GMA) grafted MNPs can be successfully used for the immobilization of Cal-B with improved efficiencies compared to those obtained with free soluble lipase. The reported enzyme immobilization method appears to be reproducible and scalable for industrial production.
Keywords: Cal-B enzymes; enzymes; Immoblization; Magnetic nanoparticles

Exploring the pharmacological potentials of biosurfactant derived from planococcus maritimus SAMP MCC 3013 - Waghmode, Samadhan; Swami, Sagar; Sarkar, Dhiman; Suryavanshi, Mangesh; Roachlani, Sneha; Choudhari, Prafulla; Satpute, Surekha (Current Microbiology, 2020)
Therapeutic potential of biosurfactant (BS) has been improved in recent years. Our present study deals with production of BS from Planococcus maritimus SAMP MCC 3013 in a mineral salt medium (MSM) supplemented with glucose (1.5% w/v). Further, BS has been purified and partially characterized as glycolipid type through our previous publication. Current research article aimed to evaluate biological potential of BS against Mycobacterium tuberculosis, Plasmodium falciparum and cancerous cell lines. Planococcus derived glycolipid BS was found to be a promising inhibitor of M. tuberculosis (MTB) H37Ra at IC50 64.11 +/- 1.64 mu g/mL and MIC at 160.8 +/- 1.64 mu g/mL. BS also showed growth inhibition of P. falciparum at EC50 34.56 +/- 0.26 mu M. Additionally, BS also displayed the cytotoxicity against HeLa (IC50 41.41 +/- 4.21 mu g/mL), MCF-7 (IC50 42.79 +/- 6.07 mu g/mL) and HCT (IC50 31.233 +/- 5.08 mu g/mL) cell lines. Molecular docking analysis was carried for the most popular glycolipid type BS namely Rhamnolipid (RHL) aiming to interpret the possible binding interaction for anti-tubercular and anti-cancer activity. This analysis revealed the involvement of RHL binding with enoyl reductase (InhA) of M. tuberculosis. Docking studies of RHL with tubulin directed several hydrophobic and Vander Waal interactions to exhibit anti-cancer potential. The present study will be helpful for further development of marine bioactive molecules for therapeutic applications. Their anti-tubercular, anti-plasmodial and cytotoxic activities make BS molecules as a noteworthy candidate to combat several diseases. To the best of our knowledge, this is the first report on projecting the pharmacological potential of Planococcus derived BS. Graphic

FeCl3-catalyzed oxidative decarboxylation of aryl/heteroaryl acetic acids: preparation of selected API impurities - Gangadurai, Chinnakuzhanthai; Illa, Giri Teja; Reddy, D. Srinivasa (Organic & Biomolecular Chemistry, 2020)
There is an ever-increasing demand for impurity compounds for use in impurity profiling as regulatory agencies seek information during registration. Herein, we report the FeCl3-catalyzed oxidative decarboxylation of aryl- and heteroaryl acetic acids to the corresponding carbonyl compounds. A variety of useful aldehydes and ketones were prepared in a simple one-pot transformation by employing an environmentally benign, low-cost, and readily available iron salt. The utility of this method has been demonstrated by preparing five valuable API impurities including a multi-gram-scale synthesis of ketorolac impurity B for the first time.

Functional stability and structural transitions of a kunitz trypsin inhibitor from chickpea (CaTI2) - Bendre, Ameya D.; Shukla, Ekta; Ramasamy, Sureshkumar (Protein Journal, 2020)
Enzymes are important tools for various applications. We have studied structural transitions and functional stability of a Kunitz trypsin inhibitor from Chickpea (CaTI2), a potent insect gut-protease inhibitor, under different stress conditions like non-neutral pH, elevated temperature and co-solvent concentrations. CaTI2 was cloned and expressed in an eukaryotic systemP. pastorisand was investigated for conformational transitions using circular dichroism spectroscopy, differential scanning fluorimetry and activity assay. Native CaTI2 has a sheet dominant structure with 40% beta sheets and possess a single tryptophan residue situated in the hydrophobic core of the enzyme. The recombinant inhibitor maintained its maximum activity under alkaline pH with its secondary structure intact between pH 6-10. CaTI2 was observed to be thermally stable up to 55 degrees C with aT(m) of 61.3 degrees C above which the protein unfolds. On treating with chemical denaturant (urea), the CaTI2 lost its inhibitory potential and native conformation beyond 2 M urea concentration. Moreover, the protein unfolded at lower temperatures as the concentration of denaturant increased, suggesting more complex structural changes. Further, the stability of the inhibitor was found to be directly proportional to the solvent polarity. The data, herein offers significant information of inhibitor stability and activity which could be exploited for its further development into an effective pesticide. [GRAPHICS] .
Keywords: Chickpea; Circular dichroism spectroscopy; Differential scanning fluorimetry; Functional stability; Kunitz trypsin inhibitor

Gas-solid interactions with reactive and inert gas molecules by NAPUPS: can work function be a better descriptor of chemical reactivity? - Ghosalya, Manoj Kumar; Reddy, Kasala Prabhakar; Mhamane, Nitin B.; Ranjan, Ravi; Gopinath, Chinnakonda S. (Physical Chemistry Chemical Physics, 2020)
The gas-phase vibrational spectra of reactive (H(2)and O-2) and inert gases (N(2)and Ar) have been studied by near-ambient pressure (NAP) ultraviolet photoelectron spectroscopy (NAPUPS) up to 0.3 mbar pressure. The results obtained are divided into two parts and discussed. In the first part, the photoelectron spectra of monoatomic Ar and some homonuclear diatomic molecules, such as H-2, O-2, and N-2, have been recorded by NAPUPS and the effect of pressure on their energy position has been studied. It has been demonstrated that NAPUPS could be an essential tool to determine the intermolecular or interatomic interactions. In the second part, we have evaluated the influence of different solid surfaces on the binding energy (BE) position, the pattern of the vibrational features of diatomic N(2)molecules, and the first atomic levels (3p(3/2)and 3p(1/2)) of monoatomic Ar. It has been observed that with a change in the (electronic/chemical) nature of the surface, the BE of the above features also changes and reflects the change in the work function (phi) of the material. It is to be noted that Ar is an inert/noble gas and N(2)is the most stable molecule, and the above changes observed underscore that they can be employed as probe atoms/molecules to explore even the minor changes that occur on a solid surface due to a variety of reasons. Further, if the solid surface undergoes any chemical/electronic changes due to gas-solid interaction, such as oxidation/reduction, the phi of the surface changes again; this highlights the precise identification of the changes that occur under the reaction/measurement conditions. Therefore, the change in the BE of the gas-phase features can be used to determine even the minor changes in the phi of solid surfaces during the reaction or due to the reaction. The present findings have implications in probing the surface changes that occur in any surface-dependent phenomena, such as heterogeneous catalysis, electrochemistry, and materials that are predominantly controlled by surface contribution, such as layered (2D) materials, nanomaterials.

Glass transition temperature of polybutadiene and polyisoprene from high temperature segmental relaxation correlation using molecular dynamics - Sharma, Pragati; Roy, Sudip (Soft Materials, 2020)
Predicting glass transition temperature for rubber and rubber composites is immensely important for tire industry for the development of products and fine-tune process conditions. Molecular dynamics simulation is been used to predict glass transition temperature as a function of molecular-level structural changes, e.g., composition (functional groups), topology, and polymerization. However, prediction of glass transition temperature within experimental error bar from molecular dynamics simulation is only possible from all atomistic description (model) of the system as united atom and coarse-grained models under-predict the values. Conventional way of calculation of glass transition temperature from density (or any other properties which show sharp transition)-temperature plots are computationally very demanding because of atomistic simulations and simulations below the glass transition point, i.e., in glassy state. Here we report a novel method for calculation of glass transition temperature using only segmental relaxation correlation functions calculated at higher temperatures, i.e., above glass transition temperature. We have presented a protocol here and shown for two polymeric systems polybutadiene and polyisoprene. We believe this method cuts the computational cost of predicting glass transition temperature by one-third and will be applicable for industrial applications for structure-property validations.
Keywords: Glass transition temperature; molecular dynamics simulation; Polymers; rubber

Hexaaminobenzene derived two-dimensional polymer supercapacitor with high specific capacitance and energy density - Wakchaure, Vivek C.; Kottaichamy, Alagar R.; Nidhankar, Aakash D.; Ranjeesh, Kayaramkodath C.; Nazrulla, Mohammed A.; Thotiyl, Musthafa O.; Babu, Sukumaran S. (ACS Applied Energy Materials, 2020)
Recent research interest has been shifted toward energy storage devices, especially supercapacitors, which provide high specific power and long cycle life. In this context, two-dimensional organic polymers are a class of versatile materials found to be useful in energy storage applications. However, the performance is not promising due to the low capacitance, energy density, and cyclic stability. Here, we report a two-dimensional polymer derived from hexaaminobenzene and pyromellitic dianhydride and its excellent supercapacitor performance. The specific capacitance of the two-dimensional polymer is found to be 805 F g(-1) at 0.5 A g(-1) current density in galvanostatic charge-discharge, which is the highest among the organic twodimensional polymer and most of the carbon-based materials. The superior performance of the 2D-polymer compared to a model derivative (350 F g(-1) at 0.5 A g(-1) current density) points to the critical role of a 2D-platform to excel. The high energy density, excellent cyclic stability, and low self-discharge rate support the 2D-polymer supercapacitor as a promising candidate for futuristic applications.
Keywords: 2D-polymer; energy density; Energy storage; hexaaminobenzene; supercapacitor

Highly dispersed MnOx nanoparticles on shape-controlled SiO2 spheres for ecofriendly selective allylic oxidation of cyclohexene - Rao, Bolla Govinda; Sudarsanam, Putla; Rao, Tumula Venkateshwar; Amin, Mohamad Hassan; Bhargava, Suresh K.; Reddy, Benjaram M. (Catalysis Letters, 2020)
Shape-controlled metal nanomaterials are considered as a unique class of catalysts because of their synergistic size- and shape-dependent catalytic properties. This work reports the synthesis of a novel size- and shape-controlled catalyst, consisting of highly dispersed MnOx nanoparticles (average particle size of 4.5 nm) on shape-controlled SiO2 nanospheres (250-300 nm) for selective cyclohexene oxidation using air as the oxidant under solvent- and base-free conditions. The MnOx/SiO2 catalyst exhibited an excellent cyclohexene conversion (92%) with a high selectivity (96%) to the allylic products (2-cyclohexene-ol and 2-cyclohexene-one) under mild conditions, outperforming various SiO2 supported CoOx, FeOx, and CuOx catalysts. The better performance of shape-controlled MnOx/SiO2 nanocatalyst is due to high redox nature of Mn, uniform dispersion of smaller sized MnOx nanoparticles, and synergetic interaction between MnOx and SiO2 spheres, as evidenced by XPS and TEM studies. Further, the MnOx/SiO2 catalyst could be reused at least 5 times for selective cyclohexene oxidation with a negligible loss in its catalytic performance, indicating the excellent stability of shape-controlled metal nanocatalysts in organic synthesis under economically viable and mild conditions.
Keywords: Cyclohexene oxidation; MnOx nanoparticles; Shape-controlled catalyst; SiO2 nanospheres; Structure-performance relationship; Synergetic interaction

Highly efficient chemoselective N-tert butoxycarbonylation of aliphatic/aromatic/heterocyclic amines using diphenylglycoluril as organocatalyst - Awasthi, Amardeep; Mukherjee, Anagh; Singh, Mandeep; Rathee, Garima; Vanka, Kumar; Chandra, Ramesh (Tetrahedron, 2020)
An efficient approach for the Chemoselective N-tert-butoxycarbonylation of a variety of amines using diphenylglycoluril as organocatalyst has been described. For the first time, a plausible mechanism for the N-tert-butoxycarbonylation has been proposed using density functional theory (DFT) calculations supported by NMR studies. The reusability of the organocatalyst and observation of the desired N-Boc protected amines being formed without the formation of side products like urea, oxazolidinone, isocyanate, and N, N-di-Boc derivatives makes the present protocol desirable. (C) 2020 Elsevier Ltd. All rights reserved.
Keywords: DFT studies; Diphenylglycouril; N-tert butoxycarbonylation; organocatalyst; Proton shuttle mechanism

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

Improving the dissolution rate of the anticancer drug dabrafenib - Rai, Sunil K.; Gunnam, Anilkumar; Mannava, M. K. Chaitanya; Nangia, Ashwini K. (Crystal Growth & Design, 2020)
Dabrafenib (DBF) is an anticancer drug with selective B-Raf (BRAF) inhibition activity. In 2013, DBF was approved by the U.S. Food and Drug Administration (US-FDA) as a dabrafenib mesylate salt (DBF center dot MS). Because of insolubility in aqueous medium, specifically at the pH 4-8 biorelevant range, DBF is a Biopharmaceutics Classification System (BCS) Class II drug (i.e., low solubility and high permeability). Therefore, screening of novel salts and cocrystals was carried out using Generally Recognized as Safe (GRAS) coformers. A total of 10 salts/cocrystals including the mesylate salt were found to be stable under the crystallization conditions. Among acidic coformers, methane sulfonic acid (MS) and saccharin (SACH) formed salts, while fumaric acid (FA), succinic acid (SA), and adipic acid (ADA) gave cocrystals. However, monoamines formed a monohydrate salt where the water molecule is hydrogen bonded with the aminopyrimidine moiety of DBF. The replacement of monoamines with ethylenediamine (EN) dislocated the water molecule near the free amine of EN in the crystal structure with a change in space group from triclinic (P (1) over bar) to monoclinic (P2(1)/n). Dissolution measurements at pH 1.2 (0.1 N HCl) showed that DBF center dot EN superset of H2O dissolved rapidly compared to the DBF.MS salt (the dissolution rate of DBF center dot EN superset of H2O and DBF center dot MS is 11 and 2 times faster than that of DBF). Structure-activity relationship analysis showed that bonding of the aminopyrimidine moiety with strong hydrogen bond synthons inhibited dissolution, whereas a loosely bound or free site at the aminopyrimidine moiety enhanced the dissolution rate. Finally, a cytotoxicity study was performed for DBF, DBF center dot MS, and DBF center dot EN superset of H2O, which showed that DBF center dot EN superset of H2O is safe for normal cells and yet equally potent against cancer cells. Crystal engineering of an improved formulation of dabrafenib center dot ethylenediamine hydrate is presented as a new anticancer drug.

Influence of gold nanorods on the structure and photonic bandgap in a twist grain boundary phase with smectic C* blocks - Sahoo, Rajalaxmi; Rao, D. S. Shankar; Hiremath, Uma S.; Yelamaggad, V. C.; Shinde, Pravin; Bhagavatula L. V. Prasad; Prasad, S. Krishna (Journal of Molecular Liquids, 2020)
We describe the first report of the influence of gold nanorods (GNR) on the induced twist grain boundary smectic C* (TGBC*) phase in a binary mixture of achiral bent-core and chiral linear liquid crystals. The GNR concentration-dependent phase diagram of these nanocomposites shows that the thermal range of this twist grain boundary phase having smectic C* blocks phase increases by 50% for an intermediate composition compared to that for the host binary mixture without nanorods. The inclusion of the nanorods is seen to have substantial effect on the structural and photonic bandgap features of the TGBC* phase. For example, the helical periodidty gets altered in all the three dimensions: while those within the block undergo a huge increase, the one which is orthogonal to the blocks, shrinks. The spacing of the square grid pattern arising normal to the TGB helix direction increases for the nanocomposites getting even doubled for a certain composition, a feature evidenced by optical microscopy as well as optical diffraction. Xray diffraction clearly brings out the feature that the presence of GNR alters the thermal character of the transition between the TGBC* and the cholesteric phase. Quantitative analysis of the data indicates that the system would remain in the vicinity of a possible tricritical point, a behavior having wider ramifications to understand the underlying critical phenomenon. Based on the experimental observations, and capturing the essence of the reported adaptive defect core targeting mechanism we propose a model wherein GNRs get confined in the grain boundary region. This feature offers a potential to have periodic and anisotropic plasmonic structure arising out of the synergetic interactions between the metal nanorod and the twisted grain boundary structure. (C) 2019 Elsevier B.V. All rights reserved.
Keywords: 3D photonic bandgap; Gold nanorods; Induced phase; TGBC* phase; Tricritical phenomena

Insights into the catalytic activity of Ru/NaY catalysts for efficient H-2 production through aqueous phase reforming - Gogoi, Pranjal; Nagpure, Atul S.; Kandasamy, Prabu; Satyanarayana, C. V. V.; Raja, Thirumalaiswamy (Sustainable Energy & Fuels, 2020)
Ruthenium nanoparticles supported on NaY zeolite catalysts were synthesized by a simple ion exchange method. The structural and morphological features of the catalysts were systematically investigated using numerous techniques such as N-2-sorption, XRD, CO2-TPD, H-2-TPR, TEM, SEM, ICP-OES, TGA, CHN analysis, XPS, in situ CO-FTIR and NMR spectroscopy. These novel Ru-NaY catalysts were highly active and selective for H-2 production through aqueous phase reforming (APR) of glycerol and ethylene glycol. Among the various catalysts evaluated for H-2 production, the 3 wt% Ru-NaY catalyst demonstrated the highest catalytic performance with excellent H-2 selectivity and this catalyst exhibits better activity as compared to many state of the art catalysts reported so far. The superior catalytic activity of 3 wt% Ru-NaY was attributed to the appropriate Ru metal loading, good metal dispersion, small size of Ru nanoparticles, better metal-support interaction, and higher availability of catalytically active sites (Ru-0) and facilitated water gas shift (WGS) reaction. This catalytic activity result clearly shows that NaY zeolite supported Ru nanoparticles catalysts have excellent potential for H-2 production from biomass-derived compounds.

Integration of heterogeneous acid and base catalysis for clean synthesis of jet-fuel precursor from carbohydrates - Shinde, Suhas; Tarade, Komal; Mitra, Gaurav; Rode, Chandrashekhar (ChemistrySelect, 2020)
C-12 branched alkane fuel precursor was produced from carbohydrates using an efficient integrated solid acid and base catalysis approach involving: i) isomerisation-dehydration of carbohydrates to 5-(hydroxymethyl)furfural (HMF) over solid acid catalyst having both Lewis and Bronsted sites) in a biphasic MIBK (methylisobutylketone): water + DMSO solvent system and ii) Claisen-Schmidt condensation of crude HMF with MIBK over solid base catalyst. Initially, high yield of jet fuel precursor, (E)-1-(5-(hydroxymethyl)furan-2-yl)-5-methylhex-1-en-3-one from pure HMF and MIBK was achieved over basic CaMgAl(231) catalyst. The glucose dehydration to HMF was optimized in biphasic MIBK: H2O-NaCl: DMSO (8:1.5:0.5; v/v/v) system, with complete glucose conversion and 42% HMF yield over Zr-Mont possessing both Lewis and Bronsted acid sites. In an integrated dehydration + Claisen-Schmidt condensation sequence, Zr-Mont catalyst was filtered off and the crude HMF with MIBK underwent Claisen-Schmidt condensation over CaMgAl(231) catalyst. The overall 32% yield of Claisen-Schmidt condensation product was achieved from glucose. MIBK acting also as a product extractant, could be recovered upto 80%.
Keywords: Claisen-Schmidt condensation; dehydration; integrated; jet-fuel precursor; renewable

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

Lauric acid sophorolipid: accelerating the gelation of silk fibroin - Hirlekar, Swarali; Ray, Debes; Aswal, Vinod K.; Prabhune, Asmita A.; Nisal, Anuya (ACS Omega, 2020)
Silk fibroin (SF) hydrogels find wide applications in tissue engineering. However, their scope has been limited due to the long gelation time in ambient conditions. This paper shows the reduction in gelation time of silk fibroin to minutes upon doping with a newly synthesized lauric acid sophorolipid (LASL). LASL comprises a fatty acid, lauric acid (with a 12-carbon aliphatic chain), that is derivatized by glucose molecules using a non-pathogenic yeast Candida bombicola. LASL was characterized using spectroscopic (Fourier transform infrared spectroscopy) and chromatographic (high-performance liquid chromatography, thin-layer chromatography, and high-resolution mass spectrometry) methods. This gelation of SF is comparable to the effect of an anionic surfactant, sodium dodecyl sulfate (SDS). The microstructure of SF-LASL hydrogels was investigated by small-angle neutron scattering (SANS) measurements and exhibited the beads-on-a-necklace model. The rheological properties of these hydrogels show similarity to SF-SDS hydrogels, therefore presenting a greener alternative for tissue engineering applications.

Ligand structure directed dimensionality reduction (2D -> 1D) in lead bromide perovskite - Bakthavatsalam, Rangarajan; Haris, Muhammed P. U.; Shaikh, Samir R.; Lohar, Amruta; Mohanty, Ashutosh; Moghe, Dhanashree; Sharma, Shivani; Biswas, Chinmoy; Raavi, Sai Santhosh Kumar; Gonnade, Rajesh G.; Kundu, Janardan (Journal of Physical Chemistry C, 2020)
Low dimensional (2D, 1D) lead halide perovskites are currently attracting huge research interest due to their enabling properties. Demonstrating synthetic control on the dimensionality/ structure of these perovskites is highly challenging. Dimensionality in these perovskites is largely dictated by the nature/structure and composition of the incorporating ligands and the utilized synthetic conditions. Here, we demonstrate chemical composition based control on reduction of dimensionality (2D -> 1D) for lead bromide perovskite utilizing 2-(2-aminoethyl)isothiourea dihydrobromide as a common precursor ligand (Isothio Bromide). Controlling the hydrothermal reaction parameters (temperature, time) at a fixed precursor ratio affords corner-shared, contorted 2D sheet perovskite and corner-shared, contorted, chiral 1D chain perovskite. Such dimensionality reduction leads to contrasting photophysical properties: 1D chain perovskite shows long-lived and self-trapped broad band emission, whereas 2D perovskite shows short-lived, band edge emission with a long tail. Mechanistic studies and single crystal structure analysis reveal the incorporation of the utilized precursor ligand (Isothio Bromide) in 2D perovskite. Surprisingly, the 1D perovskite is found to be chiral (P2(1) space group) incorporating 2-(2-aminoethyldisulfanyl)ethanamine and ammonium ions as the achiral ligands generated in situ due to hydrothermal cleavage of the precursor (Isothio Bromide) ligand. Such structural and compositional change of the ligands, which manifests a different hydrogen bonding network in the resultant perovskite structure, plays a decisive role in dictating the final molecular formula and dimensionality/structure of the perovskite which largely controls their photophysical properties.

Lignocellulose-derived platform molecules: an introduction - Shinde, Suhas H.; Hengne, Amol; Rode, Chandrashekhar V. (Recent Advances in Development of Platform Chemicals, 2020)
Fossil feedstocks such as crude oil, natural gas, and coal are formed by natural anaerobic decomposition of buried organisms for a period of more than 650 million years. On the other hand, agrobiomass is quick to grow and becomes a renewable source of chemical and fuel production through processing in a biorefinery.
Keywords: Biomass; Biorefinery Cellulose; Lignocellulose Petrofinery; Platform molecules

Magnetically separable catalyst for condensation of renewable aldehydes and 2-methylfuran to saturated cyclic oxygenates - Tarade, Komal; Shinde, Suhas; Rode, Chandrashekhar (Fuel Processing Technology, 2020)
The saturated cyclic ethers produced from biomass derived aldehydes and 2-methylfuran are the potential diesel fuel candidates. The synthesis of saturated cyclic ethers is a two step process which involves acid catalyzed condensation of aldehydes with 2-methylfuran and the subsequent selective furan ring hydrogenation of the condensation products. Here, we designed a novel recyclable magnetic solid acid catalyst such as [Fe3O4@SiO2-Pr-Py-H][2HSO(4)(2-)] and employed for the condensation of 2-methylfuran with formaldehyde as model substrates and reaction parameters were optimized. Under the set reaction conditions, condensation of 2-methylfuran with several other aldehydes were also successfully achieved with very good yields. Further, several supported noble metal catalysts were screened in order to find suitable catalyst system for selective furan ring hydrogenation of condensation products. Among those, 5% Pd/C was found to be very active and selective for furan ring hydrogenation without formation of ring opened products under very low hydrogen pressure at room temperature. Prepared catalysts were thoroughly characterized with sophisticated techniques.
Keywords: fuel additives; Hydrogenation; Hydroxyalkylation-alkylation; Magnetic solid acid; Organosilica

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

Mixed metal oxide: a new class of catalyst for methanol activation - Mehta, Shweta; Agarwal, Sheena; Kenge, Nivedita; Mekala, Siva Prasad; Patil, Vipul; Raja, T.; Joshi, Kavita (Applied Surface Science, 2020)
In this work, we propose a mixed metal oxide as a catalyst and demonstrate it's ability to not only activate the MeOH molecule upon adsorption but also dissociate O-H and one of it's C-H bonds. MeOH activation is compared on two prominent facets of ZnAl(2)O(4 )viz. (2 2 0) and (31 1). While spontaneous O-H bond dissociation is observed on both facets, C-H bond dissociates only on the (3 1 1) surface. Multiple factors like atomic arrangement and steps on the surface, coordination of surface atoms, and their effective charges have a combined effect on MeOH activation. The (3 1 1) surface offers higher catalytic activity in comparison with (2 2 0) surface. Having a stepped surface, availability of multiple sites, and variation in the charge distribution are some of the reasons for better catalytic performance of (3 1 1) facet. Effect of orientation of MeOH with respect to the surface adds both, information and complexity to the problem. Observations pertinent to understanding this effect are also reported. A detailed analysis of atomic arrangement on the two surfaces provides a rationale as to why MeOH gets dissociated spontaneously on the mixed metal oxide. The promising results reported here opens up a new class of catalyst for research.
Keywords: DFT; MeOH; Spontaneous dissociation; ZnAl2O4

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 determinant for specificity: differential interaction of alpha-amylases with their proteinaceous inhibitors - Rane, Ashwini S.; Joshi, Rakesh S.; Giri, Ashok P. (Biochimica Et Biophysica Acta-General Subjects, 2020)
Background: alpha-Amylase inhibitors (alpha-AIs) belong to the discrete classes, and exhibited differential specificities against alpha-amylases from various sources. Several alpha-amylases and their complexes with inhibitors at the molecular level have been studied in detail. Interestingly, some alpha-AIs depict specific and selective interactions amid different insect alpha-amylases. Scope of review: There are studies to understand evolutionary variability and functional differentiation of insect alpha-amylases and their cognate inhibitors. We have examined sequence, structural, and interaction diversity between various alpha-amylases and alpha-AIs. Based on these analyses, we are providing a potential basis for the functional differentiation among certain insect a-amylases concerning mammalian counterparts and their interactions with different proteinaceous alpha-AIs. Major conclusions: Insect alpha-amylases have conserved domain architecture with differences in length, number of disulfide bonds, and secondary structure. Furthermore, few of them exhibit variable characteristics like chloride dependent activity, the presence of N-terminal glutamine residue to protect against proteolytic degradation, and loop variations near the enzyme active site. Conformation of alpha-AI protein could be an essential factor for their specificity and binding affinities towards target alpha-amylase(s). Furthermore, variation into the enzyme binding pocket residues might contribute to differential interactions with inhibitors. General significance: Molecular insights in the interactions between insect alpha-amylases and plant alpha-AI will provide the details of mechanisms assisting the inhibitor specificity. Furthermore, this information will help to design potent and effective alpha-AIs against specific alpha-amylase.
Keywords: Active site; alpha-amylase; alpha-amylase inhibitor; Insect; molecular interactions

Molecular investigation of coleopteran specific alpha-amylase inhibitors from amaranthaceae members - Rane, Ashwini S.; Venkatesh, Varun; Joshi, Rakesh S.; Giri, Ashok P. (International Journal of Biological Macromolecules, 2020)
alpha-Amylase inhibitors (alpha-AIs) target alpha-amylases and interfere with the carbohydrate digestion of insects. Among different classes of alpha-AIs, a knottin-type inhibitor from Amaranthus hypochondriacus (AhAI) was found to be specific against coleopteran storage pests. In this report, we have characterized three previously unidentified knottin-type alpha-AIs from various Amaranthaceae plants namely, Amaranthus hypochondriacus (AhAI2), Alternanthera sessilis (AsAI) and Chenopodium quinoa (CqAI). They contain a signal peptide, pro-peptide, and mature peptide. The mature peptides of the new alpha-AIs shared 68 to 78% identity with AhAI and have highly variable pro-peptide regions. Along with the cystine-knot fold, they showed conservation of reactive site residues. All recombinant alpha-AIs were successfully expressed in their active form and native state using an oxidative cytoplasmic environment. Inhibition studies against various amylases revealed that these inhibitors showed selective inhibition of coleopteran recombinant insect alpha-amylases viz., Tribolium castaneum, and Callosobruchus chinensis. Tribolium castaneum alpha-amylase inhibition potency was highest for AhAI2 (Ki similar to 15 mu M) followed by AsAI (Ki similar to 43 mu M) and CqAI (Ki similar to 61 mu M). Interaction analysis of these inhibitors illustrated that the reactive site of inhibitors make several non-covalent interactions with the substrate-binding pocket of coleopteran alpha-amylases. The selectivity of these inhibitors against coleopteran a-amylases highlights their potential in storage grain pest control. (C) 2020 Elsevier B.V. All rights reserved.
Keywords: alpha-amylase; alpha-amylase inhibitor; Amaranthaceae; Coleoptera; Knottin-type

Nanocellulose reinforced flexible composite nanogenerators with enhanced vibrational energy harvesting and sensing properties - Ram, Farsa; Gudadhe, Aniket; Vijayakanth, Thangavel; Aherrao, Swapnil; Borkar, Vivek; Boomishankar, Ramamoorthy; Shanmuganathan, Kadhiravan (2020)
We report here enhanced vibration and pressure sensing properties of nanocellulose reinforced flexible composite piezoelectric nanogenerators (PENGs). Surface fluorinated nanocellulose crystals (FNC) were incorporated into poly(vinylidene fluoride) (PVDF) and electrospun into composite nanofibers. Incorporation of only 2 wt % FNC in PVDF resulted in a significant enhancement in pressure sensitivity with a very low detectable pressure limit of 10 Pa and a sensitivity of up to 18 mV/kPa. The composite PENGs also demonstrated very high sensitivity for forced continuous vibrations. 2FNC/PVDF composites resulted in an order of magnitude higher voltage response over neat PVDF for a given strain. When PENGs were mounted on a vacuum pump for transduction of mechanical vibrations into electrical energy, 2FNC/PVDF composite devices manifested similar to 3.8 times enhanced voltage output over neat PVDF and faster charging of a capacitor. The enhanced piezoelectric properties of PVDF/FNC nanocomposites could be attributed to the tailored interface between PVDF and nanocellulose and enhanced polarizability.
Keywords: Composite; Nanofiber; piezoelectric; pressure; Sensor; vibration

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

Novel hybrid cavitation process for enhancing and altering rate of disinfection by use of natural oils derived from plants - Mane, Maya B.; Bhandari, Vinay M.; Balapure, Kshama; Ranade, Vivek V. (Ultrasonics Sonochemistry, 2020)
The present study is an attempt to improvise the hydrodynamic cavitation methodology for effective disinfection of water and also to suggest prototype development for practical application. The enhancement in the disinfection efficiency was evaluated specifically for the effect of pressure, temperature, pH, microbial inoculum size and also on effect of different additives for the two model microbial strains, gram-negative (Escherichia coli) and gram-positive (Staphylococcus aureus). The efficacy of the hydrodynamic cavitation is evaluated for the two types of flows/cavitation devices - linear flow in the case of orifice and vortex flow for vortex diode. The vortex diode requires significantly lower pressures, 50% lower as compared to orifice for the similar extent of disinfection. While the bacterial disinfection at high temperature is known, the usefulness of hydrodynamic cavitation is especially evident at ambient conditions and the process is effective even at very high concentrations of bacteria, not reported so far. The reactor geometry also has significant effect on the disinfection. The present study, for the first time, reports possible use of different natural oils such as castor oil, cinnamon oil, eucalyptus oil and clove oil in conjunction with hydrodynamic cavitation. The nature of oil modifies the cavitation behavior and an order of magnitude enhancement in the cavitation rate was observed for the two oils, eucalyptus and clove oil for a very small concentration of 0.1%. The increased rates of disinfection, of the order of 2-4 folds, using oil can drastically reduce the time of operation and consequently reduce cost of disinfection. A possible mechanism is proposed for the effect of oil and hydrodynamic cavitation in cell destruction through the rupture of cell wall, oxidative damage and possible DNA denaturation. A cavitation model using per pass disinfection was used to correlate the data. The increased efficiency using oils and possible benefits of the developed process, where natural oils can be perceived as biocatalysts, can have significant advantages in practical applications.
Keywords: Antimicrobial; Cavitation; Disinfection; Oil; Wastewater treatment

Ofloxacin-loaded PLLA nanofibrous mats for wound dressing applications - Rade, Priyanka P.; Garnaik, Baijayantimala (ACS Applied Bio Materials, 2020)
Poly(l-lactide) (PLLA) was synthesized from l-lactide in the presence of a zinc salen complex. Ofloxacin (OFLX)-loaded PLLA nanofibrous mats were fabricated by electrospinning using dichloromethane/dimethyl sulfoxide (4:1 v/v) solutions containing different amounts of OFLX (1, 3, 5, and 10 w/w%). The morphology and diameter of nanofibrous mats were studied by scanning electron microscopy (SEM). The internal morphology of the nanofibers was examined by transmission electron microscopy (TEM). Miscibility between OFLX and PLLA in nanofibrous mats was confirmed by attenuated total reflection–Fourier transform infrared (ATR–FTIR) spectroscopy. Differential scanning calorimetry (DSC) confirmed the interaction of OFLX with PLLA nanofibrous mats. The presence of OFLX in PLLA nanofibrous mats increased the tensile strength significantly, which was confirmed by dynamic mechanical analysis (DMA). The in vitro drug release profile was studied at pH values 4.6, 5.8, and 7.4. OFLX-loaded PLLA nanofibrous mats showed burst release till first 12 h, and sustained release followed up to 168 h. The in vitro biocompatibility test of nanofibrous mats was carried out using the 3-(4,5-dimethylthiazol-2yl)-2,5-diphenyl tetrazolium bromide (MTT) assay against the NIH/3T3 fibroblast cell line. The results of MTT assay demonstrated cell viability and cell proliferation at a concentration as low as 10 w/w%, which proved their nontoxicity and biocompatibility. OFLX-loaded PLLA nanofibrous mats exhibited good antibacterial activity against Staphylococcus aureus and Escherichia coli. The in vivo wound healing study on rats showed 44, 65, and 88% wound closure rates on 14th day with control, PLLA, and OFLX-loaded PLLA nanofibrous mats, respectively. The results proved that the PLLA nanofibrous mats loaded with an appropriate concentration of OFLX are promising candidates for wound dressing applications.
Keywords: nanofibers nontoxic biocompatible; PLLA ofloxacin; wound dressing

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

One-pot synthesis of bimodal (macro-meso, micro-mesoporous) silica by polyHIPE: parameter studies - Wale, Apparav; Nalawade, Archana; Ponrathnam, Surendra; Rajan, C. R.; Badiger, Manohar (Journal of Porous Materials, 2020)
Porous silica with hierarchical organization of pore structure is desired for a variety of applications such as, chromatography, sensing, control release, scaffold for biomedical applications and catalysis. Highly porous polymers obtained from high internal phase emulsion (HIPE) templating route have attracted increasing attention of researchers due to their hierarchical porous and interconnected structure with high porosity and low density. The novel method adopted in our approach combines redox initiated polymerization using HIPE polymerization and an in-situ sol-gel processing technique followed by calcination to obtain highly porous materials. The obtained materials have reminiscent of polyHIPE morphology containing pores and interconnected pore throats in micrometer size range with mesopores on the wall of macropores. The effect of concentration of TEOS, volume of dispersed phase, crosslinker concentration, shear rate and surfactant concentration as well as variation in calcination temperatures on the properties of silica materials were examined.
Keywords: Mesoporous material; PolyHIPE; Polymer-silica hybrid; Porous silica

Organocatalytic cascade knoevenagel-michael addition reactions: direct synthesis of polysubstituted 2-amino-4H-chromene derivatives - Jadhav, Sanjay N.; Patil, Seema P.; Sahoo, Dipti Prava; Rath, Dharitri; Parida, Kulamani; Rode, Chandrashekhar V. (Catalysis Letters, 2020)
In this report, we documented novel strategy for the synthesis of bioactive polysubstituted 2-amino-4H-chromine derivatives under a heterogeneous Al-MCM-41-LDH@APTES (ALAM) catalysis. A synthetic procedure is developed to prepare Al-MCM-41-LDH@APTES (ALAM) heterogeneous basic catalysts. Mesoporous Al-MCM-41 is functionalized by known grafting chemistry via layered double hydroxide (LDH) nanosheets and (3-aminopropyl)triethoxysilane (APTES) moiety as a basic organocatalyst. The resulting catalysts contain amino group functionality on the external surface as well as inside the layers and the basicity can be tuned by the loading of APTES. The samples were fully characterized by Si-29 and C-13 CP/MAS NMR, infrared absorption spectroscopy, TEM, XPS, EDX, TGA, XRD, CO2-TPD, N-2 adsorption isotherms measurements, and they were successfully examined for the cascade type Knoevenagel-Michael addition reactions. The product yields associated with these substrates were optimized, and key reaction parameters affecting the yields were identified. The present catalytic method is simple and robust for diversity oriented synthesis which proceeds good to excellent yields without generating any hazards waste. The broad substrate scope, excellent functional group compatibility makes this protocol highly useful towards synthesis of polysubstituted alpha-cyanoacrylates, alpha-cyanoacrylonitriles and 2-amino-4H-chromenes with an electron-donating or electron-withdrawing group. We have also successfully established a flow reaction system, gram-scale synthesis as well as catalyst recyclability up to six catalytic cycles without appreciable loss of its activity. Graphic
Keywords: 2-Amino-4H-chromines; Amine functionalized solid catalysts; cascade synthesis; Diversity oriented syntheses (DOS); flow chemistry

Overturning the peribysin family natural products isolated from periconia byssoides OUPS-N133: synthesis and stereochemical revision of peribysins A, B, C, F, and G - Athawale, Paresh R.; Kalmode, Hanuman P.; Motiwala, Zenia; Kulkarni, Kiran A.; Reddy, D. Srinivasa (Organic Letters, 2020)
Herein we report the stereochemical revision of peribysins A, B, C, F, and G, guided by enantiospecific total synthesis starting from (+)-nootkatone. Furthermore, we reconfirmed the absolute stereochemistry of peribysin Q The highlights of the synthesis are enone transposition and kinetic iodination resulting in separation of diastereomers. Our findings coupled with synthetic and biological data previously reported by Danishefsky's group suggest that the original stereochemistries of peribysins A, B, C, F, and G were misassigned.

Oxidative rearrangement of stilbenes to 2,2-diaryl-2-hydroxyacetaldehydes - Kalshetti, Rupali G.; Ramana, V. Chepuri (ACS Omega, 2020)
A one-pot oxone-mediated/iodine-catalyzed oxidative rearrangement of stilbenes leading to 2,2-diary1-2-hydroxyacetaldehydes is described. Control experiments revealed that a 2,2-diarylacetaldehyde was initially formed that undergoes subsequent alpha-hydroxylation. The resulting alpha-hydroxyaldehydes have been subjected to a one-pot Still Gennari olefination followed by cyclization, leading to S,S-diaryl-y-butenolides.

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

Pd-catalyzed annulation of beta-iodovinyl sulfones with 2-halophenols: a general route for the synthesis of 3-sulfonyl benzofuran derivatives - Reddy, Raju Jannapu; Kumar, Jangam Jagadesh; Kumari, Arram Haritha; Krishna, Gamidi Rama (Advanced Synthesis & Catalysis, 2020)
The palladium-catalyzed annulation between beta-iodovinyl sulfones and 2-halophenols or 1-bromo-2-naphthol or 2-bromo-3-pyridinol is presented. The annulation process involving oxa-Michael addition-elimination and intramolecular Heck reaction leading to form 2,3-disubstituted benzofurans (aryl benzofuryl sulfones) in good to high yields. The regioselective tandem construction of C-O and C-C bonds has been achieved with a variety of substitution patterns. Moreover, the tandem process is reliable at gram-scale reactions and a plausible mechanism is also proposed.
Keywords: Benzofurans; beta-Iodovinyl sulfones; Heck reaction; Naphthofurans; oxa-Michael addition

Phenylboronic acid-catalyzed tandem construction of S-S and C-S bonds: a new method for the synthesis of benzyl disulfanylsulfone derivatives from S-benzyl thiosulfonates - Reddy, Raju Jannapu; Waheed, Md; Krishna, Gamidi Rama (Organic & Biomolecular Chemistry, 2020)
A unique phenylboronic acid-catalyzed dimerization-sulfonylation of S-benzyl thiosulfonates has been disclosed. A metal-free tandem construction of S-S and C-S bonds is an operationally simple method to access a wide range of benzyl disulfanylsulfone derivatives in high to excellent yields. Moreover, the robustness of this tandem transformation has been demonstrated by gram-scale reactions, and a plausible mechanism is also proposed.

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.

Photocatalytic hydrogen generation and CO2 conversion using g-C3N4 decorated dendritic fibrous nanosilica: role of interfaces between silica and g-C3N4 - Rawool, Sushma A.; Samanta, Anupam; Ajithkumar, T. G.; Kar, Yusuf; Polshettiwar, Vivek (ACS Applied Energy Materials, 2020)
We have synthesized g-C3N4 decorated over dendritic fibrous nanosilica (DFNS). The generation of C-N-Si interfaces by coating each fiber of DFNS with g-C3N4 not only provided high surface area but also affected the optical and electronic properties of the composite. The catalyst synthesis reproducibility issue of g-C3N4 was resolved using a vacuum-sealed quartz tube. The extended light absorption in the visible region, enhanced lifetime of photogenerated charge carriers due to the formation of interfaces between silica and g-C3N4 (confirmed by solid-state NMR), and increased surface area result in the improved photocatalytic activity of DFNS/g-C(3)N(4)for hydrogen generation and CO2 conversion.
Keywords: CO2 conversion; DFNS; g-C3N4; Hydrogen generation; nanocatalysts; photocatalysts; Solid-state NMR

Photocatalytic hydrogen production from H2S using nanostructured CNT blended CdZnS/Fe2O3 thin film on glass substrate - Raja, M. Anthony; Vijayarengan, Preethi; Pal, Yash; Nalajala, Naresh; Gopinath, Chinnakonda (Journal of Physics Conference Series, 2020)
<span style="color: rgb(51, 51, 51); font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">A co-precipitation method was employed to prepare the CNT blended CdZnS/Fe<span style="font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; font-size: 12px; line-height: 1; font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; height: 0px; position: relative; top: 0.5ex; color: rgb(51, 51, 51);">2<span style="color: rgb(51, 51, 51); font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">O<span style="font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; font-size: 12px; line-height: 1; font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; height: 0px; position: relative; top: 0.5ex; color: rgb(51, 51, 51);">3<span style="color: rgb(51, 51, 51); font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;"> photocatalyst. Using the powder photocatalyst, the thin film of CNT blended CdZnS/Fe<span style="font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; font-size: 12px; line-height: 1; font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; height: 0px; position: relative; top: 0.5ex; color: rgb(51, 51, 51);">2<span style="color: rgb(51, 51, 51); font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">O<span style="font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; font-size: 12px; line-height: 1; font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; height: 0px; position: relative; top: 0.5ex; color: rgb(51, 51, 51);">3<span style="color: rgb(51, 51, 51); font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;"> photocatalyst over a glass substrate was prepared using the drop-casting method. The obtained thin film was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), energy-dispersive X-ray analysis (EDAX), photoluminescence (PL), and hydrogen production activity studies in order to obtain information on their structural, morphology, chemical composition, optical and hydrogen production efficiency. The hydrogen production activity of catalyst or effective conversion of H<span style="font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; font-size: 12px; line-height: 1; font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; height: 0px; position: relative; top: 0.5ex; color: rgb(51, 51, 51);">2<span style="color: rgb(51, 51, 51); font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">S into hydrogen (H<span style="font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; font-size: 12px; line-height: 1; font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; height: 0px; position: relative; top: 0.5ex; color: rgb(51, 51, 51);">2<span style="color: rgb(51, 51, 51); font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">) and sulfur (S) using thin-film photocatalyst was evaluated using a simulated sulfide solution. The results showed that 1 mg of CNT blended CdZnS/Fe<span style="font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; font-size: 12px; line-height: 1; font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; height: 0px; position: relative; top: 0.5ex; color: rgb(51, 51, 51);">2<span style="color: rgb(51, 51, 51); font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">O<span style="font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; font-size: 12px; line-height: 1; font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; height: 0px; position: relative; top: 0.5ex; color: rgb(51, 51, 51);">3<span style="color: rgb(51, 51, 51); font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;"> catalyst coated as thin film over glass substrate (4.69 cm<span style="font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; font-size: 12px; line-height: 1; font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; height: 0px; position: relative; bottom: 1ex; color: rgb(51, 51, 51);">2<span style="color: rgb(51, 51, 51); font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">) showed the highest hydrogen production value of 3180 μmol h<span style="font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; font-size: 12px; line-height: 1; font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; height: 0px; position: relative; bottom: 1ex; color: rgb(51, 51, 51);">−1<span style="color: rgb(51, 51, 51); font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">g<span style="font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; font-size: 12px; line-height: 1; font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; height: 0px; position: relative; bottom: 1ex; color: rgb(51, 51, 51);">−1<span style="color: rgb(51, 51, 51); font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">; compared to that of 1 mg CNT blended CdZnS/Fe<span style="font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; font-size: 12px; line-height: 1; font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; height: 0px; position: relative; top: 0.5ex; color: rgb(51, 51, 51);">2<span style="color: rgb(51, 51, 51); font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">O<span style="font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; font-size: 12px; line-height: 1; font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; height: 0px; position: relative; top: 0.5ex; color: rgb(51, 51, 51);">3<span style="color: rgb(51, 51, 51); font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;"> powder of 2510 μmol h<span style="font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; font-size: 12px; line-height: 1; font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; height: 0px; position: relative; bottom: 1ex; color: rgb(51, 51, 51);">−1<span style="color: rgb(51, 51, 51); font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">g<span style="font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400; font-size: 12px; line-height: 1; font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; height: 0px; position: relative; bottom: 1ex; color: rgb(51, 51, 51);">−1<span style="color: rgb(51, 51, 51); font-family: -apple-system, BlinkMacSystemFont, "Segoe UI", Roboto, "Noto Sans", Ubuntu, "Droid Sans", "Helvetica Neue", sans-serif; font-size: 16px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">. From the above results, it is concluded that the thin film form of photocatlyst produced more hydrogen than the powder form. This is attributed to the effective charge separation and increased specific surface area in thin film photocatalyst.

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

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

Piezoelectric energy harvesting from a ferroelectric hybrid salt [Ph3MeP](4)[Ni(NCS)(6)] embedded in a polymer matrix - Vijayakanth, Thangavel; Ram, Farsa; Praveenkumar, Balu; Shanmuganathan, Kadhiravan; Boomishankar, Ramamoorthy (Angewandte Chemie-International Edition, 2020)
Organic-inorganic hybrid ferroelectrics are an exciting class of molecular materials with promising applications in the area of energy and electronics. The synthesis, ferroelectric and piezoelectric energy harvesting behavior of a 3d metal ion-containing A(4)BX(6) type organic-inorganic hybrid salt [Ph3MeP](4)[Ni(NCS)(6)] (1) is now presented. P-E hysteresis loop studies on 1 show a remnant ferroelectric polarization value of 18.71 mu C cm(-2), at room temperature. Composite thermoplastic polyurethane (TPU) devices with 5, 10, 15 and 20 wt % compositions of 1 were prepared and employed for piezoelectric energy harvesting studies. A maximum output voltage of 19.29 V and a calculated power density value of 2.51 mW cm(-3) were observed for the 15 wt % 1-TPU device. The capacitor charging experiments on the 15 wt % 1-TPU composite device shows an excellent energy storage performance with the highest stored energies and measured charges of 198.8 mu J and 600 mu C, respectively.
Keywords: energy conversion; mechanical properties; non-covalent interactions; organic-inorganic hybrid composites; Phosphorus

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

Plausible diagnostic value of urinary isomeric dimethylarginine ratio for diabetic nephropathy - Parmar, Dharmeshkumar; Bhattacharya, Nivedita; Kannan, Shanthini; Vadivel, Sangeetha; Pandey, Gautam Kumar; Ghanate, Avinash; Ragi, Nagarjuna Chary; Prabu, Paramasivam; Pramodkumar, Thyparambil Aravindakshan; Manickam, Nagaraj; Mohan, Viswanathan; Sripadi, Prabhakar; et al. (Scientific Reports, 2020)
Altered circulatory asymmetric and symmetric dimethylarginines have been independently reported in patients with end-stage renal failure suggesting their potential role as mediators and early biomarkers of nephropathy. These alterations can also be reflected in urine. Herein, we aimed to evaluate urinary asymmetric to symmetric dimethylarginine ratio (ASR) for early prediction of diabetic nephropathy (DN). In this cross-sectional study, individuals with impaired glucose tolerance (IGT), newly diagnosed diabetes (NDD), diabetic microalbuminuria (MIC), macroalbuminuria (MAC), and normal glucose tolerance (NGT) were recruited from Dr. Mohans' Diabetes Specialties centre, India. Urinary ASR was measured using a validated high-throughput MALDI-MS/MS method. Significantly lower ASR was observed in MIC (0.909) and MAC (0.741) in comparison to the NGT and NDD groups. On regression models, ASR was associated with MIC [OR: 0.256; 95% CI: 0.158-0.491] and MAC [OR 0.146; 95% CI: 0.071-0.292] controlled for all the available confounding factors. ROC analysis revealed ASR cut-point of 0.95 had C-statistic of 0.691 (95% CI: 0.627-0.755) to discriminate MIC from NDD with 72% sensitivity. Whereas, an ASR cut-point of 0.82 had C-statistic of 0.846 (95% CI: 0.800 - 0.893) had 91% sensitivity for identifying MAC. Our results suggest ASR as a potential early diagnostic biomarker for DN among the Asian Indians.

Poly (vinylpyrrolidone)-iodine engineered poly (epsilon-caprolactone) nanofibers as potential wound dressing materials - Shitole, Ajinkya A.; Raut, Piyush; Giram, Prabhanjan; Rade, Priyanka; Khandwekar, Anand; Garnaik, Baijayantimala; Sharma, Neeti (Materials Science & Engineering C-Materials for Biological Applications, 2020)
Facilitating the process of wound healing and effective treatment of wounds remains a serious challenge in healthcare. Wound dressing materials play a major role in the protection of wounds and in accelerating the natural healing process. In the present study, novel core/shell (c/s) nanofibrous mats of poly(vinyl pyrrolidone)-iodine (PVPI) and polycaprolactone (PCL) were fabricated using a co-axial electrospinning process followed by their surface modification with poly-L-lysine. The developed nanofibrous mats were extensively characterized for their physicochemical properties using various analytical techniques. The core/shell structure of the PVP-I/PCL nanofibers was confirmed using TEM analysis. The PVP-I release studies showed an initial burst phase followed by a sustained release pattern of PVP-I over a period of 30 days. The developed nanofibers exhibited higher BSA and fibrinogen adsorption as compared to pristine PCL. Cytotoxicity studies using MTT assay demonstrated that the PVP-I/PCL (c/s) nanofibers were cytocompatible at optimized PVP-I concentration (3 wt%). The PCL-poly-L-lysine and PVP-I/PCL-poly-L-lysine nanofibers exhibited higher cell viability (24.2% and 21.4% higher at day 7) when compared to uncoated PCL and PVP-I/PCL nanofibers. The PVP-I/PCL nanofibers showed excellent antimicrobial activity against both Gram-positive (S. aureus) and Gram-negative (E. coli) bacteria. The inflammatory response of Mouse RAW 264.7 macrophage cells towards the nanofibers was studied using RTPCR. It revealed that the pro-inflammatory cytokines (TNF-alpha and IL-1 beta) were significantly upregulated on PCL nanofibers, while their expression was comparatively lower on poly-L-lysine coated PCL or PVP-I/PCL(c/s) nanofibers. Overall, the study highlights the ability of poly-L-lysine coated PVP-I/PCL (c/s) nanofibers as potential wound dressing materials effectively facilitating the early stage wound healing and repair process by virtue of their selective modulation of inflammation, cell adhesion and antimicrobial properties.
Keywords: biodegradable; Controlled release; Core/shell; electrospinning; scaffolds; tissue engineering

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

Process development for 6-aminopenicillanic acid production using lentikats-encapsulated escherichia coli cells expressing penicillin V acylase - Sawant, Amol M.; Sunder, Avinash Vellore; Vamkudoth, Koteswara Rao; Ramasamy, Sureshkumar; Pundle, Archana (ACS Omega, 2020)
Penicillin V acylase (PVA, EC 3.5.1.11) hydrolyzes the side chain of phenoxymethylpenicillin (Pen V) and finds application in the manufacture of the pharmaceutical intermediate 6-aminopenicillanic acid (6-APA). Here, we report the scale-up of cultivation of Escherichia coli whole cells expressing a highly active PVA from Pectobacterium atrosepticum and their encapsulation in polyvinyl alcohol-poly(ethylene glycol) Lentikats hydrogels. A biocatalytic process for the hydrolysis of 2% (w/v) Pen V was set up in a 2 L reactor using the Lentikats-immobilized whole cells, with a customized setup to enable continuous downstream processing of the reaction products. The biocatalytic reaction afforded complete conversion of Pen V for 10 reaction cycles, with an overall 90% conversion up to 50 cycles. The bioprocess was further scaled up to the pilot-scale at 10 L, enabling complete conversion of Pen V to 6-APA for 10 cycles. The 6-APA and phenoxy acetic acid products were recovered from downstream processing with isolated yields of 85-90 and 87-92%, respectively. Immobilization in Lentikats beads improved the stability of the whole cells on storage, maintaining 90-100% activity and similar conversion efficiency after 3 months at 4 degrees C. The robust PVA biocatalyst can be employed in a continuous process to provide a sustainable route for bulk 6-APA production from Pen V.

PVDF/BaTiO3 films with nanocellulose impregnation: investigation of structural, morphological and mechanical properties - Ram, Farsa; Kaviraj, P.; Pramanik, R.; Krishnan, Amrutha; Shanmuganathan, Kadhiravan; Arockiarajan, A. (Journal of Alloys and Compounds, 2020)
Polyvinylidene fluoride (PVDF) composite films have witnessed widespread applications in biomedical and flexible electronic devices in recent years. These applications require a material that has enhanced electrical properties, mechanical flexibility along with sufficient strength. A lot of research has been carried out to enhance the piezoelectric and dielectric properties of the PVDF composite films. However, the improvements in the mechanical properties of nano filler reinforced PVDF composite films has not received due attention. In this regard, the present work focuses towards enhancing the mechanical strength and load-bearing capability of PVDF, by preparing composites of PVDF films impregnated with Cellulose Nanocrystals (CNC) and Barium Titanate (BTO) nanoparticles. Solution casting method was adapted to fabricate the PVDF/BTO/CNC films. X-ray diffractograms and FTIR (Fourier Transform infrared spectroscopy) corroborate the presence of ferroelectric gamma phase in PVDF. Mechanical and viscoelastic measurements have been carried out to examine the influence of CNC and BTO nano fillers in the PVDF matrix. The addition of CNC and BTO in PVDF film has improved the mechanical strength significantly. The stress achieved for PVDF/5% BTO and PVDF/5% BTO with 0.9% of CNC at 5% strain was 17% and 130% higher than the pristine PVDF, respectively. This study can be helpful for the design engineers to meet custom/specific requirements for a myriad of end- user applications such as piezoelectric nanogenerators. (C) 2020 Elsevier B.V. All rights reserved.
Keywords: BaTiO3; Composite films; Mechanics; Morphology; Nanocellulose; PVDF

Rapid synthesis of zwitterionic phosphonium benzoates by a three-component coupling involving phosphines, arynes and CO2 - Bhattacharjee, Subrata; Raju, Anjali; Gaykar, Rahul N.; Gonnade, Rajesh G.; Roy, Tony; Biju, Akkattu T. (Chemistry-An Asian Journal, 2020)
A mild and easy to perform multicomponent coupling involving phosphines, arynes generated from 2-(trimethylsilyl)aryl triflates, and CO(2)allowing the transition-metal-free synthesis of zwitterionic phosphonium benzoates has been developed. The reaction proceeds via the generation of 1 : 1 zwitterionic intermediates from phosphines and arynes followed by the interception with CO(2)to deliver the carboxylates in moderate to good yields instead of the anticipated benzooxaphosphol-3(1H)-ones.
Keywords: arynes; Carbon dioxide; multicomponent coupling; Phosphines; zwitterions

Reduction of trap and polydispersity in mutually passivated quantum dot solar cells - Sharma, Ashish; Mahajan, Chandan; Rath, Arup K. (ACS Applied Energy Materials, 2020)
Control over surface passivation is a key to manage the optoelectronic properties in low-dimensional nanomaterials because of their high surface-to-volume ratios. Tunable band gap quantum dots (QDs) are a potential building block for the development of optoelectronic devices like solar cells, photodetectors, and light-emitting diodes. Long and insulating surface ligands of colloidally synthesized QDs are exchanged by short ligands to attain compact arrangement in thin films to facilitate the charge transport process. However, the ligand exchange process often resulted in reduced surface passivation, inhomogeneous QD fusion, and deterioration of energy band gap, which adversely impact their performance in solar cells. Here, we introduce a surface passivation strategy where the QDs are mutually passivated by the organic ligand 3-methyl mercapto propionate and inorganic halometallate ligands to develop a conducting QD ink. The mutually passivated QDs (MPQDs) show significant improvement in optoelectronic properties in maintaining the trap-free energy band gap and size monodispersity. The photovoltaic performance of MPQDs shows a 33% average increase in power conversion efficiency (PCE) over the conventional halometallate passivation to attain 9.6% PCE in MPQD solar cells. The improvements in photovoltaic parameters are corroborated by the reduction in density of the intermediate trap states and an increase in depletion width and diffusion length in MPQD-based solar cells.
Keywords: polydispersity; quantum dot; solar cells; surface passivation; trap states

Removal of fluoride from aqueous solution by mesoporous silica nanoparticles functionalized with chitosan derived from mushroom - Srivastava, Anushree; Kumari, Madhu; Ramanathan, Alagappan; Selvaraj, Kaliaperumal; Prasad, Bablu; Prasad, Kumar Suranjit (Journal of Macromolecular Science Part A-Pure and Applied Chemistry, 2020)
In the present study, chitosan functionalized mesoporous silica nanoparticles have been synthesized. Chitosan derived from an edible mushroom, Agaricus bisporus was used during synthesis of chitosan functionalized silica nanoparticles. The functionalized silica nanoparticles were subjected to fluoride sorption using a batch method which subsequently showed removal efficiency of 95% with maximum sorption capacity, 58.8 mg/g. The characterization of nanoparticles was carried out by SEM, EDAX, XRD and FTIR analysis respectively. EDAX analysis suggested that oxygen, 51.83% and silica 37.24% was main constituent of the functionalized nanomaterials. XRD yielded characteristic diffraction pattern corresponding to the lattice planes (100), (110), (112), (120), (200) and (220) respectively. Sorption data was used to study equilibrium isotherm namely Langmuir and Freundlich model. The adsorption capacity increased with temperature while kinetics studies revealed that the adsorption process followed a pseudo-second-order rate equation. The enthalpy change (Delta H) and entropy change (Delta S) was found to be -31.36 kJmol(-1) and -7.75 Jmol(-1) K-1, showing endothermic and spontaneous nature of the fluoride adsorption. Data suggested that the nature of adsorption belonged to chemisorptions. The overall results suggested that the synthesized nanoparticles showed strong and specific affinity for fluoride and could be excellent adsorbents for defluoridation.
Keywords: Adsorption; Chitosan; EDAX; Fluoride; SEM

Renewing polyethylene: insertion copolymerization of sugar derived hydrophilic monomers with ethylene - Rajput, Bhausaheb S.; Pawal, Sandip B.; Bodkhe, V. Dnyaneshwar; Rao, I. Nagamalleswara; Sainath, Annadanam V. Sesha; Chikkali, Samir H. (European Polymer Journal, 2020)
Although highly desirable, insertion copolymerization of renewable resource derived functional olefins with ethylene has been rarely investigated. Herein, we report insertion copolymerization of challenging sugar derived isohexide mono-enes with ethylene in the presence of Pd-phosphinesulfonate acetonitrile catalyst (C1). Thus, copolymerization of ethylene with isomannide mono-ene (2a), isosorbide mono-ene (2b'), isoidide mono-ene (2c) and methacryl-2,3,4,6-tetra-O-acetyl-D glucopyranoside (2d) afforded corresponding functionalized polyethylene (P2a-1 to P2d-1). High temperature proton NMR investigations revealed enchainment of 2a-2c in polyethylene backbone and the highest incorporation of 1.45% was observed for 2c. The high temperature proton NMR results were further corroborated by solid state C-13 NMR and IR spectroscopy. Gel permeation chromatography analysis displayed weight average molecular weight in the range of 13.0-27.2 x 10(3) g/mol. The thus prepared copolymers revealed melting temperature in the range of 117-126 degrees C. Relatively reduced melting temperature compared to neat polyethylene may suggest an irregular arrangement of pendant functional group on polyethylene main chain.
Keywords: Hydrophilic polyethylene; insertion copolymerization; Isohexide mono-enes; Polyethylene; Sugar

Room temperature processed in-situ carbon-coated vanadium carbide (VC@C) as a high capacity robust Li/Na battery anode material - Mahajan, Mani; Roy, Kingshuk; Parmar, Swati; Singla, Gourav; Pandey, O. P.; Singh, K.; Vaidhyanathan, Ramanathan; Ogale, Satishchandra (Carbon, 2020)
3D carbide systems with their robust physical and mechanical properties have always attracted multiple application interests. In this report, we have synthesized a three-dimensional in-situ carbon coated cubic carbide, Vanadium Carbide (VC@C), by a very simple, scalable and cost-effective room temperature mechano-chemical ball-milling procedure and researched its promise as effective anode material for Li and Na ion batteries. We have demonstrated that VC@C shows an impressive initial discharge/lithiation capacity of 1165 mAh g(-1) with a high reversible capacity of 640 mAh g(-1) after 100 charge-discharge cycles at an applied current density of 0.1 A g(-1). We have also found that this material renders a very promising rate performance with significantly low capacity drop after exposing it to variable current densities ranging from 0.05 A g(-1) to 2 A g(-1) with an excellent stability up to 1000 cycles owing to its structural robustness, as verified by post-cycling characterizations. A Li-ion full cell study using LiCoO2 as cathode also showed excellent promise in terms of practical application demonstrating a reversible capacity of 95 mAh g(-1) after 100 cycles. Even for Na insertion/de-insertion VC@C shows a clear promise in terms of capacity, cyclic stability and rate performance. (C) 2020 Elsevier Ltd. All rights reserved.
Keywords: 3D carbide; In-situ synthesis; Li-ion battery; Post cycling characterization; Room temperature ball milling; Williamson-Hall analysis

Salts and cocrystal of etodolac: advantage of solubility, dissolution, and permeability - Rai, Sunil K.; Allu, Suryanarayana; Nangia, Ashwini K. (Crystal Growth & Design, 2020)
{Etodolac (ETD) is a nonsteroidal anti-inflammatory drug (NSAID) approved by the United States Food and Drug Administration (US-FDA) in 1991 for the treatment of rheumatoid arthritis. Because of its poor aqueous solubility and high permeability, ETD falls under Biopharmaceutics Classification System (BCS) Class II drug. The present study was aimed to screen stable salts and cocrystals of ETD using Generally Recognized as Safe (GRAS) and a few non-GRAS coformers. Crystallization of five salts (i.e.

Screening of zero valent mono/bimetallic catalysts and recommendation of Raney Ni (without reducing agent) for dechlorination of 4-chlorophenol - Raut, Sandesh S.; Shetty, Rohit; Raju, Nikhi Maria; Kamble, Sanjay P.; Kulkarni, Prashant S. (Chemosphere, 2020)
Chlorophenol (CP) is considered as environmentally hazardous material due to its acute toxicity, persistent nature and strong bioaccumulation. The dechlorination of 4-CP was investigated by using various catalysts such as bimetallic (Fe-0/Cu-0, Al-0/Fe-0), Pd/C, Raney Ni and Fe-0 at room temperature. Among the catalysts studied, Raney Ni proved to be very economical and efficient catalyst that worked without the use of an external reducing agent. The dechlorination of 4-CP by Raney Ni was therefore further explored. Complete dechlorination of 4-CP (30 mg L-1) was achieved in 6 hat an optimum Raney Ni catalyst loading of 3 g L-1. The effect of triethylamine (TEA) and tripropylamine (TPA) was also investigated and it was observed that 100% dechlorination is possible in presence of 45 mg L-1 of TEA. The kinetics of dechlorination of 4-CP was investigated and found to be first order with a rate constant of 0.017 min(-1) at 50 degrees C, and it enhances to 0.109 min(-1) with addition of TEA. In the absence of a reducing agent, acidic to neutral pH favors dechlorination of 4-CP. The final product of dechlorination was estimated to be phenol by performing HPLC, LCMS and NMR analysis. Based on the results, a probable dechlorination mechanism of 4-CP is also proposed. It can be concluded that the catalytic hydrodechlorination is an effective and economical technique for dechlorination of 4-CP and it has a potential for the dechlorination of other toxic derivatives of chlorinated aromatics. (C) 2020 Elsevier Ltd. All rights reserved.
Keywords: 4-Chlorophenol; Cl- scavenger; Hydrodechlorination; Raney Ni; Recycling of catalyst; Without reducing agent

Self-assembly of bispentadecylphenol substituted perylenediimide with PS-b-P4VP for structure-property insight into the core of core-shell micelles - Roy, Moumita; Rajamohanan, Pattuparambil R.; Ravindranathan, Sapna; Asha, S. K. (ACS Applied Polymer Materials, 2020)
We report the use of a ditopic molecular probe bispentadecylphenol substituted perylenediimide (PBI-PDP) to examine the molecular level self-assembly of polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) in tetrahydrofuran (THF). A series of complexes were prepared between PS-b-P4VP copolymers with varying lengths of the 4-vinylpyridine chain and PBI-PDP. Light scattering and NMR spectroscopic studies reveal that the self-assembled structures of the solid complexes are not fully disrupted when the complexes are dissolved in THF. NMR experimental parameters measured for the small probe molecule provide detailed insights into the structure of the assemblies in solution as well as the interaction between the small molecule and the block copolymer. Such insights can have important implications in manipulating the nanostructure of block copolymer micelles to suit various application requirements. The dynamics and distribution of the PBI-PDP molecules within the assemblies in solution show a dependence on the length of the P4VP block. Transmission electron microscopy was employed to study the evolution of morphologies in films prepared from the self-assembled structures in THF solutions.
Keywords: core corona interface; ditopic molecular probe; environment; micelles; perylenediimide; PS-b-P4VP; Self-assembly

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

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)

Solution-phase hybrid passivation for efficient infrared-band gap quantum dot solar cells - Mahajan, Chandan; Sharma, Ashish; Rath, Arup K. (ACS Applied Materials & Interfaces, 2020)
The broad tunability of the energy band gap through size control makes colloidal quantum dots (QDs) promising for the development of photovoltaic devices. Large-size lead sulfide (PbS) QDs, exhibiting a narrow energy band gap, are particularly interesting as they can be used to augment perovskite and c-Si solar cells due to their complementary NIR absorption. However, their complex surface chemistry makes them difficult to process for the development of solar cells. The shape of the QDs transformed from octahedron to cuboctahedron as their size increases, a phenomenon guided by surface energy minimization. As a result, the surface properties change drastically for large-size QDs, which exhibit nonpolar (200) facets and polar (111) facets, as opposed to only (111) facets in small-size QDs. Recent advancements in solution-phase surface passivation strategies, used for the development of high-performance solar cells using the small size and wide band gap QDs, failed to translate a similar enhancement in the case of large-size and narrow band gap QDs. Here, we report a hybrid passivation strategy for large-size and narrow band gap QDs to passivate both (111) and (200) facets, respectively, using inorganic lead triiodide (PbI3-) and organic 3-chloro-1-propanethiol (CPT). By employing charge balance calculation, we identified the desired narrow band gap for QDs to complement the perovskite and c-Si absorption. The distinct choice of the organic ligand CPT enhances the colloidal stability of QDs in the solution phase and improves surface passivation to stop QD fusion in solid films. Photophysical properties show narrower excitonic and emission peaks and a reduction in the Stokes shift. Hybrid passivation leads to a 94% increase in the power conversion efficiency of solar cells and a 74% increase in the external quantum efficiency at the excitonic peak.
Keywords: infrared band gap; polydispersity; quantum dot; solar cells; surface passivation; trap states

Spectroscopic probe of atomically thin domains of CVD-grown MoSe2 - Singh, Vineeta; Late, Dattatray J.; Rath, Shyama (AIP Conference Proceedings, 2020)
Since the discovery of graphene, two-dimensional Layered Transition Metal Dichalcogenides (TMDCs) such as MoS2, MoSe2, and WS2 having a tunable bandgap, have emerged as one of the most stable classes of materials making them attractive for various applications. We have investigated the growth mechanism and shape evolution of various domains of CVD-grown MoSe2 on insulating substrates by spectroscopic techniques. The different morphologies were analyzed using Raman and photoluminescence spectroscopies. The transformation from the precursor MoO3 to MoSe2 is found to depend on a number of growth parameters and experimental conditions.

Stronger transcription regulatory circuit of HIV-1C drives the rapid establishment of latency with implications for the direct involvement of tat - Chakraborty, Sutanuka; Kabi, Manisha; Ranga, Udaykumar (Journal of Virology, 2020)
The magnitude of transcription factor binding site variation emerging in HIV-1 subtype C (HIV-1C), especially the addition of NF-kappa B motifs by sequence duplication, makes the examination of transcriptional silence challenging. How can HIV-1 establish and maintain latency despite having a strong long terminal repeat (LTR)? We constructed panels of subgenomic reporter viral vectors with varying copy numbers of NF-kappa B motifs (0 to 4 copies) and examined the profile of latency establishment in Jurkat cells. Surprisingly, we found that the stronger the viral promoter, the faster the latency establishment. Importantly, at the time of commitment to latency and subsequent points, Tat levels in the cell were not limiting. Using highly sensitive strategies, we demonstrate the presence of Tat in the latent cell, recruited to the latent LTR. Our data allude, for the first time, to Tat establishing a negative feedback loop during the late phases of viral infection, leading to the rapid silencing of the viral promoter. IMPORTANCE Over the past 10 to 15 years, HIV-1 subtype C (HIV-1C) has been evolving rapidly toward gaining stronger transcriptional activity by sequence duplication of major transcription factor binding sites. The duplication of NF-kappa B motifs is unique and exclusive to HIV-1C, a property not shared with any of the other eight HIV-1 genetic families. What mechanism(s) does HIV-1C employ to establish and maintain transcriptional silence despite the presence of a strong promoter and concomitant strong, positive transcriptional feedback is the primary question that we attempted to address in the present manuscript. The role that Tat plays in latency reversal is well established. Our work with the most common HIV-1 subtype, HIV-1C, offers crucial leads toward Tat possessing a dual role in serving as both a transcriptional activator and repressor at different phases of viral infection of the cell. The leads that we offer through the present work have significant implications for HIV-1 cure research.
Keywords: HIV-1C; latency; LTR; NF-kappa B; positive feedback; Tat

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.

Structural and enzymatic analysis of a dimeric cholylglycine hydrolase like acylase active on N-acyl homoserine lactones - Philem, Pushparani D.; Yadav, Yashpal; Sunder, Avinash Vellore; Ghosh, Deepanjan; Prabhune, Asmita; Ramasamy, Sureshkumar (Biochimie, 2020)
The prevalence of substrate cross-reactivity between AHL acylases and beta-lactam acylases provides a glimpse of probable links between quorum sensing and antibiotic resistance in bacteria. Both these enzyme classes belong to the N-terminal nucleophile (Ntn)-hydrolase superfamily. Penicillin V acylases alongside bile salt hydrolases constitute the cholylglycine hydrolase (CGH) group of the Ntn-hydrolase superfamily. Here we report the ability of two acylases, Slac1 and Slac2, from the marine bacterium Shewanella loihica PV4 to hydrolyze AHLs. Three-dimensional structure of Slac1 reveals the conservation of the Ntn hydrolase fold and CGH active site, making it a unique CGH exclusively active on AHLs. Slac1homologs phylogenetically cluster separate from reported CGHs and AHL acylases, thereby representing a functionally distinct sub-class of CGH that might have evolved as an adaptation to the marine environment. We hypothesize that Slac1 could provide the structural framework for understanding this subclass, and further our understanding of the evolutionary link between AHL acylases and beta-lactam acylases. (C) 2020 Elsevier B.V. and Societe Francaise de Biochimie et Biologie Moleculaire (SFBBM). All rights reserved.
Keywords: AHL acylase; Cholyolglycine hydrolase; Homodimer; Ntn-fold; Shewanella loihica-PV4

Structural and physical analysis of underwater silk from housing nest composites of a tropical chironomid midge - Thorat, Leena; Joseph, Emmanuel; Nisal, Anuya; Shukla, Ekta; RaviKumar, Ameeta; Nath, Bimalendu B. (International Journal of Biological Macromolecules, 2020)
Chironomids are an abundant group of aquatic silk spinning insects. They offer a unique opportunity of silk harvestation without killing them; however, they remained underappreciated models in silk research. Here, we investigate the structural and biomechanical characteristics of silk from the midge, Chironomus ramosus. A combination of microscopic (SEM), spectroscopic (CD and IR), structural (XRD), thermal (DSC and TGA) and mechanical measurement tools and techniques were employed to gain critical insights on midge silk. Maximum yield of silk was obtained from Chironomus in similar to 2.5 h, the shortest time reported among insects. The network of water-insoluble silk fibres possessed the smallest diameter of 110 +/- 35 nm, known for any insect silk, qualifying its superiority in fibre fineness. We demonstrate a cruelty-free silk extraction method in contrast to the conventional violent techniques. Structural characterization indicated coexistence of various secondary conformations, beta sheets being predominant. We compare and contrast these features to well-characterized caddisfly and silk-worm silks and highlight the uniqueness in midge silk that render mechanical stability and potentially contribute to its multi-functionalization. We thus propose Chironomus as an emerging candidate of water-borne silk, especially in the context of the `Peace silk' industry, aiming to develop non-violent methods for silk harvestation from animals. (C) 2020 Elsevier B.V. All rights reserved.
Keywords: biopolymer; Chironomus; Commercial applications; Housing nest composite; Peace silk; Underwater silk

Structural, Hirshfeld surface and in vitro cytotoxicity evaluation of five new N-aryl-N'-alkoxycarbonyl thiocarbamide derivatives - Pandey, Sunil K.; Pratap, Seema; Rai, Sunil K.; Marverti, Gaetano (Phosphorus Sulfur and Silicon and the Related Elements, 2020)
Five new compounds, N-(2, 4-dichlorophenyl)-N'-(methoxycarbonyl) thiocarbamide (1), N-(2, 4-dichlorophenyl)-N'-(ethoxycarbonyl) thiocarbamide (2), N-(2, 4-dichlorophenyl)-N'-(2, 2, 2-trichloroethoxycarbonyl) thiocarbamide (3), N-(2,4-dichlrophenyl)-N'-(pentoxycarbonyl) thiocarbamide (4) and N-(4-nitrophenyl)-N'-(pentoxycarbonyl) thiocarbamide (5), have been synthesized by the reaction of various alkoxy chloroformates with 2, 4-dichloroaniline/4-nitroaniline.The molecular structures of the compounds were elucidated by using spectroscopic methods (FT-IR, H-1 and C-13 NMR) and single-crystal X-ray structure analysis of compounds 2 and 5. Antiperiplanar orientation of C = O and C = S group across C-N bonds of thiocarbamide core may be due to the presence of intramolecular (N-H center dot center dot center dot O-C) hydrogen bond in the crystal structure of both the compounds. The presence of intermolecular interactions (C-H center dot center dot center dot S, C-H center dot center dot center dot O and N-H center dot center dot center dot S) in the molecular structure of the compounds has been studied in detail using Hirshfeld surfaces and their associated twodimensional fingerprint plots. In vitro cytotoxicity screening of the synthesized compounds evaluated on a panel of seven human cancer cell lines (cervical carcinoma (2008, C13*), colorectal (HT29 and HCT116) and ovarian carcinoma (A2780, A2780/CP and IGROV-1)) demonstrated significant inhibitory properties.
Keywords: Hirshfeld surface analysis; In vitro cytotoxicity; Thiocarbamide; X-ray crystal structure determination

Structural studies on 10-hydroxygeraniol dehydrogenase: a novel linear substrate-specific dehydrogenase from Catharanthus roseus - Sandholu, Anand S.; Mujawar, Sharmila P.; Ramakrishnan, Krithika; Thulasiram, Hirekodathakallu V.; Kulkarni, Kiran (Proteins-Structure Function and Bioinformatics, 2020)
Conversion of 10-hydroxygeraniol to 10-oxogeranial is a crucial step in iridoid biosynthesis. This reaction is catalyzed by a zinc-dependent alcohol dehydrogenase, 10-hydroxygeraniol dehydrogenase, belonging to the family of medium-chain dehydrogenase/reductase (MDR). Here, we report the crystal structures of a novel 10-hydroxygeraniol dehydrogenase from Catharanthus roseus in its apo and nicotinamide adenine dinucleotide phosphate (NADP(+)) bound forms. Structural analysis and docking studies reveal how subtle conformational differences of loops L1, L2, L3, and helix alpha 9' at the orifice of the catalytic site confer differential activity of the enzyme toward various substrates, by modulating the binding pocket shape and volume. The present study, first of its kind, provides insights into the structural basis of substrate specificity of MDRs specific to linear substrates. Furthermore, comparison of apo and NADP(+) bound structures suggests that the enzyme adopts open and closed states to facilitate cofactor binding.
Keywords: 10-hydroxygeraniol dehydrogenase; iridoid biosynthesis; medium-chain dehydrogenase; monoterpene indole alkaloids; reductase; X-ray crystallography

Structure and regulation of SWEET transporters in plants: an update - Anjali, Anjali; Fatima, Urooj; Manu, M. S.; Ramasamy, Sureshkumar; Senthil-Kumar, Muthappa (Plant Physiology and Biochemistry, 2020)
Sugar will eventually be exported transporters (SWEETs), a novel family of sugar transporters found in both eukaryotes and prokaryotes, facilitate sugar flux across the cell membrane. Although these transporters were first discovered in plants, their homologs have been reported in different organisms. SWEETs have critical roles in various developmental processes, including phloem loading, nectar secretion, and pathogen nutrition. The structure of bacterial homologs, called SemiSWEETs, has been well studied thus far. Here, we provide an overview of SWEET protein structure and dynamic function by analyzing the solved crystal structures and predicted models that are available for a few SWEETs in a monocot plant (rice) and dicot plant (Arabidopsis thaliana). Despite the advancement in structure-related studies, the regulation of SWEETs remains unknown. In light of reported regulatory mechanisms of a few other sugar transporters, we propose the regulation of SWEETs at the post-translational level. We then enumerate the potential post-translational modification sites in SWEETs using computational tools. Overall, in this review, we critically analyze SWEET protein structure in plants to predict the post-translational regulation of SWEETs. Such findings have a direct bearing on plant nutrition and defense and targeting the regulation at these levels will be important in crop improvement.
Keywords: oligomerization; Phosphorylation; Post-translational modification; Sugar transporters; Sugar will eventually be exported transporters

Synthesis and biological activity of imidazole based 1,4-naphthoquinones - Choudhari, Dinkar; Salunke-Gawali, Sunita; Chakravarty, Debamitra; Shaikh, Samir R.; Lande, Dipali N.; Gejji, Shridhar P.; Rao, Pradeep Kumar; Satpute, Surekha; Puranik, Vedavati G.; Gonnade, Rajesh (New Journal of Chemistry, 2020)
Design and development of drugs in multi-drug resistant (MDR) infections have been of growing interest. We report the syntheses, and antibacterial and antifungal activities of imidazole-based 1,4-naphthoquinones (I-1 to I-4; 1-alkyl-2-methyl-1H-naphtho[2,3-d]imidazole-4,9-dione (alkyl = methyl to butyl)) and their precursors (B-3; N-(3-chloro-1,-dioxo-1,4-dihydronaphthalen-2-yl)acetamide) and A-1 to A-4; N-(3-(alkylamino)-1,4-dioxo-1,4-dihydronaphthalen-2-yl)acetamide (alkyl = methyl to butyl). Crystal structures of B-3, A-1 to A-3 and I-2 to I-4 were obtained through single crystal X-ray diffraction experiments. Electronic structure and charge distribution have further been characterized with the use of Density Functional Theory. Seven of these derivatives display a broad spectrum of antibacterial activity against few selected bacterial strains (Gram-positive and Gram-negative). As demonstrated MIC values with B-2 and B-3 against bacterial isolates were 8-64 mu g ml(-1) and those against pathogenic yeast, C. albicans, were observed in the range of 128-256 mu g ml(-1). MIC data of these derivatives suggest them to be promising against pathogens.

Synthesis and characterization of biocompatible poly (L-lactide) using zinc (II) salen complex - Rade, Priyanka P.; Garnaik, Baijayantimala (International Journal of Polymer Analysis and Characterization, 2020)
A biocompatible zinc (II) complex based on a tetradentate N,N,O,O-type salen ligand was synthesized, characterized and used for the solvent-free ring-opening polymerization (ROP) of L-lactide in bulk at 180 degrees C to prepare high molecular weight poly(L-lactide) (M-n: 82,600 Da;M-w: 140,000 Da; PDI: 1.70). Poly(L-lactide) (PLLA) was characterized using FTIR,H-1 NMR,C-13 NMR, GPC, TGA, DSC, WAXD, and MALDI-ToF. Kinetic measurement was carried out and first-order behavior to monomer was observed. Thek(app)was found as 6 +/- 0.001 x 10(-4 )s(-1). The biocompatibility of the PLLA was confirmed byin vitrocytotoxicity against NIH/3T3 fibroblast cell line and can be used in biomedical applications.
Keywords: Biocompatible; Biomedical Applications; in vitro; PLLA; zinc (II) salen complex

Synthesis and characterization of nylon 6 polymer nanocomposite using organically modified Indian bentonite - Kumaresan, S.; Rokade, Dhammaraj S.; Marathe, Yogesh N.; Ingole, Pravin G.; Pawar, Radheshyam R.; Pol, Harshawardhan V.; Bajaj, Hari C. (SN Applied Sciences, 2020)
In this present research work two different organic compounds are applied for the modification of Indian origin bentonite. One is with n-hexadecyltrimethylammonium bromide (CTAB), intercalated with an interlayer of bentonite via cation exchange mechanism. Whereas, another with 3-Aminopropyl trimethoxysilane (APTES) interlayer functionalization with bentonite –OH group. APTES and CTAB–intercalated bentonites samples were further cross modified with CTAB and APTES to obtain novel co-surfactant locked organo bentonite modeling (CLOM) like matrices. Original and modified bentonite samples were comparatively evaluated by advanced characterization techniques such as, powder X-ray diffraction, Fourier-transform infrared spectroscopy, thermal gravimetric analysis (TGA). Moreover, the applicability of the developed CLOM like materials were investigated in nylon 6 nanocomposite preparation by melt compounding method using a micro twin co-rotated extruder. Additionally, CLOM-nylon-6 polymer nanocomposites were characterized by wide angle X-ray diffraction, TGA, differential scanning calorimetry, atomic force microscopy and tensile strength measurement. The observed thermograph results confirmed no significant difference in the thermal properties of the developed composites. Whereas, the significant variation observed in the tensile strength results particularly for developed composite 5% of N6-OAMSB and N6 AMOSB 5 showed 111.5 and 76.6% respective enhancement in tensile strength results when compared with a bare nylon-6 polymer.

Synthesis, characterisation, Hirshfeld surface and in vitro cytotoxicity evaluation of new N-aryl-N `-Alkoxycarbonyl thiocarbamide derivatives - Pandey, Sunil K.; Pratap, Seema; Rai, Sunil K.; Marverti, Gaetano; Kaur, Manpreet; Jasinski, Jerry P. (Journal of Molecular Structure, 2020)
Four new compounds N-(4-nitrophenyl)-N'-(isobutoxycarbonyl) thiocarbamide (1), N-(2, 4-nitrophenyl)-N'-(isobutoxycarbonyl) thiocarbamide (2), N-(4-nitrophenyl)-N'-(ethoxycarbonyl) thiocarbamide (3) and N-(2-Chloro- 4-nitrophenyl)-N'-(ethoxycarbonyl) thiocarbamide (4) were prepared and their structures confirmed by using various spectroscopic (FT-IR, UV-Visible, H-1 and C-13 NMR) and single crystal X-ray studies of 1 and 3. The presence of intramolecular (N-H center dot center dot center dot O=C) hydrogen bond in the crystal structure of both the compounds causes planarity of carbonyl thiocarbamide unit and trans orientation of C=O and C=S group. The intermolecular contacts (C-H center dot center dot center dot S, C-H center dot center dot center dot O and N-H center dot center dot center dot S) present in crystal structures have been examined by Hirshfeld surface analysis and their associated 2D fingerprint plots. All the compounds were assessed for their in vitro cytotoxic properties against a panel of seven human cancer cells such as cervical carcinoma (2008, C13*), colorectal (HT29 and HCT116) and ovarian carcinoma (A2780, A2780/CP and IGROV-1). Among them, compounds 2 and 4 exhibited better activity than 1 and 3 against all the cell lines tested. (C) 2019 Elsevier B.V. All rights reserved.
Keywords: Hirshfeld surface analysis; In vitro cytotoxicity; Thiocarbamide; X-ray crystal structure

Synthesis of alpha-ketoamides using potassium superoxide (KO2) as an oxidizing agent - Vasudevan, N.; Routholla, Ganesh; Illa, Giri Teja; Reddy, D. Srinivasa (Tetrahedron, 2020)
A simple and convenient method for the synthesis of alpha-ketoamides by the oxidation of aryl acetamides using potassium superoxide (KO2) as an oxidizing agent is disclosed here. The scope of the developed method is successfully tested with fifteen substrates. In addition, the utility of method has been demonstrated by synthesizing an orexin receptor antagonist, a medicinally interesting compound. (C) 2020 Published by Elsevier Ltd.
Keywords: alpha-Ketoamide; Orexin receptor; Oxidation; Potassium superoxide (KO2)

Synthesis of silver nanoparticles colloids in imidazolium halide ionic liquids and their antibacterial activities for gram-positive and gram-negative bacteria - Patil, Virendra; Mahajan, Swapnil; Kulkarni, Mohan; Patil, Kashinath; Rode, Chandrashekhar; Coronas, Alberto; Yi, Gi-Ra (Chemosphere, 2020)
Four 1-butyl-3-methylimidazolium halide ionic liquids were synthesized via metathesis and anion exchange reactions. Silver nanoparticles (AgNPs) colloids were synthesized in four ionic liquids in the pressurized reactor by reduction of silver nitrate with hydrogen gas, without adding solvents or stabilizing agents. Antibacterial activities of base ionic liquids and AgNPs colloids in ionic liquids were reviewed by well-diffusion method for gram-positive Bacillus cereus (NCIM-2155) and gram-negative Escherichia coli (NCIM-2931) bacteria. Antibacterial activities of ionic liquids and AgNPs colloids in ionic liquids were observed to be controlled by ionic liquids anions and AgNPs particle size. The 1 -butyl-3-methylimidazolium iodide ionic liquid exhibited higher antibacterial activities among the studied ionic liquids. Further, the presence of AgNPs in 1-butyl-3-methylimidazolium iodide, ionic liquid enhanced its antibacterial activity for Bacillus cereus and Escherichia coli bacteria. (C) 2019 Elsevier Ltd. All rights reserved.
Keywords: Anion effect; antibacterial activity; Imidazolium halides; ionic liquids; silver nanoparticles

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

Teixobactin: a paving stone toward a new class of antibiotics? - Gunjal, Vidya B.; Thakare, Ritesh; Chopra, Sidharth; Reddy, D. Srinivasa (Journal of Medicinal Chemistry, 2020)
Antimicrobial resistance is a serious threat to human health worldwide, prompting research efforts on a massive scale in search of novel antibiotics to fill an urgent need for a remedy. Teixobactin, a macrocyclic depsipeptide natural product, isolated from uncultured bacteria (Elef theria terrae), displayed potent activity against several Gram-positive pathogenic bacteria. The distinct pharmacological profile and interesting structural features of teixobactin with nonstandard amino acid (three Damino acids and L-allo-enduracididine) residues attracted several research groups to work on this target molecule in search of novel antibiotics with new mechanism. Herein, we present a comprehensive and critical perspective on immense possibilities offered by teixobactin in the domain of drug discovery. Efforts made by various research groups since its isolation are discussed, highlighting the molecule's considerable potential with special emphasis on replacement of amino acids. Critical analysis of synthetic efforts, SAR studies, and the way forward are provided hereunder.

Temperature assisted reorganization of silver nanoparticles in free-standing, flexible chitosan functionalized reduced graphene oxide thick films: A potential SERS probe for folic acid sensing - Asha, S.; Ananth, A. Nimrodh; Jose, Sujin P.; Rajan, Michael Anjello Jothi (Materials Science and Engineering B-Advanced Functional Solid-State Materials, 2020)
Chitosan and silver functionalized free standing reduced graphene oxide (rGO) films were prepared using simple soak and dry strategy. Redistribution of silver aggregates on chitosan functionalized rGO films were observed by thermally annealing these films at 450 degrees C, in an inert atmosphere. The re-organization / redistribution of silver aggregates in the rGO films were studied using in-situ Raman scattering signals. The redistribution of silver particles occurs through melting of micron sized silver aggregates during annealing. The rearrangement of the micro-sized silver aggregates to spherical silver nanoparticle on chitosan functionalized rGO film, as a result of temperature was assisted through factors such as graphene surface ripple rearrangement and the denaturation of rGO surface interacting chitosan chains. These free-standing films with redistributed silver nanoparticles showed excellent surface enhanced Raman scattering (SERS) effect with enhanced Raman signals for folic acid sensing, showcasing its potentiality to be utilized as flexible SERS based sensors.
Keywords: Free-standing; graphene oxide; sensing; SERS; silver nanoparticles; Thick-films

Ti-superoxide catalyzed oxidative amidation of aldehydes with saccharin as nitrogen source: synthesis of primary amides - Kamble, Rohit B.; Mane, Kishor D.; Rupanawar, Bapurao D.; Korekar, Pranjal; Sudalai, A.; Suryavanshi, Gurunath (RSC Advances, 2020)
A new heterogeneous catalytic system (Ti-superoxide/saccharin/TBHP) has been developed that efficiently catalyzes oxidative amidation of aldehydes to produce various primary amides. The protocol employs saccharin as amine source and was found to tolerate a wide range of substrates with different functional groups. Moderate to excellent yields, catalyst reusability and operational simplicity are the main highlights. A possible mechanism and the role of the catalyst in oxidative amidation have also been discussed.

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 (+)-petromyroxol (vol 56, pg 3933, 2015) - Mullapudi, Venkannababu; Ramana, Chepuri V. (Tetrahedron Letters, 2020)

Towards in situ continuous feeding via controlled release of complete nutrients for fed-batch culture of animal cells - Rawat, Jyoti; Gadgil, Mugdha (Biochemical Engineering Journal, 2020)
Small-scale culture of animal cells in suspension is of importance for many applications. At a small-scale, fed-batch is achieved either by manual bolus feeding or the use of liquid handling robots. In this study, we report an alternate application of a hydrogel for in situ continuous delivery of a nutrient feed comprising 18 amino acids, vitamins, antioxidants, and trace elements. We show that amino acid release is sustained for at least seven days. Importantly, release rates of individual amino acids can be independently modulated by changing their loading. We demonstrate the application of this hydrogel for complete in situ feeding of nutrients to a suspension adapted CHO cell line expressing IgG leading to 2.7-fold and 4-fold improvement in integral viable cell density (IVCD) and volumetric productivity respectively. This is similar to improvements obtained by bolus liquid feeding. Further, supplying glucose from the same hydrogel to eliminate manual feeding led to a 1.8-fold increase in IVCD accompanied by a 3-fold increase in volumetric productivity as compared to batch culture. In summary, this study provides a proof-of-concept that hydrogels can enable completely closed in situ feeding for mammalian cell culture requiring no external intervention. Such continuous in situ delivery can potentially enable closed culture systems maintaining nutrients at low levels mimicking physiological concentrations.
Keywords: Amino acids; CHO cells; Closed system; Fed-batch; Hydrogel for continuous feeding; In situ nutrient release

Towards lignin-derived chemicals using atom-efficient catalytic routes - Sudarsanam, Putla; Ruijten, Dieter; Liao, Yuhe; Renders, Tom; Koelewijn, Steven-Friso; Sels, Bert F. (Trends in Chemistry, 2020)
Lignin is a potential non-fossil resource of diverse functionalized phenolic units. The most important lignin- derived monomers are 4-alkylphenols, 4- hydroxybenzaldehydes, 4-hydroxybenzoic acids, and 4-hydroxycinnamic acids/esters. Efficient transformation of lignin and/or its monomers into valuable aromatics and their derivatives is crucial, not only for a sustainable lignocellulose biorefinery, but also to reduce our dependence on fossil feedstocks. This review provides a concise account of the recent advances in lignocellulose fractionation/lignin depolymerization processes towards lignin-derived monomers. Subsequently, numerous potential atom-efficient catalytic routes for upgrading lignin monomers into drop-in chemicals and new polymer building blocks are discussed.

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.

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

Tunable light emission from chemical vapor deposited two-dimensional MoSe2 by layer variation and S incorporation - Singh, Vineeta; Late, Dattatray J.; Rath, Shyama (Journal of Vacuum Science & Technology A, 2020)
Mono- and few-layer thick MoSe2 and MoSxSe2-x domains were grown on insulating SiO2/Si substrates by chemical vapor deposition. Scanning electron microscopy and optical contrast images were used to determine the domain size and morphology. The structure, crystallinity, and the thickness (number of layers) of the as-synthesized domains were determined from Raman spectroscopy. The light emission was determined from photoluminescence (PL) spectroscopy. The PL emission started appearing only in domains having four layers or less, with the intensity increasing as the number of layers decreased. The PL peak position varied between 1.48eV (similar to 838nm) for four layers to 1.55eV (similar to 800nm) in the monolayer limit. Sulfur incorporation was done to enable a further tunability of the bandgap. The monolayer bandgap changed from 1.55eV for MoSe2 to 1.64eV (similar to 756nm) for MoS0.32Se0.68. The other effect of S incorporation was the formation of larger area domains in the alloy as compared to binary MoSe2 with an improvement in the structural properties, thus providing a pathway to improve the properties of two-dimensional semiconductors by mixing of two materials with similar atomic arrangements.

Ultrahigh sensitive carbon-based conducting rubbers for flexible and wearable human-machine intelligence sensing - Ajeev, Arya; Javaregowda, Bharathkumar H.; Ali, Ashik; Modak, Mrudul; Patil, Shreya; Khatua, Saumyakanta; Ramadoss, Marimuthu; Kothavade, Premkumar Anil; Arulraj, Arul Kashmir (Advanced Materials Technologies, 2020)
The wearable strain sensors with multifunctional applications can fuel the rapid development of human-machine intelligence for various sectors like healthcare, soft robotics, and Internet of Things applications. However, achieving the low-cost and mass production of wearable sensors with ultra-high performance remains challenging. Herein, a simple, cost-effective, and scalable methodology to fabricate the flexible and highly sensitive strain sensors using carbon black and latex rubbers (LR) is presented. The LR-based strain sensor demonstrates excellent flexibility, fast response (approximate to 600 ms), ultra-high sensitivity (maximum gauge factor of 1.2 x 10(4) at 250% strain), and long-term stability over 1000 cycles. The LR-based strain sensors are sensitive to monitor subtle human motions such as heart pulse rate and voice recognition along with high-strain human joint operations. Additionally, the sensing mechanism of LR bands is investigated by surface topographies and electromechanical response under various strained/unstrained conditions. Further, a smart glove-based sensor module made of LR strain bands with an Arduino reader for the human-machine intelligence device for non-verbal communication in military applications is demonstrated.
Keywords: conducting rubbers; gauge factor; human– machine interfacing; voice recognition; wearable strain sensors

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)

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.

Wide thermal range, exclusive occurrence of technically significant chiral nematic phase: synthesis and mesomorphism of cholesterol-based non-symmetric dimers - Nayak, Rashmi Ashwathama; Bhat, Sachin A.; Rao, D. S. Shankar; Yelamaggad, V. C. (Bulletin of Materials Science, 2020)
Fifteen new non-symmetric chiral dimers belonging to three different series have been synthesized and evaluated for their mesomorphic properties. They are formed by interlinking cholesterol with salicylaldimine (SAN) cores (with reverse imine groups) via an omega-oxyalkanoyloxy spacer. Within a series, the length of the terminaln-alkoxy tails has been varied for a fixed even-parity spacer. Three even-parity spacers such as 4-oxybutanoyloxy, 6-oxyhexanoyloxy and 8-oxyoctanoyloxy have been used to join two cores, whereas the terminal tails such asn-butyloxy,n-hexyloxy,n-octyloxy,n-decyloxy andn-dodecyloxy chains have been attached to the SAN core. Microscopic and calorimetric experimental results show that all the dimers behave identically exhibiting the chiral nematic (N*) phase solely, which was authenticated by powder X-ray diffraction studies carried out on some selected samples. In the vast majority of the cases, this phase is thermodynamically stable, and while cooling, it exists over a wide thermal range covering room temperature (RT) due to supercooling. This finding is notable given the fact that the N* phase possesses technologically significant optical properties. At RT, the N* phase displayed one of the iridescent colours characteristically caused by interference and diffraction of the reflected and scattered light. A comparative study reveals that the lengths of both the terminal chain and central spacer influence the clearing temperature of the dimers, and also the temperature range of the N* phase. The selective reflection measurements revealed that the pitch of the N* phase is either temperature sensitive or temperature insensitive. Temperature-dependent circular dichroism (CD) spectra were recorded for the planar texture of the N* phase formed by a dimer, as a representative case. The presence of an intense negative CD band suggests the left-handed screw sense of the N* phase helix.
Keywords: CD activity; cholesteric phase; dimers; liquid crystals; selective reflection

Amyloid-beta-derived peptidomimetics inhibits tau aggregation - Gorantla, V. Nalini; Sunny, Lisni P.; Rajasekhar, Kolla; Nagaraju, Pramod G.; Priyadarshini, Poornima C. G.; Govindaraju, Thimmaiah; Chinnathambi, Subashchandrabose (ACS Omega, 2021)
The aggregation of tau protein is one of the hallmarks for Alzheimer's disease, resulting in neurodegeneration. The peptidomimetics strategy to prevent tau aggregation is more specific over other small molecules. In the present study, we analyzed the effect of amyloid-beta-derived peptidomimetics for inhibiting heparin-induced tau aggregation in vitro. These peptides and their derivatives were known to prevent aggregation of amyloid-beta. KLVFF is a hydrophobic sequence of the pentapeptide that prevented tau aggregation as observed by thioflavin S fluorescence, transmission electron microscopy, and circular dichroism spectroscopy. P4 and P5 also prevented assembly of tau into aggregates and formed short fibrils. The beta-sheet breaker LPFFD was however ineffective in preventing tau aggregation. The peptides further demonstrated reversal of tau-induced cytotoxicity in a dose-dependent manner. Our results suggested that these peptides can also be used to inhibit tau aggregation and also, toxicity induced by tau could be considered as potential molecules that have an effect on tau as well as amyloid-beta.

Antimicrobial synergy of silver-platinum nanohybrids with antibiotics - Ranpariya, Bansi; Salunke, Gayatri; Karmakar, Srikanta; Babiya, Kaushik; Sutar, Santosh; Kadoo, Narendra; Kumbhakar, Pathik; Ghosh, Sougata (Frontiers in Microbiology, 2021)
Various bacterial pathogens are responsible for nosocomial infections resulting in critical pathophysiological conditions, mortality, and morbidity. Most of the bacterial infections are associated with biofilm formation, which is resistant to the available antimicrobial drugs. As a result, novel bactericidal agents need to be fabricated, which can effectively combat the biofilm-associated bacterial infections. Herein, for the first time we report the antimicrobial and antibiofilm properties of silver-platinum nanohybrids (AgPtNHs), silver nanoparticles (AgNPs), and platinum nanoparticles (PtNPs) against Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus. The AgPtNHs were synthesized by a green route using Dioscorea bulbifera tuber extract at 100 degrees C for 5 h. The AgPtNHs ranged in size from 20 to 80 nm, with an average of similar to 59 nm. AgNPs, PtNPs, and AgPtNHs showed a zeta potential of -14.46, -1.09, and -11.39 mV, respectively. High antimicrobial activity was observed against P. aeruginosa and S. aureus and AgPtNHs exhibited potent antimicrobial synergy in combination with antibiotics such as streptomycin, rifampicin, chloramphenicol, novobiocin, and ampicillin up to variable degrees. Interestingly, AgPtNHs could inhibit bacterial biofilm formation significantly. Hence, co-administration of AgPtNHs and antibiotics may serve as a powerful strategy to treat bacterial infections.
Keywords: antibiofilm; antimicrobial synergy; biogenic synthesis; Characterization; silver-platinum nanohybrids

Antitumor effects of Ir(III)-2H-indazole complexes for triple negative breast cancer - Panchangam, Rajeeva Lochana; Rao, Ramdas Nishanth; Balamurali, Musuvathi Motilal; Hingamire, Tejashri B.; Shanmugam, Dhanasekaran; Manickam, Venkatraman; Chanda, Kaushik (Inorganic Chemistry, 2021)
In this work, we have synthesized a series of novel C,N-cyclometalated 2H-indazole-ruthenium(II) and -iridium(III) complexes with varying substituents (H, CH3, isopropyl, and CF3) in the R4 position of the phenyl ring of the 2H-indazole chelating ligand. All of the complexes were characterized by 1H, 13C, high-resolution mass spectrometry, and elemental analysis. The methyl-substituted 2H-indazole-Ir(III) complex was further characterized by single-crystal X-ray analysis. The cytotoxic activity of new ruthenium(II) and iridium(III) compounds has been evaluated in a panel of triple negative breast cancer (TNBC) cell lines (MDA-MB-231 and MDA-MB-468) and colon cancer cell line HCT-116 to investigate their structure–activity relationships. Most of these new complexes have shown appreciable activity, comparable to or significantly better than that of cisplatin in TNBC cell lines. R4 substitution of the phenyl ring of the 2H-indazole ligand with methyl and isopropyl substituents showed increased potency in ruthenium(II) and iridium(III) complexes compared to that of their parent compounds in all cell lines. These novel transition metal-based complexes exhibited high specificity toward cancer cells by inducing alterations in the metabolism and proliferation of cancer cells. In general, iridium complexes are more active than the corresponding ruthenium complexes. The new Ir(III)-2H-indazole complex with an isopropyl substituent induced mitochondrial damage by generating large amounts of reactive oxygen species (ROS), which triggered mitochondrion-mediated apoptosis in TNBC cell line MDA-MB-468. Moreover, this complex also induced G2/M phase cell cycle arrest and inhibited cellular migration of TNBC cells. Our findings reveal the key roles of the novel C–N-cyclometalated 2H-indazole-Ir(III) complex to specifically induce toxicity in cancer cell lines through contributing effects of ROS-induced mitochondrial disruption along with chromosomal and mitochondrial DNA target inhibition.

Assessing the impact of deviations in optimized multistep flow synthesis on the scale-up (vol 5, pg 838, 2020) - Sharma, M. K.; Raval, J.; Ahn, Gwang-Noh; Kim, Dong-Pyo; Kulkarni, A. A. (Reaction Chemistry & Engineering, 2021)

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

Co-decorated tellurium nanotubes for energy storage applications - Bhol, Prangya; Swain, Swarnalata; Jena, Satyaranjan; Bhatte, Kushal; Rout, Chandra Sekhar; Saxena, Manav; Jadhav, Arvind H.; Samal, Akshaya K. (ACS Applied Nano Materials, 2021)
This paper explicitly discusses the synthesis of Co-decorated Te nanotubes (NTs) using Te NTs as the sacrificial template and the evaluation of their electrochemical performance. First, one-dimensional (1D) Te NTs were synthesized and characterized by spectroscopic and microscopic tools such as UV-visible spectroscopy, X-ray diffraction spectroscopy, X-ray photoelectron spectroscopy, field-emission scanning electron microscopy, high-resolution transmission electron microscopy, and energy-dispersive X-ray spectroscopy analyses. The as-prepared hexagonal Te NTs (h-Te NTs) possess diameters of about 35 +/- 5 nm and lengths of about 500 +/- 50 nm and were used for the synthesis of Co-decorated Te NTs. The 1D nanostructure with excellent conductivity enables the material to show excellent electrochemical performance. The asymmetric assembly of the CoTe-2//AC electrode material displayed a high specific capacitance of 147 F g(-1) (specific capacity, 162 C g(-1) at a current density of 2 A g(-1) in 4 M KOH electrolyte. In addition to that, the assembly of CoTe-2//AC achieved an excellent energy density of 51.1 W h kg(-1) at a power density of 2294 W kg(-1) and confirmed the as-synthesized Co-decorated Te NTs to be an excellent electrode material.
Keywords: cobalt; nanotubes; pseudocapacitors; surfactant; Tellurium; template

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.

Comparison of glycoprofiles of rituximab versions licensed for sale in India and an analytical approach for quality assessment - Kaur, Tejinder; Shukla, Bhupendra Nath; Yadav, Vinay Kumar; Kulkarni, Mahesh J.; Rao, Alka (Journal of Proteomics, 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;">Glycosylation affects clinical efficacy and safety; therefore, is a critical quality attribute of therapeutic monoclonal antibodies. Glycans are often labile and complex in patterns, giving rise to macro- and micro-heterogeneity. Recombinant production, diverse geographical locations, associated transportation and storage conditions further compound the problem. Two-way studies comparing glycoprofile of the originator and its given biosimilar are aplenty. However, the extent of analytical variation and similarity in glycoprofile across all approved versions of a drug is hardly explored. Using UHPLC and mass spectrometry, we compared the glycoprofiles of eight rituximab drug samples licensed for sale in India. While the types of glycans were found identical, the abundance of some glycans varied significantly within the tested population. The quality range of glycosylation parameters of the tested sample population differed significantly from the previously established values for US/EU licensed rituximab. As the mean abundance of the 90% of identified glycans falls within ±3SD, the extent of mutual variations amongst tested lots is less significant compared to the extreme deviation from previously established QR limits. Thus, we propose this approach as an orthogonal method to capture glycan variations in licensed versions of mAbs for quality surveillance and in cases where originator samples' are limiting. SIGNIFICANCE: As fluctuation in glycosylation may be of clinical significance, we identify that a one-to-one comparison with originator alone is insufficient in sensing the extent of variations in glycosylation parameters in licensed biosimilars of a given therapeutic mAb. Here we propose that future biosimilarity analysis may include an orthogonal approach of generating an additional combined QR range representing variations across the originator and its biosimilars. The glycosylation profiles of eight rituximab drug samples of different make obtained from the point of sale in India were found identical amongst the tested rituximab versions. However, the QR limits corresponding to important glycosylation parameters differed significantly across all tested samples from the previously established QR limits of US- and EU-licensed rituximab in statistical terms. Such an approach may be useful in defining the true range of glycan variations in licensed versions of therapeutic mAbs.

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

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

CuO as a reactive and reusable reagent for the hydrogenation of nitroarenes - Rajendran, K.; Pandurangan, N.; Vinod, C. P.; Khan, Tuhin S.; Gupta, Shelaka; Haider, M. Ali; Jagadeesan, D. (Applied Catalysis B-Environmental, 2021)
{Copper oxide (CuO) is used as a reusable solid reagent for hydrogenation of nitroarenes to aminoarenes. The use of CuO resulted in 100 % conversion of 2.9 mmol of nitrobenzene to aniline in 45 s at room temperature using hydrazine hydrate as the reducing agent. During the reaction, CuO is converted to inactive metallic Cu which can be regenerated to active CuO by thermal oxidation. DFT simulations indicated facile formation of oxygen vacancies (EO
Keywords: Copper vacancy; CuO; Hydrogenation; Nitroarene reduction; Oxygen defects; Reactive solids

DBU/O-2-mediated oxidation of dienones - Athawale, Paresh R.; Kalmode, Hanuman P.; Reddy, D. Srinivasa (Journal of Organic Chemistry, 2021)
Herein, we describe a DBU/O-2-promoted novel method for oxidation of dienones to 2,6-dione derivatives. The reaction involves treatment of a dienone with DBU in acetonitrile employing molecular oxygen as the oxidant. Metal free conditions and an eco-friendly reagent are the striking features of this protocol. This transformation proceeds through a peroxide intermediate that upon Kornblum-DeLaMare rearrangement produces 2,6-diones. The method was successfully utilized for the synthesis of (+/-)-pleodendione with improved yields versus those of the traditional PDC-TBHP method.

Density functional theory-based study of the magnetic and optical properties of PbMO3 (M = Cr, Fe) using the modified BeckeJohnson mBJ functional (vol 128, pg 275, 2019) - Mahmood, Q.; Hassan, M.; Bhamu, K. C.; Yaseen, M.; Ramay, S. M.; Mahmood, A. (Journal of Physics and Chemistry of Solids, 2021)

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

Direct synthesis of mesoporous siliceous phosphotungstic acid and its superior catalytic activity on the cyclohexylation of phenol - Ilbeygi, Hamid; Sawant, Dhanashri P.; Ruban, Sujanya M.; Reshma, Kokane S.; Umbarkar, Shubhangi B.; Halligudi, Shivappa B.; Vinu, Ajayan (Journal of Physical Chemistry C, 2021)
The synthesis of highly active and reusable mesoporous siliceous phosphotungstic acid materials (mPTA-Si) which are prepared through a simple self-assembly between phosphotungstic acid (PTA), the polymeric surfactant, and the silica precursor assisted by KCl for cyclohexylation of phenol is reported. The surface area and the acidity of these materials are tuned with a simple adjustment of PTA in the silica framework. The prepared samples exhibit mesoporous structure with a high surface area, but the structure is collapsed when the loading of PTA is high. It is established that the Keggin structure of PTA is retained on the final mPTA-Si. mPTA-Si with different loadings of PTA are employed as the catalysts for the cyclohexylation of phenol under liquid phase conditions. Among the catalysts studied, 10.0-mPTA-8.3Si calcined at 350 degrees C is found to be highly active, selective, and recyclable and offers 100% conversion of phenol with the highest selectivity for p-cyclohexylphenol (96.8%).

Diverse reactivity of hypersilylsilylene with boranes and threecomponent reactions with aldehyde and HBpin - Bisai, Milan Kumar; Swamy, V. S. V. S. N.; Raj, K. Vipin; Vanka, Kumar; Sen, Sakya S. (Inorganic Chemistry, 2021)
The recently reported hypersilylsilylene PhC-(NtBu)(2)SiSi(SiMe3)(3) (1) reacts with BH3, 9-BBN, and PhBCl2 to yield the respective Lewis acid base adducts 2-4, respectively. Compound 4 undergoes isomerization to form a ring expansion product 5. The same silylene was found to initially form an adduct with HBpin (6) and subsequently isomerized to 7 via the rupture of the B-H bond of HBpin (7), where the hydride was bound to the carbon atom of the amidinate ligand and the Bpin unit was attached to the silicon center. Surprisingly, the reaction of 1 with HBcat results in PhC(NtBu)(2)Bcat (8). Subsequently, we have shown that HBcat forms the same product when it reacts with related silylene PhC(NtBu)(2)SiN(SiMe3)(3) (1'). With all of these reactions in hand, we ponder if silylene can activate two small molecules at one time. In this work, we delineate the three-component reactions of silylenes 1 and 1' with 4-fluorobenzaldehyde and HBpin, which afforded unusual coupling products, 9 and 10, respectively. Note that 9 and 10 were prepared from the cleavage of the B-H and C=O bonds by silylene in a single reaction and are the first structurally attested Si-C-O-B coupled products.

Durable metalloporphyrin 2D-polymer for photocatalytic hydrogen and oxygen evolution from river and sea waters - Ranjeesh, Kayaramkodath Chandran; George, Leena; Maibam, Ashakiran; Krishnamurty, Sailaja; Babu, Sukumaran Santhosh (ChemCatChem, 2021)
It is highly imaginary that the outcome of a combination of two complementary resources leads to answer an alarming global issue. One such possible example is the solar seawater splitting for `clean fuel' H-2 generation. Since the catalytic activity and stability of the photocatalysts are substantially challenged in seawater, the design of an efficient and stable photocatalyst is highly desirable. Herein, we demonstrate the solar seawater splitting by a two-dimensional polymer catalyst derived from metalloporphyrin bearing multi-hydroxyl groups. A bimetallic (Co and Ni) porphyrin 2D-polymer exhibits excellent long-term durability of 15 cycles of H-2 and O-2 generation in 200 days from pure water without a considerable decrease in efficiency. Detailed studies using river and seawaters also show the reliable performance of the catalyst over repeated cycles. Here the deactivation modes of catalytic activity have been nullified by the layered metalloporphyrin polymer structure through stable pi-pi stacking, signifying the molecular design of 2D-polymer photocatalyst.
Keywords: 2D-polymer; Photocatalyst; porphyrin; Self-assembly; water splitting

Effect of rice husk particle size on ZSM-5 physico-chemical properties for selective formation of 1,3,5-trimethyl-2-benzylbenzene (Pharmaceutical Intermediate) - Ghuge, Gorakh; Niphadkar, Prashant; Rathod, Simmy; Bokade, Vijay V. (ChemistrySelect, 2021)
Rice husk, rich in silica and abundantly available as waste, is presently destroyed by burning, which creates environmental issues. Thus, it will be advantageous if this rice husk waste can be used for preparation of valuable products. One of the application is its use as silica source in the synthesis of zeolites like ZSM-5, which are silico-aluminates. Rice husk waste is available in wide range of particle sizes in agricultural farms. There is no study available in open literature on use of these wide particle ranges for its direct application. This paper is an attempt to use wide particle size rice husk, its effect on ZSM-5 synthesis and its physico-chemical properties. Further these prepared ZSM-5 catalyst was evaluated for benzylation of mesitylene reaction. The study found that, rice husk of 600 mu m particle size is optimum as far as ZSM-5 synthesis, its physicochemical properties and further its application in mesitylene benzylation reaction.
Keywords: Mesitylene; Particle size; rice husk; Silica Source; ZSM-5

Effectors of root-knot nematodes: an arsenal for successful parasitism - Jagdale, Shounak; Rao, Uma; Giri, Ashok P. (Frontiers in Plant Science, 2021)
Root-knot nematodes (RKNs) are notorious plant-parasitic nematodes first recorded in 1855 in cucumber plants. They are microscopic, obligate endoparasites that cause severe losses in agriculture and horticulture. They evade plant immunity, hijack the plant cell cycle, and metabolism to modify healthy cells into giant cells (GCs) – RKN feeding sites. RKNs secrete various effector molecules which suppress the plant defence and tamper with plant cellular and molecular biology. These effectors originate mainly from sub-ventral and dorsal oesophageal glands. Recently, a few non-oesophageal gland secreted effectors have been discovered. Effectors are essential for the entry of RKNs in plants, subsequently formation and maintenance of the GCs during the parasitism. In the past two decades, advanced genomic and post-genomic techniques identified many effectors, out of which only a few are well characterized. In this review, we provide molecular and functional details of RKN effectors secreted during parasitism. We list the known effectors and pinpoint their molecular functions. Moreover, we attempt to provide a comprehensive insight into RKN effectors concerning their implications on overall plant and nematode biology. Since effectors are the primary and prime molecular weapons of RKNs to invade the plant, it is imperative to understand their intriguing and complex functions to design counter-strategies against RKN infection.

Elastic piezoelectric aerogels from isotropic and directionally ice-templated cellulose nanocrystals: comparison of structure and energy harvesting - Ram, Farsa; Biswas, Bipul; Torris, Arun; Kumaraswamy, Guruswamy; Shanmuganathan, Kadhiravan (Cellulose, 2021)
We report the preparation of highly compressible and elastic piezoelectric aerogels of carboxylated cellulose nanocrystals (CNCs). Aqueous CNC dispersions containing polyethyleneimine and crosslinker were frozen isotropically to yield isotropic aerogels, while oriented aerogels were prepared by directional freezing. These aerogels were highly flexible and porous (similar to 85% void fraction), exhibiting greater than 90% recovery at 50% compressive strain even after 100 compression-decompression cycles. Since such aerogels with low bulk modulus and high anisotropy would be an ideal platform for leveraging the piezoelectric properties of CNCs, we used them to prepare piezoelectric nanogenerator devices and determined their energy transduction behavior. Anisotropic aerogels led to an enhanced open-circuit voltage of 840 mV (at similar to 8 N applied force), which is over 2.6 times higher than isotropic aerogels (320 mV). The energy density of anisotropic aerogels was around 52 nW/cm(2), representing outstanding piezoelectric performance for cellulose-based aerogels. Such aerogels with high compressibility, elastic recovery and exceptional piezoelectric performance could have potential applications in sensors, wearable electronics, etc.
Keywords: Aerogel; Anisotropic; Cellulose nanocrystals; energy harvesting; Piezoelectricity

Electronically integrated mesoporous Ag-TiO2 nanocomposite thin films for efficient solar hydrogen production in direct sunlight - Mani, Sunesh S.; Rajendran, Sivaraj; Nalajala, Naresh; Mathew, Thomas; Gopinath, Chinnakonda S. (Energy Technology, 2021)
The synthesis of mesoporous TiO2 by a solution-based assembly process and Ag/TiO2 nanocomposites is provided. The efficacy of Ag/TiO2 nanocomposite as photocatalyst in thin-film form is demonstrated for solar hydrogen generation in sunlight. Integration of Ag with TiO2 dramatically enhanced the H-2 production: with 1 wt% Ag on TiO2 (TiAg-1), the H-2 yield was observed to be 4.59 mmol h(-1) g(-1), which is 2.3 (30) times larger than 0.5 wt% Ag on TiO2. TiAg-1 shows 4.3 times higher activity in film form compared with its powder counterpart. High photocatalytic efficiency is attributed to the surface plasmon resonance effect of Ag, electronic integration of Ag with TiO2, and subsequent valence band broadening, large distribution of Ag nanoparticles and abundant Ag-TiO2 Schottky junctions, and the later minimizes electron-hole recombination. Interparticle mesoporous network increases necking and the high surface area offers easy accessibility of the reactants to a large number of active sites.
Keywords: heterogeneous catalysis; heterojunctions; plasmon effect; Silver; solar energy conversion; Solar hydrogen

Enhanced electrocatalytic activity of PtRu/nitrogen and sulphur co-doped crumbled graphene in acid and alkaline media - Pang, Liuqing; Miao, Yuanyuan; Bhange, Siddheshwar N.; Barras, Alexandre; Addad, Ahmed; Roussel, Pascal; Amin, Mohammed A.; Kurungot, Sreekumar; Szunerits, Sabine; Boukherroub, Rabah (Journal of Colloid and Interface Science, 2021)
The low mass activity and high price of pure platinum (Pt)-based catalysts predominantly limit their large-scale utilization in electrocatalysis. Therefore, the reduction of Pt amount while preserving the electrocatalytic efficiency represents a viable alternative. In this work, we prepared new PtRu2 nanoparticles supported on sulphur and nitrogen co-doped crumbled graphene with trace amounts of iron (PtRu2/PF) electrocatalysts. The PtRu2/PF catalysts exhibited enhanced electrocatalytic performance and stability for the hydrogen evolution reaction (HER) at pH = 0. Moreover, the prepared PtRu2/PF electrocatalyst displayed higher HER activity than commercial 20% Pt/C. The PtRu2/PF catalyst achieved a current density of 10 mA cm(-2) at an overpotential value of only 22 mV for HER, performing better activity than many other Pt-based electrocatalysts. Besides, the PtRu2/PF revealed a good performance for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline media. The PtRu2/PF catalyst recorded a current density of 10 mA cm(-2) at an overpotential of only 270 mV for OER in KOH (1.0 M) solution and an onset potential of 0.96 V vs. RHE (at 1 mA cm(-2)) for ORR in KOH (0.1 M) solution. (C) 2021 Elsevier Inc. All rights reserved.
Keywords: HER; OER; ORR; PtRu2; Sulphur and nitrogen co-doped crumbled graphene

Entacapone polymorphs: crystal structures, dissolution, permeability, and stability - Bommaka, Manish Kumar; Mannava, M. K. Chaitanya; Rai, Sunil K.; Suresh, Kuthuru; Nangia, Ashwini K. (Crystal Growth & Design, 2021)
Entacapone (ETP) is a catechol-O-methyltransferase (COMT) drug used to treat Parkinson's disease. ETP is available in the marketplace under the brand name Comtan since 2010, and ETP form-I was first reported in a patent published in 2001. However, analysis of its Xray crystal structures and stability relationship of ETP polymorphs and their dissolution and permeability profile have not yet been reported. We crystallized two new conformational polymorphs of ETP from a water and acetone mixture and studied the structural origin of polymorphism and their phase transformations, stability, equilibrium solubility, dissolution, and permeability properties. The ETP molecule adopts different conformations in the polymorphic structures with slight changes in carbonyl and nitrile group orientations. Thermal analysis suggests that form-III and form-IV are enantiotropically related to form-I, which is the thermodynamically stable form at ambient conditions. In contrast, form-II is monotropically related to form-I. Equilibrium solubility, dissolution, and permeability studies show that form-II persists in the slurry medium and dissolves faster with a high flux rate compared to the stable form-I in phosphate buffer solution at 37 +/- 0.5 degrees C.

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.

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

gamma-Al2O3/triflic acid as cooperative catalysts for the tandem Michael addition/carbocyclization: an easy access to 2-substituted pyrrolo[2,1-a]isoquinolines and 3-substituted pyrrolidine-2,5-diones - Rao, Ramana Sreenivasa; Sahani, Anita; Ali, Sheikh Haider; Pradhan, Sumanta; Ramanathan, Chinnasamy Ramaraj (Journal of Heterocyclic Chemistry, 2021)
A tandem Michael addition/carbocyclization of 3,4-dimethoxyphenethyl maleimide with carbon and sulfur nucleophiles is accomplished via a relay catalysis using gamma-Al2O3/TfOH binary system. The X-ray Photoelectron Spectroscopy (XPS) analysis of binary system indicates the presence of AlF3, AlO(OH) species(.) This approach provides an easy access to 2-aryl or 2-thio aryl pyrrolo[2,1-a]isoquinolines in good yields in a tandem fashion. With suitable ratio of gamma-Al2O3/TfOH binary system, the Michael addition of N/C/S nucleophiles to N-benzyl maleimide is also achieved. A key to the success of these reactions would be the generation of AlF3, AlO(OH) species from gamma-Al2O3 and TfOH, which might have delineated the disadvantageous background reactions usually displayed by a strong Bronsted acid such as TfOH.
Keywords: 1-a]isoquinolines; 3-substituted pyrrolidine-2; 5-diones; carbocyclization; gamma-Al2O3/TfOH binary system; Michael addition; pyrrolo[2

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

Green route for carbonylation of amines by CO2 using Sn-Ni-O bifunctional catalyst and theoretical study for finding best suited active sites - Kulal, Nagendra; Vetrivel, Rajappan; Gopinath, Chinnakonda S.; Ravindran, Rahul K.; Rao, Vinod N.; Shetty, Manjunath; Shrikanth, R.; Rangappa, Dinesh; Shanbhag, Ganapati V. (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;">Reaction between n-alkylamine and CO<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;"> has gained interest due to the demand for the dialkylurea for various applications. For the first time, the tool <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;">Mathematica<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;"> was used to analyze the experimental data with an idea to derive an equation which determines the best suited active sites for any given input set of dependent parameters. The equation can further be used to predict the product yield with the known values of active sites for a reaction. Among several Sn containing mixed oxides, Sn-Ni oxide (Sn-Ni-O) was found to be the better performing catalyst. The studies indicate that the formation of new defect sites when NiO and SnO<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;"> are in the mixed state and possibly a solid solution enhances the catalytic efficiency. There are two main reasons for improved catalytic performance; one, mixing of SnO<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;"> into NiO which reduces the number of holes (h<span style="font-size: 13.5px; line-height: 0; position: relative; top: -0.5em; 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;">+<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;">) localized on lattice oxygen (O<span style="font-size: 13.5px; line-height: 0; position: relative; top: -0.5em; 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;">+ h<span style="font-size: 13.5px; line-height: 0; position: relative; top: -0.5em; 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;">+<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; top: -0.5em; 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;">•−<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 two, smaller SnO<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;"> particles are dispersed on the bigger particle NiO which alters the acidic and basic active sites in the catalyst. FT-IR adsorption study with amine and CO<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;"> helped in deriving a plausible mechanism for this reaction. Under optimized reaction condition, Sn1.1-Ni-O-600 gave 77.3% of n-butylamine conversion and 75.7% of yield for 1,3-dibutylurea. The versatility of the catalyst was tested for carbonylation of different aliphatic and aromatic amines, diamine and hydroxy amine with CO<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;">.
Keywords: amines; CO2; Mixed oxide catalyst and bi-functional catalyst; Substituted urea

Green synthesis of methoxy-poly(ethylene glycol)-block-poly(l-lactide-co-glycolide) copolymer using zinc proline as a biocompatible initiator for irinotecan delivery to colon cancer in vivo - Giram, Prabhanjan S.; Wang, Julie Tzu-Wen; Walters, Adam A.; Rade, Priyanka P.; Akhtar, Muhammad; Han, Shunping; Faruqu, Farid N.; Abdel-Bar, Hend M.; Garnaik, Baijayantimala; Al-Jamal, Khuloud T. (Biomaterials Science, 2021)
Poly(lactic-co-glycolic acid) (PLGA) is the most commonly described biocompatible copolymer used in biomedical applications. In this work, a green synthetic approach based on the biocompatible zinc proline complex, as an initiator for PLGA synthesis, is reported for the first time for the synthesis of methoxy-poly(ethylene glycol)-block-poly(l-lactic-co-glycolic acid) (mPEG-PLGA). mPEG-PLGA with controlled molecular weight and narrow polydispersity was synthesised. Its potential for delivery of irinotecan (Ir), a poorly water-soluble chemotherapeutic drug used for the treatment of colon and pancreatic cancer, was studied. Nanoparticles of controlled size (140-160 nm), surface charge (similar to-10 mV), release properties and cytotoxicity against CT-26 (colon) and BxPC-3 (pancreatic) cancer cells, were prepared. Tumor accumulation was confirmed by optical imaging of fluorescently labelled nanoparticles. Unlike Tween (R) 80 coated NP-Ir, the Pluronic (R) F-127 coated NP-Ir exhibits significant tumor growth delay compared to untreated and blank formulation treated groups in the CT-26 subcutaneous tumor model, after 4 treatments of 30 mg irinotecan per kg dose. Overall, this proof-of-concept study demonstrates that the newly synthesized copolymer, via a green route, is proven to be nontoxic, requires fewer purification steps and has potential applications in drug delivery.

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.

Highly compressible ceramic/polymer aerogel-based piezoelectric nanogenerators with enhanced mechanical energy harvesting property - Ram, Farsa; Suresh, Karthika; Torris, Arun; Kumaraswamy, Guruswamy; Shanmuganathan, Kadhiravan (Ceramics International, 2021)
Ceramic piezoelectric materials have orders of magnitude higher piezoelectric coefficients compared to polymers. However, their brittleness precludes imposition of large strains in mechanical energy harvesting applications. We report here that ice templating affords low bulk modulus lead-free aerogel piezoelectric nanogenerators (PENG) with unprecedented combination of flexibility and high piezoelectric response (voltage and power density). A modified ice templating protocol was used to fabricate piezoelectric nanocomposites of surface modified BaTiO3 (BTO) nanoparticles in crosslinked polyethylene imine. This protocol allowed incorporating a significantly high fraction of BTO particles (up to 83 wt %) in the aerogel, while retaining remarkably high compressibility and elastic recovery up to 80% strain. The output voltage, at an applied compressive force of 20 N (100 kPa), increased with BTO loading and a maximum output voltage of 11.6 V and power density of 7.22 ?W/cm2 (49.79 ?W/cm3) was obtained for PENG aerogels containing 83 wt% BTO, which is orders of magnitude higher than previously reported values for foam-based piezoelectric energy harvesters. The BTO/PEI PENGs also showed cyclic stability over 900 cycles of deformation. PENGs with higher porosity showed better elastic recovery and piezoelectric properties than lower porosity and higher BTO content aerogels. To the best of our knowledge, this is the first report to demonstrate the piezoelectric properties of high ceramic content aerogels having very high compressibility and elastic recovery.
Keywords: Ceramic polymer aerogels; energy harvesting; ice templating; piezoelectric

Highly efficient and reusable Ru-NaY catalyst for the base free oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic acid - Kandasamy, Prabu; Gogoi, Pranjal; Venugopalan, Aswathy Thareparambil; Raja, Thirumalaiswamy (Catalysis Today, 2021)
Oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is an important reaction for the production of recyclable bio-based polymers. Herein, we report a series of Ru nanoparticles supported on NaY zeolites catalysts for the oxidation of HMF to FDCA. The catalysts were prepared by simple ion exchanged method. Among all the catalysts, the optimized 3 wt % Ru-NaY catalyst showed superior catalytic activity under base free conditions with a shorter period of reaction time. The conversion of HMF was 100 % with 94 % FDCA yield. This catalyst was reused for fourth cycles, with an insignificant decrease in the yield of FDCA. H2-chemisorption and HRTEM studies confirmed that high metal dispersion and small size of Ru nanoparticles play vital roles for the HMF oxidation. In addition, the acidic hydroxyl groups of the supercage as well as higher amount of metallic Ru° are also responsible for the high yield and productivity of FDCA.

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.

Hypervalent iodine(iii) induced oxidative olefination of benzylamines using Wittig reagents - Ramavath, Vijayalakshmi; Rupanawar, Bapurao D.; More, Satish G.; Bansode, Ajay H.; Suryavanshi, Gurunath (New Journal of Chemistry, 2021)
We have developed hypervalent iodine(iii) induced oxidative olefination of primary and secondary benzylamines using 2C-Wittig reagents, which provides easy access to alpha,beta-unsaturated esters. Mild reaction conditions, good to excellent yields with high (E) selectivity, and a broad substrate scope are the key features of this reaction. We have successfully carried out the gram-scale synthesis of alpha,beta-unsaturated esters.

Identification of a novel series of potent organosilicon mosquito repellents - Kulkarni, Akshay S.; Ramesh, Remya; Walia, Safal; Sayyad, Shahebaz I.; Gathalkar, Ganesh B.; Balamkundu, Seetharamsing; Joshi, Manali; Sen, Avalokiteswar; Reddy, D. Srinivasa (ACS Omega, 2021)
Mosquito control by personal protection is one of the most efficient ways of curtailing deadly diseases such as malaria and dengue with the potential to save millions of lives per year. DEET (N,N-diethyl-3-methyl benzamide) is currently considered as the gold standard for mosquito repellents, being used for the past several decades. Control by DEET, however, is being threatened by emerging resistance among mosquitoes. To address this concern and also to improve protection times, we synthesized a novel series of 25 silicon-containing acyl piperidines using acid–amine coupling protocol and tested their activity against Aedes aegypti in mosquito-repellent assays. Several compounds from this series appear to possess good mosquito-repellent properties. Most notably, at 0.5 mg/cm2 concentrations, the mean protection time for NDS100100 was 756 min, which was higher than that of DEET (616 min). The details of design, synthesis, and biological evaluation are discussed herein.

Improved photocatalytic efficiency of TiO2 by doping with tungsten and synthesizing in ionic liquid: precise kinetics-mechanism and effect of oxidizing agents - Raut, Sandesh S.; Kamble, Sanjay P.; Kulkarni, Prashant S. (Environmental Science and Pollution Research, 2021)
The degradation of nitroaromatics/toxic energetic compounds contaminated water is a major cause of concern. W-doped TiO2 nanoparticles (NPs) were synthesized in ionic liquid, ethyl methyl imidazolium dicyanamide (EMIM-DCA) by a solvothermal method. The developed NPs were sintered at 500 degrees C and characterized by UV-Vis-DRS, FT-IR, FE-SEM, XRD, XPS, and BET techniques. The 30-40-nm-sized NPs were subjected to photocatalytic degradation of the toxic energetic compound, tetryl (2,4,6-trinitrophenylmethylnitramine) under UV-Vis light. Various operating parameters such as the effect of concentration of catalyst, pH of feed phase, oxidizing agents, and recycling of catalyst were studied in detail. For the first time, the degradation-mechanism pathway and kinetics of tetryl were evaluated. The degradation products were precisely analyzed by using HPLC, GC-MS, and TOC techniques. The USEPA has prescribed a drinking water limit of 0.02 mg L-1, and it was found that 0.5 g of 4% W-TiO2 could totally degrade tetryl (50 mg L-1) within 8 h. The kinetic rate constant of 4% W-TiO2 was 0.356 h(-1), whereas pure TiO2 showed 0.207 h(-1).
Keywords: Ionic liquid; Nitroaromatics; Photocatalysis; Recycling of catalyst; W-doped TiO2; wastewater

Improvement in serum amylase and glucose levels in diabetic rats on oral administration of bisdemethoxycurcumin from Curcuma longa and limonoids from Azadirachta indica - Ramkumar, Sudha; Thulasiram, V. H.; RaviKumar, Ameeta (Journal of Food Biochemistry, 2021)
Curcuma longa and Azadirachta indica are traditionally used in Indian cuisine and Ayurvedic medicine as nutraceuticals against diabetes. The crude C. longa isopropanol extract, bisdemethoxycurcumin (BDMC), the purified bioactive component from C. longa, and limonoids azadiradione, gedunin from A. indica, are able to inhibit in vitro the antidiabetic target human pancreatic alpha-amylase independently. However, no reports on their in vivo efficacy in animal models exist. Thus, the antidiabetic effect of these orally administered human pancreatic alpha-amylase inhibitors was performed on streptozotocin-induced Sprague-Dawley rats. Initially, the normal rats were treated with test compounds (10-100 mg/kg of body weight) in corn oil (5 ml/kg), and as no lethality was observed in these doses, further studies were carried out with lowest concentration of 10 mg/kg of body weight. A reduction in area under curve (AUC) suggested glucose-lowering effect of these compounds in starch fed diabetic rats. The efficacy study showed a significant improvement in body weight, blood glucose levels, serum amylase, and fructosamine levels as well in other serum parameters associated with diabetes with respect to liver and renal functions. Hence, under in vivo conditions, inhibition of alpha-amylase activity by BDMC and limonoids affirms it as one of the mechanisms of action resulting in reduction of blood glucose levels. Practical applications Bisdemethoxycurcumin from C. longa and limonoids, namely, azadiradione and gedunin, from A. indica are potent inhibitors of the antidiabetic target human pancreatic alpha-amylase. Oral Starch Tolerance Test (OSTT) and 28-day efficacy study to check the effect of these orally administered inhibitors in diabetic rat models showed significant improvements in serum blood glucose and amylase levels as well as in other diabetes related serum parameters, namely, bilirubin, lipids, lactate dehydrogenase, alkaline phosphatase, and urea. The study contributes to understanding the action and efficacy of these pancreatic alpha-amylase inhibitors and suggests a potential role for them as nutraceuticals/therapeutics in management of post-prandial hyperglycemia.
Keywords: ‐ α Amylase inhibitors; Azadiractha indica; BDMC; Curcuma longa; in vivo rat studies; Limonoids

Improving efficiency for removal of ammoniacal nitrogen from wastewaters using hydrodynamic cavitation - Patil, Pravin B.; Bhandari, Vinay M.; Ranade, Vivek V. (Ultrasonics Sonochemistry, 2021)
The present study reports significant improvements in the removal of ammoniacal nitrogen from wastewater which is an important problem for many industries such as dyes and pigment, distilleries and fisheries. Pilot plant studies (capacity, 1 m(3)/h) on synthetic wastewater using 4-amino phenol as model nitrogen containing organic compound and two real industrial effluents of high ammoniacal nitrogen content were carried out using hydrodynamic cavitation. Two reactor geometries were evaluated for increased efficiency in removal-orifice and vortex diode. Effect of initial concentration (100-500 mg/L), effect of pressure drop (0.5-5 bar) and nature of cavitating device (linear and vortex flow for cavitation) were evaluated along with effect of salt content, effect of hydrogen peroxide addition and aeration. Initial concentration was found to have significant impact on the extent of removal: similar to 5 g/m(3) removal for initial concentration of 100 mg/L and up to 12 g/m(3) removal at high concentration of 500 mg/L. Interestingly, significant improvement of the order of magnitude (up to 8 times) in removal of ammoniacal nitrogen could be obtained by sparging air or oxygen in hydrodynamic cavitation and a very high removal of above 80% could be achieved. The removal of ammoniacal nitrogen by vortex diode was also found to be effective in the industrial wastewaters and results on two different effluent samples of distillery industry indicated up to 75% removal, though with longer time of treatment compared to that of synthetic wastewater. The developed methodology of hydrodynamic cavitation technology with aeration and vortex diode as a cavitating device was found to be highly effective for improving the efficiency of the conventional cavitation methods and hence can be highly useful in industrial wastewater treatment, specifically for the removal of ammoniacal nitrogen.
Keywords: Amino phenol; Cavitation; Oxidation; pollution; Wastewater treatment

In vitro antitubercular screening and in silico study of germacradienolide from blainvillea latifolia - Honmore, Varsha; Kalyankar, Vidya; Natu, Arun; Khedkar, Vijay; Sarkar, Dhiman; Rojatkar, Supada (Asian Journal of Chemistry, 2021)
Bioassay-guided isolation from acetone extract of Blainvillea latifolia yielded one compound. The acetone extract, fractions and the compound 1 were investigated for antitubercular activity against Mycobacterium tuberculosis H37Ra. Compound 1 showed the activity with IC50 and MIC values at 8.9 and >100 μg/mL. However, the acetone extract of Blainvillea latifolia was inactive against two Gram negative (E. coli, P. flurescence) and two Gram-positive (S. aureus, B. subtilis) bacterial strains. Hence, it was concluded that the extract and the compound 1 are specifically active against MTB and not against bacterial strains. Molecular docking study was performed against crucial mycobacterial target MtInhA to gain an insight into the binding mode and the thermodynamic interactions governing the binding affinity of this molecule.

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.

An innovative light assisted production of acetic acid from CO2 and methanol: a first photocatalytic approach using a reusable cobalt(ii) molecular hybrid at atmospheric pressure - Saini, Sandhya; Samal, Pragnya Paramita; Krishnamurty, Sailaja; Ray, Anjan; Jain, Suman L. (Green Chemistry, 2021)
Acetic acid is an important commodity chemical that is produced either by fermentation processes, or more commonly, through chemical routes such as methanol carbonylation with CO and H-2, acetaldehyde oxidation, or hydrocarbon oxidation. More recently, methanol hydrocarboxylation with CO2 and H-2 under thermal catalytic conditions has attracted interest. The synthesis of acetic acid from easily available CO2 is of great significance yet rarely reported. The present paper describes the first photocatalytic approach for the synthesis of acetic acid from methanol and CO2 under ambient reaction conditions without using molecular hydrogen. The maximum conversion of methanol achieved is 60% with a selectivity of 81% towards acetic acid using an octa-sulfur bound cobalt phthalocyanine (CoPc/S8) photocatalyst without an additional sacrificial electron donor. Product analysis, controlled experiments and DFT calculations suggest the formation of methylene carbene as a reactive intermediate. The developed methodology represents a potentially exciting approach for synthesizing acetic acid utilizing CO2 in a sustainable manner.

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 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

In-situ experimental and computational approach to investigate the nature of active site in low-temperature CO-PROX over CuOx-CeO2 catalyst - Adak, Shubhadeep; Rabeah, Jabor; Ranjan, Ravi; Khan, Tuhin Suvra; Poddar, Mukesh Kumar; Gupta, Rishi Kumar; Sasaki, Takehiko; Kumar, Sagar; Bordoloi, Ankur; Gopinath, Chinnakonda S.; Bruckner, Angelika; Bal, Rajaram (Applied Catalysis A-General, 2021)
Preferential oxidation (PROX) of carbon monoxide (CO) in presence of excess hydrogen is a necessity to prevent poisoning of the Pt-anode by CO in PEMFCs (Polymer Electrolyte Membrane Fuel Cell). A highly active catalyst, 5 wt% Cu-CeO2 showed 100 % CO conversion at 65 degrees C without any undesirable oxidation of H-2. The catalyst showed no deactivation even after 100 h on stream, making it viable for practical fuel cell application. Operando EPR in the PROX reaction condition revealed highly dispersed mixed valent cations with oxygen vacancies, responsible for the low-temperature PROX activity. At the active site, both Cu and Ce ions were shown to reversibly change their valence states to facilitate the abstraction of bridging lattice oxygen for CO oxidation to CO2. This surface oxygen mediated CO oxidation was found to be much faster than that of H-2 to H2O, which could explain the complete selectivity of oxygen for CO2 formation.
Keywords: CuOx-CeO2; interface; Oxygen vacancy; PROX; Synergistic

Integrated genetic and metabolic landscapes predict vulnerabilities of temozolomide resistant glioblastoma cells - Immanuel, Selva Rupa Christinal; Ghanate, Avinash D.; Parmar, Dharmeshkumar S.; Yadav, Ritu; Uthup, Riya; Panchagnula, Venkateswarlu; Raghunathan, Anu (npj Systems Biology and Applications, 2021)
Metabolic reprogramming and its molecular underpinnings are critical to unravel the duality of cancer cell function and chemo-resistance. Here, we use a constraints-based integrated approach to delineate the interplay between metabolism and epigenetics, hardwired in the genome, to shape temozolomide (TMZ) resistance. Differential metabolism was identified in response to TMZ at varying concentrations in both the resistant neurospheroidal (NSP) and the susceptible (U87MG) glioblastoma cell-lines. The genetic basis of this metabolic adaptation was characterized by whole exome sequencing that identified mutations in signaling pathway regulators of growth and energy metabolism. Remarkably, our integrated approach identified rewiring in glycolysis, TCA cycle, malate aspartate shunt, and oxidative phosphorylation pathways. The differential killing of TMZ resistant NSP by Rotenone at low concentrations with an IC50 value of 5 nM, three orders of magnitude lower than for U87MG that exhibited an IC50 value of 1.8 mM was thus identified using our integrated systems-based approach.

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

Lead-free zero dimensional tellurium(iv) chloride-organic hybrid with strong room temperature emission as a luminescent material - Biswas, Anupam; Bakthavatsalam, Rangarajan; Bahadur, Vir; Biswas, Chinmoy; Mali, Bhupendra P.; Raavi, Sai Santosh Kumar; Gonnade, Rajesh G.; Kundu, Janardan (Journal of Materials Chemistry C, 2021)
Despite the current progress in `Pb-free' low dimensional main group metal halide based luminescent materials, it is challenging to synthesize Te(iv) halide hybrids with strong ambient emission with excitation features in the visible range as efficient and stable phosphors for potential lighting applications. Reported here is a (benzyltriethylammonium)(2)TeCl6 zero dimensional hybrid material with excitation features in the visible range and strong room temperature, broadband, intrinsic luminescence (PLQY similar to 15%) arising due to self-trapped excitons (STEs). Furthermore, a proof-of-concept LED architecture demonstrates successful optical down-conversion with a visible light excitation source. Here, exclusive adoption of a `regular' octahedral Te(iv)-halide unit structure with minimal static distortion provides a unique opportunity to unmask the role played by 5s(2) lone pair electrons in shaping the emissive properties. This effort may open up new avenues towards unravelling the role of lone pair stereoactivity in controlling the PLQY in low dimensional hybrids that has proven to be challenging for the reported (Sb, Sn) based low dimensional 5s(2) metal halide hybrid materials.

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

Mechanism of adhesion of natural polymer coatings to chemically modified siloxane polymer - Joseph, Emmanuel; Rajput, Shatruhan Singh; Patil, Shivprasad; Nisal, Anuya (Langmuir, 2021)
Surface coatings play an important role in improving the performance of biomedical implants. Polydimethylsiloxane (PDMS) is a commonly used material for biomedical implants, and surface-coated PDMS implants frequently face problems such as delamination or cracking of the coating. In this work, we have measured the performance of nano-coatings of the biocompatible protein polymer silk fibroin (SF) on pristine as well as modified PDMS surfaces. The PDMS surfaces have been modified using oxygen plasma treatment and 3-amino-propyltriethoxy-silane (APTES) treatment. Although these techniques of PDMS modification have been known, their effects on adhesion of SF nano-coatings have not been studied. Interestingly, testing of the coated samples using a bulk technique such as tensile and bending deformation showed that the SF nano-coating exhibits improved crack resistance when the PDMS surface has been modified using APTES treatment as compared to an oxygen plasma treatment. These results were validated at the microscopic and mesoscopic length scales through nano-scratch and nano-indentation measurements. Further, we developed a unique method using modified atomic force microscopy to measure the adhesive energy between treated PDMS surfaces and SF molecules. These measurements indicated that the adhesive strength of PDMS-APTES-SF is 10 times more compared to PDMS-O-2-SF due to the higher number of molecular linkages formed in this nanoscale contact. This lower number of molecular linkages in the PDMS-O-2 indicates that only fewer numbers of surface hydroxyl groups interact with the SF protein through secondary interactions such as hydrogen bonding. On the other hand, a larger number of amine groups present on PDMS-APTES surface hydrogen bond with the polar amino acids present on the silk fibroin protein chain, resulting in better adhesion. Thus, APTES modification to the PDMS substrate results in improved adhesion of nano-coating to the substrate and enhances the delamination and crack resistance of the nano-coatings.

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

Metal halide structure and the extent of distortion control the photo-physical properties of luminescent zero dimensional organic-antimony(iii) halide hybrids - Biswas, Anupam; Bakthavatsalam, Rangarajan; Mali, Bhupendra P.; Bahadur, Vir; Biswas, Chinmoy; Raavi, Sai Santosh Kumar; Gonnade, Rajesh G.; Kundu, Janardan (Journal of Materials Chemistry C, 2021)
Antimony(iii) halide based zero dimensional hybrids have gained attention as broadband emitters. Until now, quadrangular pyramidal SbX5 based and octahedral SbX6 based 0D hybrids have been reported utilizing different organic ligands demonstrating some structural tunability affecting their emissive properties. Utilizing a common organic ligand, here we demonstrate the structural tunability (quadrangular pyramidal, octahedral, or a combination thereof) of the metal halide unit in Sb(iii)Cl 0D hybrids with contrasting photo-physical properties (broadband, Stokes shift, strong/weak colored emission). The structure-property-mechanism correlation of the synthesized compounds [1 (C12H52Cl18N8O4Sb3; tris Sb green); 2 (C12H50Cl14N8O3Sb2; tris Sb red); 3 (C24H88Cl25N16O4Sb3; tris Sb yellow)] identifies crucial factors that control their emissive properties. The X-ray analysis reveals the structure (1-octahedral; 2-quadrangular pyramidal; 3-combination thereof) and the order of the extent of structural distortion as 1-3 MUCH LESS-THAN 2. The metal halide coordination environment asymmetry and its structure are observed to dictate PL emission energy (1-green; 2-red; 3-yellow) as supported by a qualitative Molecular Orbital scheme. The extent of structural distortion guides the observed Stokes shifts (1-165 nm; 2-290 nm; 3-200 nm; 1-3 < 2). Interestingly, the extent of distortion is found to be well correlated with the observed PLQY (1-45%; 2-6%; 3-43%; 1-3 >> 2). This report clearly demonstrates the structural tunability and the effect of the metal halide unit structure/distortion in shaping the emissive properties of 0D organic Sb(iii) halide hybrids.

Metal-free, acid-catalyzed 1,6-conjugate addition of NH-sulfoximines to para-quinone methides: accessing to diarylmethine imino sulfanone - More, Satish G.; Rupanawar, Bapurao D.; Suryavanshi, Gurunath (Journal of Organic Chemistry, 2021)
We have reported an efficient and metal-free method for the construction of alpha-diarylmethine imino sulfanone using acid-catalyzed 1,6-conjugate addition of sulfoximines on para-quinine methides (p-QMs). This method showed broad functional group tolerance and a wide range of substrate scope with good to excellent yield. The excellent protocol exhibits mild reaction conditions with high atom economy. The practicability of the present method was supported by a Gram-scale reaction.

Methyl esters of fungal biomass-derived lipids produced via solid-state fermentation of sugarcane bagasse and assessment as a blend component in diesel fuel. - Khot, Mahesh; RaviKumar, Ameeta; Kumar, V. Ravi (Journal of the American Oil Chemists Society, 2021)

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