One-pot three-component synthesis and photophysical properties of highly fluorescent novel 4-alkyl-3-aryl-2,6-dicyanoanilines by using tris(hydroxymethyl)aminomethane as a catalyst - Kudale, A. S.; Kamble, S. B.; Gore, A. H.; Pisal, M. M.; Salokhe, A. T.; Kolekar, G. B.; Helavi, V. B. (Chemical Data Collections, 2019)
Novel 4-alkyl-3-aryl-2,6-dicyanoanilines were synthesized by a multi-component one-step reaction of aromatic aldehyde, malononitrile and aliphatic aldehyde using tris(hydroxymethyl)aminomethane (THAM) as a catalyst under microwave (MW) irradiation or conventional heating. The optimized reaction condition involved use of 2.5 equivalents of THAM under MW irradiation at 140 W using 20% MW power for 5 min or conventional heating at 80 °C for 8 h in dimethylformamide. The photophysical properties including λmax, quantum yield and Stokes’ shifts of newly synthesized molecules were studied. All compounds exhibited quantum yield in the range of 0.04–0.52 with respect to standard quinine sulphate having quantum yield 0.54. The Stokes’ shifts of all compounds were found in the range of 41–105 nm. The current strategy provides operationally simple protocol using THAM as a catalyst to synthesize 4-alkyl-3-aryl-2,6-dicyanoanilines with diverse structural features to make them available for exploration of their photophysical as well as biological applications.

Ortho-oxygenative 1,2-difunctionalization of diarylalkynes under merged gold/organophotoredox relay catalysis - Sancheti, Shashank P.; Akram, Manjur O.; Roy, Rupam; Bedi, Vaibhav; Kundu, Shubhankar; Patil, Nitin T. (Chemistry-An Asian Journal, 2019)
Reported herein is an ortho-oxygenative 1,2-difunctionalization of diarylalkynes under merged gold/organophotoredox catalysis to access highly functionalized 2-(2-hydroxyaryl)-2-alkoxy-1-arylethan-1-ones. Detailed mechanistic studies suggested a relay process, initiating with gold-catalyzed hydroalkoxylation of alkynes, to generate enol-ether followed by a key formal [4+2]-cycloaddition reaction. The successful application of the present methodology was also shown for the synthesis of benzofurans.
Keywords: binary catalyst system; Gold catalysis; organocatalyst; photoredox; synthetic methodology

Oxidative disproportionation of MoS2/GO to MoS2/MoO3-x/RGO : integrated and plasmonic 2D-multifunctional nanocomposites for solar hydrogen generation from near-infrared and visible regions - Patra, Kshirodra Kumar; Ghosalya, Manoj Kumar; Bajpai, Himanshu; Raj, Sreeya; Gopinath, Chinnakonda S. (Journal of Physical Chemistry C, 2019)
Two dimensional (2D) semiconductor materials have been recently demonstrated to be effective plasmonic materials and alternatives to costly noble metals. However, tuning the plasmon resonance of 2D semiconductors and integrating with another material or semiconductor for various applications, such as solar light harvesting, remains a challenge. Herein, we designed a simple and attractive method, which facilitates the diffusion of oxygen from the graphene oxide (GO) layers of the MoS2/GO (MG) composite to oxidize the MoS2 layers significantly due to thermal treatment under inert atmosphere. This is the key step in the formation of MoS2/MoO3-x/RGO (MMR) (x = 0, 0.5, and 1, and all stoichiometries co-exist), due to disproportionation of MoS2/GO, with bulk heterojunctions among the components. The observed behavior is attributed to the oxidation of Mo4+ cations (of MoS2) to higher oxidation states in MMR (Mo(5+ )and Mo6+ of MoO3-x), which also alters the valence-band electronic structure and work function of the resulting composite. The 2D MoO3-x layers with a large amount of Mo5+ oxidation states enables facile charge carrier generation due to plasmonic effect, whereas MoS2 provides active sites for catalysis. The solar H-2 generation was demonstrated in the visible and near-infrared region by combining both the plasmonic and catalytic effects in one composite. These results demonstrate the important role of RGO to provide energy-level alignment, charge carrier diffusion, and help to generate plasmonic effect in the composite.

Palladium impregnated amine Co-condensed hexagonal mesoporous silica: a novel catalyst in tailoring suzuki and heck coupling reactions in base free condition - Das, Prangya Paramita; Prabhakaran, Vinod C.; Nanda, Samik; Sen, Debasis; Chowdhury, Biswajit (ChemistrySelect, 2019)
Palladium impregnated amine co-condensed hexagonal mesoporous silicas (HMS-X) were synthesized (sol-gel process) using different amines (Ethylene diamine and pyridine) of various concentrations (0.25 equiv. and 2 equiv.). The effect of amine concentration on the local structure of hexagonal mesoporous silica was studied. The catalyst shows excellent catalytic activity and high TOF towards both Suzuki and Heck coupling reactions without using any base in reaction medium with the solvent DMF:water in (1:1) ratio. The catalyst was reused and it was recyclable up to three cycle without any appreciable loss of activity and the kinetics of the reaction varying different parameters also have been studied thoroughly.
Keywords: Amine functionalized silica; Base free; Heck reaction; Palladium supported catalysts; Suzuki reaction

Pathways to defense metabolites and evading fruit bitterness in genus Solanum evolved through 2-oxoglutarate-dependent dioxygenases - Cardenas, Pablo D.; Sonawane, Prashant D.; Heinig, Uwe; Jozwiak, Adam; Panda, Sayantan; Abebie, Bekele; Kazachkova, Yana; Pliner, Margarita; Unger, Tamar; Wolf, Dalia; Ofner, Itai; Vilaprinyo, Ester; et al. (Nature Communications, 2019)
The genus Solanum comprises three food crops (potato, tomato, and eggplant), which are consumed on daily basis worldwide and also producers of notorious anti-nutritional steroidal glycoalkaloids (SGAs). Hydroxylated SGAs (i.e. leptinines) serve as precursors for leptines that act as defenses against Colorado Potato Beetle (Leptinotarsa decemlineata Say), an important pest of potato worldwide. However, SGA hydroxylating enzymes remain unknown. Here, we discover that 2-OXOGLUTARATE-DEPENDENT-DIOXYGENASE (2-ODD) enzymes catalyze SGA-hydroxylation across various Solanum species. In contrast to cultivated potato, Solanum chacoense, a widespread wild potato species, has evolved a 2-ODD enzyme leading to the formation of leptinines. Furthermore, we find a related 2-ODD in tomato that catalyzes the hydroxylation of the bitter a-tomatine to hydroxytomatine, the first committed step in the chemical shift towards downstream ripening-associated non-bitter SGAs (e.g. esculeoside A). This 2-ODD enzyme prevents bitterness in ripe tomato fruit consumed today which otherwise would remain unpleasant in taste and more toxic.

Phase transfer ceria-supported nanocatalyst for nitrile hydration reaction - Gupta, Nikitra N.; Punekar, Amrin S.; Raj, Karthik Raja E. K.; Ghodekar, Medha M.; Patil, Vipul S.; Gopinath, Chinnakonda S.; Raja, Thirumalaiswamy (ACS Omega, 2019)
The present study elaborates the catalytic effect of rare-earth metal oxides (Sm2O3 and La2O3) over ceria as a support phase transfer catalyst. The synthesized catalysts have been subjected to different characterization techniques, such as field-emission scanning electron microscopy, high-resolution transmission electron microscopy, powder X-ray diffraction, N-2 adsorption-desorption (BET surface analysis), temperature-programmed desorption study (NH3/CO2-TPD), Fourier transform infrared, Raman analysis, and X-ray photoelectron spectroscopy to get better insights into the catalytic activity of the catalysts for hydration of nitrile.

pH-responsive “supra-amphiphilic” nanoparticles based on homoarginine polypeptides - Praveen, Korra; Das, Soumen; Dhaware, Vinita; Pandey, Bhawana; Mondal, Basudeb; Sengupta, Sayam (ACS Applied Bio Materials, 2019)
pH-responsive “supra-amphiphiles” based on double hydrophilic, positively charged block copolypeptides such as PEG-b-poly-l-lysine together with low molecular weight stimuli-sensitive partners that contain phosphate and carboxylate groups have been widely studied. In contrast, the other widely used cationic polypeptide poly-l-arginine whose cell-penetrating properties are well-known has been much less explored for the synthesis of supra-amphiphile-based nanomaterials. It is also known that the guanidine side chain of arginine binds to carboxylate anions with binding constants that are 2.5 times higher than the corresponding amines of poly-l-lysine. Here, we demonstrate the fabrication of pH-sensitive supra-amphiphilic nanoparticles by simple mixing of PEG2k-b-poly(homoarginine) block copolymer and carboxylic acid containing functional low molecular weight organic compounds. A high yielding three-step methodology was developed for the synthesis of ε-N,N′-di-Boc-l-homoarginine-α-N-carboxyanhydride which was polymerized using amine-terminated PEG (2000 MW) to yield 100% guanine-functionalized polypeptide (PEG2k-b-PHR30) with controlled molecular weights and low PDIs. Incubation of PEG2k-b-PHR30 with four different carboxylic acids (including dexamethasone a glucocorticoid receptor used in cancer therapy) in water leads to the formation of “supra-amphiphilic” nanoparticles (<200 nm size) due to the charge neutralization resulting from the strong interaction between the guanidine group and the carboxylate group. All these nanoparticles were able to encapsulate the hydrophobic dye Nile red with varying efficiency. Although these assemblies were stable at neutral pH, upon lowering the pH of the solution between 4 and 5, the protonation of the carboxylic acids leads to disassembly of these nanoparticles. The cytotoxicity of all four “supra-amphiphilic” nanoparticles varied depending on the carboxylic acid used for their fabrication. While the nanoparticle formed using dioctylbenzoic acid displayed 80% cell viability at concentration of 60 μg/mL, those formed with the steroid deoxycholic acid or dexamethasone showed only 40% cell viability at similar concentrations. Colocalization studies performed using epifluorescence microscopy demonstrate the successful uptake of intact dye-encapsulated nanoparticle inside the cell.

pi-Extended cis-configured unsynimetrical squaraine dyes for dye-sensitized solar cells: panchromatic response - Punitharasu, Vellimalai; Kavungathodi, Munavvar Fairoos Mele; Singh, Ambarish Kumar; Nithyanandhan, Jayaraj (ACS Applied Energy Materials, 2019)
{Light absorbing sensitizer is the heart of the third generation photovoltaic technologies such as dye sensitized solar cells. Despite possessing large extinction coefficients for the metal-free organic dyes, the light harvesting efficiency is limited with the narrow absorption 20 profile in either visible or NIR regions of the solar spectrum. Though monolayer formation of organic sensitizers on semiconducting metal oxide surface leads to dye-dye interaction that leads to broadening the absorption profile, the contribution of the aggregated state to the power conversion process is found out to be poor. Here, we have engineered far-red active pi-extended cis-configured unsymmetrical squaraine dyes with carboxylic acid and cycnoacetic acid as anchoring groups with controlled aggregation and panchromatic light absorption by including the steric and electronic factors. The presence of sp(3)-C (out-of-plane) and N-alkyl (in-plane) groups played an important role in modulating the assembly of the dyes on the TiO2 electrode; the cis-squaraine unit helps to extend the conjugation in the NIR region besides enhancing the visible transition and the incident photon-to-current conversion efficiency profile that showed the importance of anchoring groups for the panchromatic response. Dye PSQ10 showed solar-to electric conversion with an onset of 850 nm with the device performance of 7.0% (V-oc = 0.581 V, J(sc) = 17.06 mA/cm(2)
Keywords: cis-squaraine dyes; Dye aggregation; Dye-sensitized solar cells; extended far-red absorption; panchromatic response

Polyesteramide of neem oil and its blends as an active nanomaterial for tissue regeneration - Killi, Naresh; Pawar, Anil Tukaram; Gundloori, Rathna V. N. (ACS Applied Bio Materials, 2019)
Neem oil gained importance due to its antibacterial properties. Therefore, it is extensively being used for various applications. Oils can be polymerized as a polyesteramide to extend their utility as biomaterials. In our studies, we synthesized polyesteramide from neem oil and various compositions of blends were prepared with the drug, chlorohexidine digluconate (CH) to develop a nanomaterial for tissue regeneration. The studies such as cytotoxicity, biodegradable, antibacterial, in vitro drug release, in vivo wound healing, and histopathological studies were performed to identify their potential for tissue regeneration. In vivo wound healing studies of the nanofiber mats with and without CH recorded a faster healing rate as compared to the commercial cream (povidone–iodine). Most importantly, there was no requirement of repeated application of nanofiber mats during the treatment. The histopathology studies also suggested the re-epithelialization of the wounds. Hence, these nanomaterials are considered to be environmentally safe scaffolds for efficient tissue regeneration applications.

Population balance-enabled model for batch and continuous crystallization processes - Pandit, Ajinkya; Bhambure, Rahul; Ranade, Vivek V. (Chemical Engineering in the Pharmaceutical Industry, 2019)
Crystallization is a critical unit operation in manufacturing of various active pharmaceutical ingredients and drugs. Irrespective of the large-scale use of crystallization in pharmaceutical manufacturing industry, crystallization is still considered as an art. Recently, quality by design (QbD) is gaining industry acceptance as an approach toward development and commercialization of the pharmaceutical drug molecules. In QbD, the unit operations and the process are designed and controlled to deliver specified quality attributes consistently. The proposed chapter is motivated by the necessity of the prediction of crystallization events like onset of the crystallization, nucleation, and growth during crystallization of active pharmaceutical ingredients. The chapter demonstrates the integrated use of population balance modeling framework for developing a fundamental understanding of the kinetic aspects of crystallization and correlating the developed understanding for scale-up and design for the crystallization processes. Efforts are made to discuss the impact of various critical process parameters like metastable zone width, scale effects, and residence time on crystal size during batch and continuous modes with the help of couple of case studies. The presented model and approach will be useful for implementing QbD for crystallizers.

Population genetic and phytochemical dataset of Saraca asoca: a traditionally important medicinal tree - Hegde, Satisha; Pai, Sandeep Ramchandra; Bhagwat, Rasika M.; Sainia, Archana; Rathore, Poonam Kanwar; Jalalpure, Sunil Satyappa; Hegde, Harsha Vasudev; Sugunan, Attayoor Purushottaman; Gupta, Vidya S.; Kholkute, Sanjiva D.; Roy, Subarna (Data in Brief, 2019)
The data presented in this article is in support of the research paper “Genetic and phytochemical investigations for understanding population variability of the medicinally important tree Saraca asoca to help develop conservation strategies” Hegde et al., 2018. This article provides PCR based Inter-Simple Sequence Repeat (ISSR) and HPLC datasets of 106 individual samples of Saraca asoca collected from various geographical ranges of the Western Ghats of India. The ISSR data includes information on genetic diversity and images of population structures generated through amplified DNA products from samples of Saraca asoca leaf. Phytochemical data obtained from HPLC includes concentration (mg/g) of gallic acid (GA), catechin (CAT), and epicatechin (EPI). The data also presents information obtained from various statistical analysis viz. standard error of the mean values, distribution variables, prediction accuracy, and multiple logistic regression analysis.

Porosity switching in polymorphic porous organic cages with exceptional chemical stability - Bera, Saibal; Dey, Kaushik; Pal, Tapan K.; Halder, Arjun; Tothadi, Srinu; Karak, Suvendu; Addicoat, Matthew; Banerjee, Rahul (Angewandte Chemie-International Edition, 2019)
Porous solids that can be switched between different forms with distinct physical properties are appealing candidates for separation, catalysis, and host-guest chemistry. In this regard, porous organic cages (POCs) are of profound interest because of their solution-state accessibility. However, the application of POCs is limited by poor chemical stability. Synthesis of an exceptionally stable imine-linked (4+6) porous organic cage (TpOMe-CDA) is reported using 2,4,6-trimethoxy-1,3,5-triformyl benzene (TpOMe) as a precursor aldehyde. Introduction of the -OMe functional group to the aldehyde creates significant steric and hydrophobic characteristics in the environment around the imine bonds that protects the cage molecules from hydrolysis in the presence of acids or bases. The electronic effect of the -OMe group also plays an important role in enhancing the stability of the reported POCs. As a consequence, TpOMe-CDA reveals exceptional chemical stability in neutral, acidic and basic conditions, even in 12m NaOH. Interestingly, TpOMe-CDA exists in three different porous and non-porous polymorphic forms (, , and ) with respect to differences in crystallographic packing and the orientation of the flexible methoxy groups. All of the polymorphs retain their crystallinity even after treatment with acids and bases. All the polymorphs of TpOMe-CDA differ significantly in their properties as well as morphology and could be reversibly switched in the presence of an external stimulus.
Keywords: chemical stability; Morphology; organic cages; polymorphism; porosity switching

Pressure-induced phase transitions in germanium telluride: raman signatures of anharmonicity and oxidation - Pawbake, Amit; Bellin, Christophe; Paulatto, Lorenzo; Beneut, Keevin; Biscaras, Johan; Narayana, Chandrabhas; Late, Dattatray J.; Shukla, Abhay (Physical Review Letters, 2019)
Pressure-induced phase transitions in GeTe, a prototype phase change material, have been studied to date with diffraction which is not sensitive to anharmonicity-induced dynamical effects. GeTe is also prone to surface oxidation which may compromise surface sensitive measurements. These factors could be responsible for the lack of clarity about the phases and transitions intervening in the phase diagram of GeTe. We have used high-pressure Raman scattering and ab initio pseudopotential density functional calculations to unambiguously establish the high-pressure phase diagram and identify three phases up to 57 GPa, a low-pressure rhombohedral phase, an intermediate pressure cubic phase, and a high-pressure orthorhombic phase. We detect substantial broadening and softening of Raman modes at low pressure and identify the transition regions and possible intermediate phases.

Probing the effect of selenium substitution in kesterite-Cu2ZnSnS4 nanocrystals prepared by hot injection method - Pandharkar, Subhash; Rondiya, Sachin; Bhorde, Ajinkya; Nair, Shruthi; Aher, Rahul; Vairale, Priti; Waghmare, Ashish; Naik, Dhirsing; Waykar, Ravindra; Jadhav, Yogesh (Journal of Materials Science-Materials in Electronics, 2019)
In this paper, we report the effect of sulfur (S) substitution with selenium (Se) in CZTS nanocrystals prepared by hot injection method. The formation of kesterite-copper zinc tin sulfide (Cu2ZnSnS4, CZTS) and copper zinc tin selenide (Cu2ZnSnSe4, CZTSe) nanocrystals is confirmed by X-ray diffraction (XRD), Raman spectroscopy and transmission electron microscopy (TEM) analysis. The XRD, TEM and atomic force microscopy (AFM) analysis shows an overall increase in average crystallite size upon Se substitution. AFM images revealed an increase in root mean square surface roughness (S-q) and average surface roughness (S-a) when S in CZTS is replaced by Se. The substitution of S by Se in host CZTS narrows the optical band gap from 1.56 to 1.03 eV. The ultraviolet photoelectron spectroscopy (UPS) analysis shows shift in valence band and conduction band edge in CZTSe compared to CZTS. The photocurrent density measurement in synthesized CZTSe thin films is similar to 4 to 5 times higher than CZTS thin films. The obtained results show that CZTSe can be a promising candidate as absorber material in photovoltaic applications.

Process of fruit peel waste biorefinery: a case study of citrus waste biorefinery, its environmental impacts and recommendations - Joglekar S.N., , ,; Pathak, P. D.; Mandavgane, S. A.; Kulkarni, B. D. (Environmental Science and Pollution Research, 2019)
Fruit peels are a rich source of cellulose, hemicellulose, phenolic compounds, and terpenic compounds. Thus, they have the potential to be a novel renewable, sustainable, and low-cost raw material (source) for the production of several value-added products based on framework and concepts such as waste hierarchy that includes biofertilizers, dietary fiber, animal feed, industrial enzymes, substrate for the bioactive compounds production, synthesis of nanomaterials, and clean energy (from residual biomass). With a view of evaluating the environmental burden of biorefinery, a life cycle assessment (LCA) is performed for a representative citrus waste (CW) biorefinery. The functional unit used for LCA was set as 2500 kg of CW processed. The overall GWP was observed to be 937.3 kg CO2 equivalent per 2500 kg of CW processed. On further analysis of the environmental impact, it was found that different steps contributed significantly, as shown by the various environmental indicator values. Alternative advanced process intensification technologies like microwave and ultrasound-assisted steps replacing the conventional steps when implemented show considerable reduction in environmental indicator values. The variations in the contribution to environmental indicators should be considered during the design and process selection of biorefineries.

Protein α-amylase inhibitor from withania somnifera and its role in overall quality and nutritional value improvement of potato chips during processing - Kasar, S. S.; Giri, A. P.; Pawar, P. K.; Maheshwari, V. L. (Food and Bioprocess Technology, 2019)
Cold storage and processing increase the reducing sugar level in potato (Solanum tuberosum L.) which is responsible for browning and acrylamide formation that adversely affect sensory and nutrient quality of chips. Effect of α-amylase inhibitor from Withania somnifera (WSAI) treatment on the overall quality improvement of potato chips during processing was studied. WSAI treatment to potato slices at 200 ppm for 30 min was found to reduce browning (60%), residual amylase, and polyphenol oxidase activities (~ 40%) and reduce sugar level by 25%, respectively, over control. Color match analysis indicated an improvement in whiteness and brightness indices and a significant reduction in yellowness index of potato chips. The treatment proved to be superior over blanching and reduction in acrylamide generation during frying was which also observed in chips treated with it. Furthermore, our results were comparable to that of treatment with α-amylase inhibitor of Triticum aestivum and better than synthetic inhibitor, acarbose.
Keywords: Acrylamide; alpha-amylase inhibitor; Browning of potato; Reducing sugars; Sensory and nutrient quality

Proteins as nanocarriers to regulate parenteral delivery of tramadol - Agrawal, Shubhang; Patel, Pratikshkumar R.; Gundloori, Rathna Venkata Naga (ACS Omega, 2019)
Tramadol (Td) is a centrally acting opioid analgesic drug used for the treatment of moderate to severe pain. However, the half-life of Td is about 6-8 h, which is a major drawback. To increase the half-life of Td, it needs to be entrapped in a suitable substrate with the capability to release the drug for an extended period of time. Accordingly, in our studies, new protein blends in various compositions were prepared using hydrophilic (egg albumin) and hydrophobic (zein) proteins and fabricated them as nanoparticles with Td by the desolvation method. The prepared nanoparticles were characterized using analytical techniques. The morphology and diameter of the nanoparticles were determined by an environmental scanning electron microscope. The interactions between Td and proteins were confirmed by fluorescence spectroscopy, and the secondary structural changes were evaluated by circular dichroism. The hemolysis test and MTT assay indicated that the nanoparticles were nontoxic, and drug release studies showed an extended duration of release of Td for more than 48 h. The mechanism of the drug release followed the zero order. The overall studies inferred that these protein based nanoparticles have potential to release Td at a slow rate for an extended period of time. Further manipulation of the protein composition may regulate the duration of Td release for an effective therapy.

Puzzle of highly virulent Metarhizium anisopliae strains from Annona squamosa fields against Helicoverpa armigera - Pathan, Ejaj K.; Deshpande, Mukund V. (Journal of Basic Microbiology, 2019)
In our search for indigenous virulent strains of the entomopathogenic fungi, we observed that Metarhizium isolates from soils associated with Annona squamosa (custard apple) have higher virulence (>90% mortality of Helicoverpa armigera larvae at 1/10(th) spore concentration) than strains isolated from Solanum lycopersicum (tomato) fields. Proteomic analysis revealed two insecticidal cyclopeptides of A. squamosa origin in the M. anisopliae strains that led to higher virulence against H. armigera. Transcriptomic and genomic data indicated that M. anisopliae strains and A. squamosa had more than 20 genes in common, including those for cyclic hexapeptide synthase, non-ribosomal peptide synthetase, and plant cyclotide genes, which are involved in the biosynthesis of insecticidal cyclopeptides. These genes were absent in M. anisopliae strains isolated from the S. lycopersicum fields. Further, these strains can establish an endophytic relationship with A. squamosa suggesting that these rhizospheric strains originally could be endophytes, which were eventually released into the soil. Further, Metarhizium strains associated with Capsicum annuum (chili), Azadirachta indica (neem), and Carica papaya (papaya) - plants with insecticidal properties - also had higher virulence against H. armigera. Thus exploration of rhizospheres of plants producing insecticidal metabolites to isolate entomopathogenic fungi, per se, could be a viable strategy in agricultural for crop protection.
Keywords: Annona squamosa; Biocontrol; endophyte; entomopathogen; Helicoverpa armigera; horizontal gene transfer; insecticidal peptides; Metarhizium; natural transformation

Quantitative comparison of strategies to delay clogging in straight capillaries - Pal, S.; Kulkarni, A. A. (Chemical Engineering Science, 2019)
It is challenging to achieve non-stop flow of a liquid-solid suspension through small channels as it eventually leads to clogging. This paper presents a quantitative comparison of four different techniques for enhancement of solid handling processes in microchannels of two different diameters. These techniques include dosing of the inert gas phase, dosing of the inert and immiscible liquid phase, and changing the wall wettability and multi-point injection, which, in principle, individually follow different mechanisms to delay clogging. An antisolvent based method for precipitation of salt was used to generate solid particles during flow. Clogging time at various flow rates from all the methods was measured and analysed. Irrespective of the method of delaying clogging, the scaling law of clogging time as a function of residence time was seen to remain unchanged. Among these methods, dosing of an inert, immiscible liquid has been identified as the most effective and robust method to delay clogging while enhancing transport of particles in segmented flow.

Rapid and greener method for utilization of plaster of paris (POP) waste generated from biomedical samples - Navale, G.R.; Gohil, K.N.; Puppala, K.R.; Shinde, S.S.; Umbarkar, S.; Dharne, M.S. (International Journal of Environmental Science and Technology, 2019)
Plaster of Paris (POP) is one of the recalcitrant wastes generated from dentistry and orthopaedic materials used in healthcare sector. The current practice of disposal of POP waste-harbouring biomedical material by incineration is very critical and environmentally unfriendly. The eco-friendly and rapid disintegration of such biomedical-related POP waste was done by treating with ammonium bicarbonate solution (20% w/v ABC) to form non-hazardous products like ammonium sulphate and calcium carbonate in the form of sludge. The ammonium sulphate (NH4)2SO4 is generally used in agriculture as a chemical fertilizer and calcium carbonate (CaCO3) as an additive in construction sector making this process cost-effective and value addition. Interestingly, 20% ABC solution also had significant antibiofilm, antimicrobial activity against fungi, yeast and bacterial strains probably due to its high pH-driven osmotic effect. Therefore, 20% ABC solution finds dual eco-friendly application in disinfection of used POP, especially arising from biomedical waste from patients.
Keywords: Biomedical waste; Eco-friendly disintegration; Plaster of Paris waste

Regioselective one-pot synthesis of 3-fluoro-imidazo[1,2-a]pyridines from styrene - Said, Madhukar S.; Mishra, Ankita; Pandole, Satish; Nayak, Rashmi A.; Kumar, Pradeep; Gajbhiye, Jayant M. (Asian Journal of Organic Chemistry, 2019)
A one-pot synthesis of C-3 fluorinated imidazopyridines (F-IMPY) is reported under the additive-free conditions from commercially available styrene and 1-fluoropyridinium tetrafluoroborate as a fluorine source. The substrate styrene undergoes keto-bromination/condensation/fluorination transformation in three sequential steps to furnish F-IMPY. This one-pot synthesis method exhibits broad substrate scope and good functional group tolerance with a good yield (up to 82%).
Keywords: fluorination; imidazopyridines (F-IMPY); One-pot synthesis

Relativistic coupled-cluster investigation of parity (P) and time-reversal (T) symmetry violations in HgF - Talukdar, Kaushik; Nayak, Malaya K.; Vaval, Nayana; Pal, Sourav (Journal of Chemical Physics, 2019)
We employ the Z-vector method in the four-component relativistic coupled-cluster framework to calculate the parity (P) and time-reversal (T) symmetry violating scalar-pseudoscalar nucleus-electron interaction constant (W-s), the effective electric field (E-eff) experienced by the unpaired electron, and the nuclear magnetic quadrupole moment-electron interaction constant (W-M) in the open-shell ground electronic state of HgF. The molecular frame dipole moment and the magnetic hyperfine structure (HFS) constant of the molecule are also calculated at the same level of theory. The outcome of our study is that HgF has a high value of E-eff (115.9 GV/cm), W-s (266.4 kHz), and W-M (3.59 x 10(33) Hz/e cm(2)), which shows that it can be a possible candidate for the search of new physics beyond the standard model. Our results are in good agreement with the available literature values. Furthermore, we investigate the effect of the basis set and the virtual energy functions on the computed properties. The role of the high-energy virtual spinors is found to be significant in the calculation of the HFS constant and the P,T-odd interaction coefficients. Published under license by AIP Publishing.

Resolving the conformational dynamics of ErbB growth factor receptor dimers - Pawar, Aiswarya B.; Sengupta, Durba (Journal of Structural Biology, 2019)
The combinatorial dimerization of the ErbB growth factor receptors (ErbB(1) - ErbB(4)) are critical for their function. Here, we have characterized the conformational dynamics of ErbB transmembrane homo-dimers and hetero-dimers by using a coarse-grain simulation framework. All dimers, except ErbB (4-4) and ErbB(1-4), exhibit at least two conformations. The reported NMR structures correspond to one of these conformations, representing the N-terminal active state in ErbB(1-1) (RH2), ErbB(2-2) (RH1) and ErbB(4-4) (RH) homo-dimers and the LH dimer in ErbB(3-3) homo-dimer, validating the computational approach. Further, we predict a right-handed ErbB(4) dimer conformer that warrants experimental testing. The five hetero-dimers that have not yet been experimentally resolved display prominent right-handed dimers associating by the SmXXXSm motif. Our results provide insights into the constitutive signaling of ErbB(4) after cleavage of the extracellular region. The presence of the inactive-like dimer conformers leading to symmetric kinase domains gives clues on the autoinhibition of the receptor dimers. The dimer states characterized here represent an important step towards understanding the combinatorial cross associations in the ErbB family.
Keywords: Martini coarse-grained simulations; Membrane protein structure; Transmembrane dimer

Retraction: a highly concise and practical route to clavaminols, sphinganine and (+)-spisulosine via indium mediated allylation of α-hydrazino aldehyde and a theoretical insight into the stereochemical aspects of the reaction - Pandey, M.; Chowdhury, P. S.; Dutta, A. K.; Kumar, P.; Pal, S. (RSC Advances, 2019)
A conceptually different approach has been employed for the synthesis of 1,2-amino alcohols by proline-catalyzed α-amination of aldehyde and one-pot indium mediated allylation of the crude α-hydrazino aldehydes. DFT based quantum chemical calculations have been performed to obtain a quantitative explanation of the stereoselectivity of the reaction.

Retraction: organocatalytic stereoselective synthesis of passifloricin A (Retraction of Vol 10, Pg 1820, 2012) - Kumar, Pradeep; Pandey, Menaka; Gupta, Priti; Dhavale, Dilip D. (Organic & Biomolecular Chemistry, 2019)

Role of structural distortion in stabilizing electrosynthesized blue emitting phosphorene quantum dots - Valappil, Manila Ozhukil; Joshi, Krati; John, Lisa; Krishnamurthy, Sailaja; Jana, Bikash; Patra, Amitava; Pillai, Vijayamohanan K.; Alwarappan, Subbiah (Journal of Physical Chemistry Letters, 2019)
Luminescent phosphorene quantum dots (PQDs) have emerged as fascinating nanomaterials for potential applications in optoelectronics, catalysis, and sensing. Herein, we investigate the structural distortion of black phosphorus (BP) under an applied electric field to yield blue luminescent PQDs [average diameter 8 +/- 1.5 nm (N = 60)]. The electrosynthesized PQDs exhibit photoluminescence emission independent of excitation wavelength with 84% quantum efficiency. Structural distortion that occurred during the transformation of BP to PQDs is confirmed by results obtained during transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. Further, using first-principles-based density functional theory, calculations on oxygenated and nonoxygenated PQDs augment the experimental observations that an optimum oxygen content maintains the structural integrity of PQDs, above which the structural robustness of PQDs is drastically diminished.

Scope and mechanistic aspect of nickel-catalyzed alkenylation of benzothiazoles and related azoles with styryl bromides - Patel, Ulhas N.; Jagtap, Rahul A.; Punji, Benudhar (Organometallics, 2019)
Alkenylation of benzothiazoles and related azoles with alkenyl bromides is achieved employing the well-defined and air-stable nickel complexes, (bpy)NiBr2 and [Ni(bpy)(3)] [NiBr4], as catalysts. Numerous electronically distinct alkenyl bromides efficiently coupled with substituted benzothiazoles, oxazoles, and benzimidazoles under the catalytic conditions to afford 2-alkenylated azoles. An extensive mechanistic study of the alkenylation of benzothiazole using (bpy)NiBr2 highlights a single-electron transfer process for the reaction involving the two-step one-electron oxidative addition of alkenyl bromide. The substrate benzothiazole plays a significant and diverse role in the reaction, and C-H bond cleavage is reversible in nature. Detailed kinetic analysis and control reactivity studies are indicative of a Ni(I)/Ni(III) pathway for the alkenylation comprising the rate-influencing reductive elimination step.

Selective synthesis of secondary amines from nitriles by a user-friendly cobalt catalyst - Sharma, Dipesh M.; Punji, Benudhar (Advanced Synthesis & Catalysis, 2019)
Selective hydrogenation/reductive amination of nitriles to secondary amines catalyzed by an inexpensive and user-friendly cobalt complex, (Xantphos)CoCl2, is reported. The use of (Xantphos)CoCl2 and ammonia borane (NH3-BH3) combination affords the selective reduction of nitriles to symmetrical secondary amines, whereas the employment of (Xantphos)CoCl2 and dimethylamine borane (Me2NH-BH3) along with external amines produce unsymmetrical secondary amines and tertiary amines. The general applicability of this methodology is demonstrated by the synthesis of 43 symmetrical and unsymmetrical secondary and tertiary amines bearing diverse functionalities.

Self-assembly of Di-guanine peptide nucleic acid amphiphiles into fractal patterns - Abraham, Jancy N.; Pawar, Prabhakar; Kootteri, Dilna K. (ChemistrySelect, 2019)
Peptide nucleic acids (PNAs) amphiphiles have been reported to assemble into different nanostructures; however, there is immense untapped potential to control their supramolecular assemblies by altering their lipid chain. Here, we functionalized di-guanine PNA with various hydrophobic appendages, namely dodecyl, p-dodecylbenzoyl and pentadecyl phenol groups, to investigate the effect of aromatic linkers, long alkyl and alkoxyl substituents on hierarchical self-assembly of di-guanine PNA. Systematic electron microscopy and atomic force microscopy studies revealed that while all three derivatives of di-guanine-PNA formed nanospheres, only nanospheres of dodecylamide and pentadecyl phenol derivatives matured into nanorods, these later formed higher order fractal assemblies. Furthermore, we observed that inclusion of a positively charged lysine at the C-terminus prevented fractal assembly, possibly due to electrostatic repulsion between the head groups. Thus, the findings of the present work might guide rational design of PNA amphiphiles to obtain specific self-assembled morphology.
Keywords: Fractal pattern; Guanine; pentadecylphenol; Peptide nucleic acid; Self-assembly

Silk fibroin-sodium dodecyl sulfate gelation: molecular, structural, and rheological insights - Hirlekar, Swarali; Ray, Debes; Aswal, Vinod K.; Prabhune, Asmita; Nisal, Anuya; Ravindranathan, Sapna (Langmuir, 2019)
A gelling agent is necessary to accelerate sol to gel transition in an aqueous solution of silk fibroin (SF), which otherwise takes several days to complete. In this paper, we investigate the mechanism of gelation of Bornbyx mori SF by a model anionic surfactant, sodium dodecyl sulfate (SOS). Even though interactions between SDS and proteins have been extensively investigated, most of these studies have focused on globular proteins, which undergo denaturation. The interaction with a fibrous protein such as SF is different and results in an altered secondary structure leading to gelation. In this work, the concentration-dependent gelation process of the SF-SDS system is examined using rheology, SANS, FTIR, and NMR. We observed preferential binding of SDS to specific regions on the SF chain, which aids structural changes favoring beta-sheet formation. We propose a mechanism for the accelerated sol-gel transition in the SF-SDS system.

Size-controlled cobalt ferrite nanocrystals: magnetically separable reusable nanocatalysts for selective oxidation of styrene - Jeyavani, Vijayakrishnan; Pawar, Sayali; Dadwal, Arun; Joy, Pattayil Alias; Mukherjee, Shatabdi Porel (ChemistrySelect, 2019)
Superparamagnetic cobalt ferrite (CFO) nanocrystals (NCs) with sizes similar to 6 nm and similar to 4 nm were synthesized using a facile solvothermal method using fatty acids, lauric acid and stearic acid, as the capping agents. The synthesized nanocrystals were well characterized by XRD, FT-IR, XPS, SEM and TEM. The formation mechanism was explored and it was shown that the fatty acid was actually chemisorbed as a carboxylate onto the surface of CFO NCs. The experimental results specify that the size and size distribution of the CFO NCs were highly dependent on the length of fatty acid hydrophobic chain. Corresponding changes of the magnetic properties were investigated by measuring magnetization as a function of field and temperature, which suggest that the CFO NCs were superparamagnetic in nature. The catalytic properties for the oxidation of styrene in organic medium were examined by using the synthesized CFO NCs with sizes similar to 6 nm and similar to 4 nm. The synthesized CFO NCs, well dispersible in organic media, were demonstrated to be highly catalytically active, reached 100% conversion of styrene in 12 h with similar to 77% and similar to 82% selectivity for styrene oxide respectively. The magnetic CFO nanocatalysts were easily separated and recovered from the reaction medium by an external magnet, and reused for several cycles without losing catalytic selectivity for styrene oxide.
Keywords: Cobalt ferrite; epoxidation; Fatty acids; magnetic properties; nanocrystals

Solvothermal growth of PbBi2Se4 nano-flowers: a material for humidity sensor and photodetector applications - Aher, Rahul; Bhorde, Ajinkya; Nair, Shruthi; Borate, Haribhau; Pandharkar, Subhash; Naik, Dhirsing; Vairale, Priti; Karpe, Smita; Late, Dattatray; Prasad, Mohit; Jadkar, Sandesh (Physica Status Solidi A-Applications and Materials Science, 2019)
In the present work, lead bismuth selenide (PbBi2Se4) nano-flowers are synthesized by using a simple solvothermal method. Humidity sensor and photodetector based on PbBi2Se4 nano-flowers are fabricated on indium tin oxide (ITO) substrates and their sensing properties are investigated. Formation of PbBi2Se4 is confirmed by XRD, EDS, and XPS whereas formation of nano-flowers is confirmed by SEM and TEM analysis. XRD analysis reveals the hexagonal crystal structure of PbBi2Se4 phase with a = b = 4.22 angstrom, and c= 17.42 angstrom. The surface morphology of PbBi2Se4 clearly shows the formation of well-organized flower-like nanostructures which closely resembles the shape of Dahlia. The elemental mapping of chemical constituents obtained from SEM-EDS analysis shows uniform distribution of chemical constituents for the Pb, Bi, and Se in PbBi2Se4 nano-flowers. The PbBi2Se4 nano-flowers based humidity sensor has a typical response time of approximate to 65s and recovery time of approximate to 75 s. In case of PbBi2Se4 nano-flowers-based photodetector, the response and recovery time are observed approximate to 121 and approximate to 123 s, respectively, under visible light illumination with photoresponsivity (5 x 10(-6)), photosensitivity (2.16%), and quantum efficiency (1.5 x 10(4)). The obtained results demonstrate the potential applications of solvothermally grown PbBi2Se4 nano-flowers-based devices for humidity sensors and photodetectors. The ease of the present work is to develop novel material to obtain device quality humidity sensors and photodetectors.
Keywords: humidity sensor; PbBi2Se4; photodetector; XPS; XRD

Special issue: membrane and receptor dynamics - Prakash, Shikha; Sengupta, Durba (Journal of Membrane Biology, 2019)

Stereoselective construction of deoxy-cruciferane alkaloids by NHC-catalyzed intramolecular annulation of homoenolate with quinazolinone - Ahire, Milind M.; Pol, Mahesh D.; Kavale, Dattatry S; Gonnade, Rajesh G.; Mhaske, Santosh B. (Organic & Biomolecular Chemistry, 2019)
Chiral N-heterocyclic carbene (NHC)-catalyzed intramolecular [3 + 2] annulation of enals with an unactivated imine moiety of quinazolinone via formal homoenolate cycloaddition has been demonstrated. It is an excellent approach for stereoselective syntheses of deoxy-cruciferane alkaloids comprising a biologically important pyrroloindoline scaffold. Notably, this is the first report on the NHC-catalyzed asymmetric intramolecular homoenolate annulation with cyclic N-acyl amidine.

Studies toward the total synthesis of parvifolals A/B: an intramolecular o-quinone methide [4 + 2]-cycloaddition to construct the central tetracyclic core - Paymode, D. J.; Ramana, C. V. (ACS Omega, 2019)
Two different approaches funded upon the intramolecular [4 + 2]-cycloaddition of in situ generated o-quinone methides have been explored to construct the central tetracyclic core of parvifolals A/B. At the outset, a cross-pinacol coupling of 2-formyl tri-O-methyl resveratrol with 4-methoxysalicylaldehyde followed by acid treatment was found to provide the desired tetracyclic core with an internal olefin. The requisite pendant aryl group has been introduced by a Pd-catalyzed direct coupling of corresponding diazonium salt.

Superfluous glutamine synthetase activity in Chinese Hamster Ovary cells selected under glutamine limitation is growth limiting in glutamine-replete conditions and can be inhibited by serine - Maralingannavar, Vishwanathgouda; Parmar, Dharmeshkumar; Panchagnula, Venkateswarlu; Gadgil, Mugdha (Biotechnology Progress, 2019)
Passaging and expansion of animal cells in lean maintenance medium could result in periods of limitation of some nutrients. Over time, such stresses could possibly result in selection of cells with metabolic changes and contribute to heterogeneity. Here, we investigate whether selection of Chinese Hamster Ovary (CHO) cells under glutamine limitation results in changes in growth under glutamine-replete conditions. In glutamine-limiting medium, compared to control cells passaged in glutamine-rich medium, the selected cells showed higher glutamine synthetase (GS) activity and attained a higher peak viable cell density (PVCD). Surprisingly, in glutamine-replete conditions, selected cells still showed a higher GS activity but a lower PVCD. We show that in glutamine-replete medium, PVCD of selected cells was restored on (a) inhibition of GS activity with methionine sulfoximine, (b) supplementation of aspartate-without affecting GS activity, and (c) supplementation of serine, which is reported to inhibit GS in vitro. Consistent with the reported effect of serine, inhibition of GS activity was observed upon serine supplementation along with reduced growth of cells under glutamine-limiting conditions. The latter observation is important for the design of glutamine-free culture medium and feed used for GS-CHO and GS-NS0. In summary, we show that CHO cells selected under glutamine limitation have superfluous GS activity in glutamine-replete medium, which negatively affects their PVCD. This may be due to its effect on availability of aspartate which was the limiting nutrient for the growth of selected cells in glutamine-replete conditions.
Keywords: C-13 tracer analysis; CHO cells; glutamine limitation; Glutamine synthetase; GS-CHO; GS-NS0; selection under nutrient limitation; serine

Superior humidity sensor and photodetector of mesoporous ZnO nanosheets at room temperature - Gupta, Shobhnath P.; Pawbake, Amit S.; Sathe, Bhaskar R.; Late, Dattatray J.; Walke, Pravin S. (Sensors and Actuators B-Chemical, 2019)
Miniaturized sensor technology is vastly demanding multifunctional materials to fulfill many requirements simultaneously; instead of integrating various sensors into a single device. Efficient operation of these miniaturized sensors at room temperature is highly feasible and cost-effective. The humidity sensing and photodetection is precise merit of sensing in special usage like artificial skin. Sensitivity enhancement in both humidity and photodetection required the high surface area for adsorption as well as a high charge transfer mechanism. The two dimensional (2D) zinc oxide nanosheets (ZnO NS) is the ultimate structure for dimensionally confined transport properties owing to the specific surface atomic configuration that results in high sensitivity, low operating temperature, fast response and recovery, and improved selectivity. Furthermore, introducing porosity into 2D nanostructures has opened new opportunities to enhance the efficiency of sensors and detectors via increasing large surface area and tunable physical and chemical properties. Here we report preparation of mesoporous and highly crystalline 2D ZnO NS by a single step, template free, cost-effective chemical method. The structural and morphological characterizations of ZnO NS are carried out using XRD, FESEM, XPS, TEM respectively. The high-resolution TEM images emphasize sheet-like morphology with a thickness of around 18-22 nm. Further the mesoporous ZnO NS (MZNS) with the pore size between 5-10 nm are achieved by simple heat-treatment. XPS and PL study is confirming the oxygen deficiency in MZNS. The MZNS exhibits an excellent responsivity than PZNS with a fast response and rapid recovery time of 25 s and 5 s respectively along with good cyclic stability which is highly crucial for smart humidity sensor. Furthermore, it considerably enhances photo-sensor performance than pristine ZnO NS (PZNS) with (similar to)1 s response time as well as (similar to)1 s recovery time along with better stability. These promising results illustrate the great potential of MZNS for next-generation humidity sensors and photodetectors.
Keywords: humidity sensor; Mesoporous; nanosheets; Photo-detector

Sustained release insect repellent microcapsules using modified cellulose nanofibers (mCNF) as pickering emulsifier - Kadam, Sandip L.; Yadav, Prashant; Bhutkar, Siddhant; Patil, Vishal D.; Shukla, Parshuram G.; Shanmuganathan, Kadhiravan (Colloids and Surfaces A-Physicochemical and Engineering Aspects, 2019)
We report here an approach to encapsulate N, N-diethyl-3-methylbenzamide (DEET), an insect repellent, through interfacial polycondensation using modified cellulose nanofiber (CNF) as pickering emulsifier. We found that stearic acid functionalized CNF (mCNF) can be used to form stable pickering emulsions (oil-in-oil and water-in-oil), and further encapsulate DEET using interfacial polycondensation with very high encapsulation efficiency of about 98%. Another major advantage of this approach is that mCNF can act both as pickering emulsifier and also strengthen the barrier properties of microcapsules resulting in significant reduction in release rate of DEET. Interpretation of the release profiles using standard mathematical models proposed by Ritger-Peppas show a factor of three reduction in release rate constant for the microcapsules reinforced with mCNF.
Keywords: Cellulose nanofiber; Controlled release; Microcapsules; Nanocomposite; nanoparticle; Pickering emulsion

Synthesis and antimycobacterial evaluation of new 5-(1-benzyl-1H-1,2,3-triazol-4-yl)-4-methyl-2-arylthiazole derivatives - Shinde, Vikas; Mahulikar, Pramod; Mhaske, Pravin C.; Chakraborty, Shakti; Choudhari, Amit; Phalle, Siddharth; Choudhari, Prafulla; Sarkar, Dhiman (Medicinal Chemistry Research, 2019)
A new series of 5-(1-benzyl-1H-1,2,3-triazol-4-yl)-4-methyl-2-arylthiazole derivatives, 6a-w have been synthesized by click reaction of substituted benzylazide, 5a-d with 5-ethynyl-4-methyl-2-substituted phenylthiazole, 4a-f. The starting compounds 4-ethynyl-2-substituted phenylthiazole (4a-f) were synthesized from the corresponding thiazole aldehyde by using the Ohira-Bestmann reagent. The structure of the synthesized compounds was determined by spectral analysis. All the synthesized compounds were screened for their preliminary antitubercular activity against Mycobacterium tuberculosis H37Ra (MTB, ATCC 25177). Most of the synthesized compounds reported good activity against M. tuberculosis H37Ra strain with IC50 range of 0.58-8.23 mu g/mL. Compounds 6g and 6k reported good antitubercular activity with MIC90 values of 4.71 and 2.22 mu g/mL, respectively. Potential antimycobacterial activity suggested that these compounds could serve as good lead compounds for further optimization and development of a newer antitubercular candidate. [GRAPHICS] .
Keywords: 1; 2; 3-Triazole; Antitubercular activity; Molecular docking; Ohira-Bestmann reagent; Thiazole

Synthesis and characterization of zinc oxide nanoparticles by using polyol chemistry for their antimicrobial and antibiofilm activity - Mahamuni, P. P.; Patil, P. M.; Dhanavade, M. J.; Badiger, M. V.; Shadija, P. G.; Lokhande, A. C.; Bohara, R. A. (Biochemistry and Biophysics Reports, 2019)
The present investigation deals with facile polyol mediated synthesis and characterization of ZnO nanoparticles and their antimicrobial activities against pathogenic microorganisms. The synthesis process was carried out by refluxing zinc acetate precursor in diethylene glycol(DEG) and triethylene glycol(TEG) in the presence and in the absence of sodium acetate for 2 h and 3 h. All synthesized ZnO nanoparticles were characterized by X-ray diffraction (XRD), UV visible spectroscopy (UV), thermogravimetric analysis (TGA), fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy(FESEM), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX) technique. All nanoparticles showed different degree of antibacterial and antibiofilm activity against Gram-positive Staphylococcus aureus (NCIM 2654)and Gram-negative Proteus vulgaris (NCIM 2613). The antibacterial and antibiofilm activity was inversely proportional to the size of the synthesized ZnO nanoparticles. Among all prepared particles, ZnO nanoparticles with least size (~ 15 nm) prepared by refluxing zinc acetate dihydrate in diethylene glycol for 3 h exhibited remarkable antibacterial and antibiofilm activity which may serve as potential alternatives in biomedical application.

Synthesis, biological evaluation and molecular modeling studies of novel chromone/Aza-chromone fused α-aminophosphonates as Src kinase inhibitors - Bapat, Sanket; Viswanadh, N.; Mujahid, M.; Shirazi, Amir Nasrolahi; Tiwari, Rakesh; Parang, Keykavous; Karthikeyan, Muthukumarasamy; Muthukrishnan, M.; Vyas, Renu (Journal of Scientific and Industrial Research, 2019)
A series of novel chromone/aza-chromone fused α-aminophosphonate derivatives were synthesized in good yields using silica chloride as the catalyst. All the synthesized compounds were tested for their c-Src kinase inhibitory activity. Aza-chromone compound showed Src kinase inhibition with an IC50 value of 15.8 µM. The compounds were subjected to molecular docking and dynamics simulations to study the atomic level interactions with an unphosphorylated proto-oncogenic tyrosine protein kinase Src (PDB code 1Y57) as well as phosphorylated tyrosine protein kinase Src (PDB code 2H8H). Docking and molecular dynamic results revealed phosphorylated Src tyrosine kinase protein better results than unphosphorylated tyrosine Src kinase protein. Chemoinformatics study revealed the compounds had lead like properties. Machine learning (SVR) models were built to study the structure activity correlations. A CC of 0.835 was obtained when the SVR model was applied to the 17 synthesized compounds. It is envisaged that the work will provide guidelines for future drug design efforts for Src kinase inhibitors.

Synthesis, biological evaluation and molecular modeling studies of novel chromone/Aza-Chromone fused alpha-aminophosphonates as src kinase inhibitors - Bapat, S.; Viswanadh, N.; Mujahid, M.; Shirazi, A. N.; Tiwari, R. K.; Parang, K.; Karthikeyan, M.; Muthukrishnan, M.; Vyas, Renu (Journal of Scientific & Industrial Research, 2019)
A series of novel chromone/aza-chromone fused alpha-aminophosphonate derivatives were synthesized in good yields using silica chloride as the catalyst. All the synthesized compounds were tested for their c-Src kinase inhibitory activity. Aza-chromone compound showed Src kinase inhibition with an IC50 value of 15.8 mu M. The compounds were subjected to molecular docking and dynamics simulations to study the atomic level interactions with an unphosphorylated proto-oncogenic tyrosine protein kinase Src (PDB code 1Y57) as well as phosphorylated tyrosine protein kinase Src (PDB code 2H8H). Docking and molecular dynamic results revealed phosphorylated Src tyrosine kinase protein better results than unphosphorylated tyrosine Src kinase protein. Chemoinformatics study revealed the compounds had lead like properties. Machine learning (SVR) models were built to study the structure activity correlations. A CC of 0.835 was obtained when the SVR model was applied to the 17 synthesized compounds. It is envisaged that the work will provide guidelines for future drug design efforts for Src kinase inhibitors.

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 2-Aryl naphthoquinones by the cross-dehydrogenative coupling involving an NHC-catalyzed endo-stetter reaction - Ghosh, Arghya; Patra, Atanu; Mukherjee, Subrata; Biju, Akkattu T. (Journal of Organic Chemistry, 2019)
An N-heterocyclic carbene (NHC)-catalyzed intramolecular Stetter reaction proceeding via the endo-fashion was the key step for the transition-metal-free and mild cross-dehydrogenative coupling of 2-cinnamoyl benzal-dehydes allowing for the synthesis of 2-aryl naphthoquinones. In this transformation, the carbene generated from the triazolium salt using Na2CO3 catalyzes the intramolecular Stetter reaction, which was followed by air oxidation to reinstall the C-C double bond.

Synthesis of artemisinin derived glycoconjugates inspired by click chemistry - Goswami, Lakshmi; Paul, Sayantan; Kotammagari, Tharun K.; Bhattacharya, Asish K. (New Journal of Chemistry, 2019)
Herein we describe the synthesis of artemisinin based glycoconjugates (9a-i) through employing a Cu(i)-catalysed reaction between -propargylated dihydroartemisinin (7a) and azido sugars (8a-i), with moderate to excellent yields. Our synthesized artemisinin based glycoconjugates (9a-i) could prove to be an interesting class of bioactive molecules, suitable for the study of their various biological activities.

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 biphasic nanomaterials based on ZnO and SnO2: application towards photocatalytic degradation of acid red dye - Kudale, Ananada S.; Kamble, Santosh B.; Gore, Anil H.; Pisal, Mahesh M.; Salokhe, Anil T.; Kolekar, Govind B.; Helavi, Vasant B. (Nano-Structures & Nano-Objects, 2019)
Zn2SnO4/SnO2 and ZnO/SnO2 biphasic nanocatalysts have been synthesized by a facile solvothermal method using ethylene glycol (EG) as solvent in three different ways maintaining the pH of the solution at either 3 or 9 followed by calcination at 700 °C. The nanocatalysts are characterized by different techniques to investigate their structure, composition, morphology and optical properties. The XRD results indicate the formation of pristine biphasic composites. The UV-absorbance and photoluminescence spectra confirms the formation of biphasic composites as well as presence of large number of defects in the prepared nanocatalysts. The biphasic nanocomposites possess better photocatalytic activity towards the degradation of Acid Red-183 (AR-183) dye than pristine SnO2 and ZnO nanoparticles. This is mainly due to better charge separation, minimal recombination rate of charge carriers and defect-riched structures of nanocatalysts.

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 Raman spectroscopy and sensor applications of PtSe2 nanosheets synthesized by wet chemistry - Pawar, Mahendra S.; Late, Dattatray J. (Beilstein Journal of Nanotechnology, 2019)
We report on a wet chemistry method used to grow PtSe2 nanosheets followed by thermal annealing. The SEM and TEM analysis confirms the formation of PtSe2 nanosheets. Furthermore, XRD, Raman, XPS and SAED patterns were used to analyze the crystal structure and to confirm the formation of the PtSe2 phase. The temperature-dependent Raman spectroscopy investigations were carried out on PtSe2 nanosheets deposited on Si substrates in the temperature range 100-506 K. The shifts in Raman active E-g and A(1g) modes as a function of temperature were monitored. The temperature coefficient for both modes was calculated and was found to match well with the reported 2D transition metal dichalcogenides. A PtSe2 nanosheet-based sensor device was tested for its applicability as a humidity sensor and photodetector. The humidity sensor based on PtSe2 nanosheets showed an excellent recovery time of approximate to 5 s, indicating the great potential of PtSe2 for future sensor devices.
Keywords: nanosheets; PtSe2; Raman spectroscopy; Sensor; thermal effect

Terpene profiling, transcriptome analysis and characterization of cis–terpineol synthase from Ocimum - Anand, Atul; Jayaramaiah, Ramesha H.; Beedkar, Supriya D.; Dholakia, Bhushan B.; Lavhale, Santosh G.; Punekar, Sachin A.; Gade, Wasudeo N.; Thulasiram, Hirekodathakallu V.; Giri, Ashok P. (Physiology and Molecular Biology of Plants, 2019)
Ocimum species produces a varied mix of different metabolites that imparts immense medicinal properties. To explore this chemo-diversity, we initially carried out metabolite profiling of different tissues of five Ocimum species and identified the major terpenes. This analysis broadly classified these five Ocimum species into two distinct chemotypes namely, phenylpropanoid-rich and terpene-rich. In particular, -caryophyllene, myrcene, limonene, camphor, borneol and selinene were major terpenes present in these Ocimum species. Subsequently, transcriptomic analysis of pooled RNA samples from different tissues of Ocimum gratissimum, O. tenuiflorum and O. kilimandscharicum identified 38 unique transcripts of terpene synthase (TPS) gene family. Full-length gene cloning, followed by sequencing and phylogenetic analysis of three TPS transcripts were carried out along with their expression in various tissues. Terpenoid metabolite and expression profiling of candidate TPS genes in various tissues of Ocimum species revealed spatial variances. Further, putative TPS contig 19414 (TPS1) was selected to corroborate its role in terpene biosynthesis. Agrobacterium-mediated transient over-expression assay of TPS1 in the leaves of O. kilimandscharicum and subsequent metabolic and gene expression analyses indicated it as a cis–terpineol synthase. Overall, present study provided deeper understanding of terpene diversity in Ocimum species and might help in the enhancement of their terpene content through advanced biotechnological approaches.
Keywords: Agro-infiltration assay; Metabolite profiling; Ocimum; Terpene synthase; Terpenes; Transcriptome

TiCl4-n-Bu3N-mediated cascade annulation of ketones with alpha-ketoesters: a facile synthesis of highly substituted fused gamma-alkylidene-butenolides - Palange, Megha N.; Gonnade, Rajesh G.; Kontham, Ravindar (Organic & Biomolecular Chemistry, 2019)
A facile protocol for the synthesis of highly substituted fused gamma-alkylidene butenolides using direct annulation of ketones with alpha-ketoesters, which proceeds through TiCl4-n-Bu3N mediated aldol addition followed by an intramolecular enol-lactonization/cyclization cascade, is reported. Diverse 6-5, 7-5 and 8-5 fused bicyclic gamma-ylidene butenolides and highly substituted monocyclic analogs related to biologically relevant natural products were prepared from readily accessible ketone and alpha-ketoester building blocks. The highly step-economic cascade nature, good substrate scope, easy access to complex products with good to excellent yields, gram-scalability, demonstration of synthetic utility, and unambiguous structural confirmation through X-ray crystallography analyses and analogy are the salient features of this work.

Trans-A(2)B(2) Zn(II) porphyrin dyes with various donor groups and their Co-sensitization for highly efficient dye-sensitized solar cells - Prakash, Kamal; Sudhakar, Vediappan; Sankar, Muniappan; Krishnamoorthy, Kothandam (Dyes and Pigments, 2019)
{We have designed and synthesized four donor-acceptor based trans-A(2)B(2) Zn(II) porphyrin dyes with various donor moieties and phenylcarboxy as acceptor group in three steps. Two strong electron-donating groups (carbazole, phenothiazine, pyrene and bisthiophene) were attached to porphyrin core to enhance the light absorption of dye molecules and phenylcarboxy acted as acceptor group on TiO2 surface. The alkyl chains present in KP-Zn-CBZ and KP-Zn-PTZ dyes are helpful to suppress the aggregation of dyes at the semiconductor surface. The synthetic route of these dyes was facile, high yield and three steps procedure which involved MacDonald condensation followed by hydrolysis and Zn insertion. The absorption and emission bands of all four dyes were broadened and red shifted due to the charge transfer from donor groups to porphyrin moiety. A wide range of power conversion efficiency was shown by dyes and the order of eta was as followed KP-Zn-PTZ (5.48%) > KP-Zn-PYR (3.38%) > KP-Zn-CBZ (2.64%) > KP-Zn-BTP (1.71%). Co-sensitization of porphyrin dyes with N719 dye promoted the complementary absorption in the visible region and put a restriction on dye aggregation also which improved the cell performance. Co-sensitized KP-Zn-PTZ with N719 dye showed the highest PCE efficiency up to 8.80% with a J(SC) = 17.4 mA cm(-2)

Transcriptomics analysis of propiconazole-treated Cochliobolus sativus reveals new putative azole targets in the plant pathogen - Somani, Deepika; Adhav, Ragini; Prashant, Ramya; Kadoo, Narendra Y. (Functional & Integrative Genomics, 2019)
Cochliobolus sativus (anamorph: Bipolaris sorokiniana) is a filamentous fungus from the class Dothideomycetes. It is a pathogen of cereals including wheat and barley, and causes foliar spot blotch, root rot, black point on grains, head blight, leaf blight, and seedling blight diseases. Annual yields of these economically important cereals are severely reduced due to this pathogen attack. Evolution of fungicide resistant pathogen strains, availability of a limited number of potent antifungal compounds, and their efficacy are the acute issues in field management of phytopathogenic fungi. Propiconazole is a widely used azole fungicide to control the disease in fields. The known targets of azoles are the demethylase enzymes involved in ergosterol biosynthesis. Nonetheless, azoles have multiple modes of action, some of which have not been explored yet. Identifying the off-target effects of fungicides by dissecting gene expression profiles in response to them can provide insights into their modes of action and possible mechanisms of fungicide resistance. Moreover it can also reveal additional targets for development of new fungicides. Hence, we analyzed the global gene expression profile of C. sativus on exposure to sub-lethal doses of propiconazole in a time series. The gene expression patterns were confirmed using quantitative reverse transcriptase PCR (qRT-PCR). This study revealed overexpression of target genes from the sterol biosynthesis pathway supporting the reported mode of resistance against azoles. In addition, some new potential targets have also been identified, which could be explored to develop new fungicides and plant protection strategies.
Keywords: Bipolaris sorokiniana; Cochliobolus sativus; Fungicide resistance; Propiconazole; RNA-seq; Transcriptomics analysis

Two-step sequence of acetalization and hydrogenation for synthesis of diesel fuel additives from furfural and diols. - Patil, Anil; Shinde, Suhas; Kamble, Sanjay; Rode, Chandrashekhar, V (Energy & Fuels, 2019)
Acetalization of diols with furfural and subsequent hydrogenation of acetal products provided potential fuel additives that could be blended into commercial diesel. Glycerol could be an interesting polyol for acetalization with furfural due to its low cost, and it is produced as a byproduct in very large amount in the process of biodiesel production. In this work, glycerol acetalization with furfural has been selected as a model reaction. Acetalization reaction was performed under neat conditions (solventless) with 1:1 molar ratio of furfural and glycerol at room temperature over various acid catalysts, including homogeneous and heterogeneous acids. Among several catalysts, Zr-Mont, a heterogeneous solid acid having controlled acidity, gave as high as 78% isolated yield of acetal products. Interestingly, acetal products can be isolated in pure form by performing extraction using cyclohexane that enables selective extraction of product, and unreacted glycerol and furfural were left in aqueous phase, which can be recycled. Further, to make fuel components from isolated acetal product of glycerol and furfural, hydrogenation was performed over a series of supported noble-metal catalysts under low H-2 pressure at room temperature. Among them, 5% Pd/C showed very high activity for ring hydrogenation that resulted in high yield of hydrogenation products. However, hydrogenated product contains free hydroxyl group that needs to be subsequently etherified or acetylated. Interestingly, etherified derivative was obtained in high yield compared to acetylated derivative. In addition, several other diols were treated with furfural and their products were subsequently hydrogenated over 5% Pd/C under very low H-2 pressure. The properties of resulting compounds were investigated so as to find most suitable candidates as additives to commercial diesel.

Unusual epimerization in styryllactones: synthesis of (-)-5-hydroxygoniothalamin, (-)-5-acetylgoniothalamin, and O-TBS-goniopypyrone - Kotammagari, Tharun K.; Paul, Sayantan; Bhattacharya, Asish K. (ACS Omega, 2019)
(-)-5-Hydroxygoniothalamin, (-)-5-acetylgoniothalamin, and (+)-5-hydroxygoniothalamin, isolated from the Goniothalamus genus, are synthesized from triacetyl-O-D-glucal by employing the Ferrier reaction, Mitsunobu reaction, and Jones oxidation as key steps. The synthetic procedure also yields the epimers of (-)-5-hydroxygoniothalamin and (+)-5-hydroxygoniothalamin employing acid-mediated transition-metal-free epimerization at C-5 of styryllactones. Further studies reveal that the epimerization is facilitated by the phenyl group present on the styryllactones. Also, depending on the dihydroxylation reaction conditions, various analogues of saturated styryllactones are synthesized utilizing oxa-Michael reaction conditions.

Use of Plackett-Burman design for enhanced phytase production by Williopsis saturnus NCIM 3298 for applications in animal feed and ethanol production - Pable, Anupama A.; Shah, Sarah; Kumar, V. Ravi; Khire, Jayant M. (3 Biotech, 2019)
Distiller-dried grain solid (DDGS), a co-product of alcohol production, contains cereal grain residues, proteins, and yeast metabolites, which make it suitable in poultry feeding. However, high phytate content of DDGS limits its applicability in poultry feed. In this study, Plackett-Burman design was used to improve cell-bound phytase production by Williopsis saturnus NCIM 3298, and we achieved an enzyme activity of 269IU/g of dry-wet biomass. The effect of this enhanced phytase-displaying yeast strain on hydrolysis of corn phytate and subsequently on ethanol production and DDGS quality was then investigated. Results of saccharification in the presence of phytase showed that reducing sugar content of liquefied mash increased by 11%, which subsequently improved the ethanol production by 18% (w/v) (p<0.01) compared with the control. Notably, phytase treatment decreased the phytate content of corn by 70% (p<0.01) compared with the control, thereby improving the availability of free phosphate in fermentation broth and DDGS. Thus, the results obtained suggest that the addition of W. saturnus NCIM 3298 strain has the potential of providing a new source of phytase that would be useful in the feed and ethanol industries.
Keywords: DDGS; Ethanol; Phytase; Plackett-Burman Design; Williopsis saturnus NCIM 3298

Vanadium-based highly active and selective catalysts for oxidative dehydrogenation of ethyl lactate to ethyl pyruvate - Doke, Dhananjay; Khomane, Sonali B.; Pandhare, Swati; Dongare, Mohan K.; Dumeignil, Franck; Umbarkar, Shubhangi (Applied Catalysis A: General, 2019)
<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;">Pyruvates are important intermediates for various bioactive and pharmaceutical molecules. Synthesis of pyruvates is challenging due to low selectivity, as the pyruvates are prone to polymerisation. In the present work, oxidative dehydrogenation of ethyl lactate to ethyl pyruvate was carried out under very mild conditions using vanadium-based homogeneous and heterogeneous catalysts in the presence of aqueous <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;">t<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;">-butyl hydroperoxide as an oxidant. Homogenous vanadium-based catalyst, VO(acac)<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;"> in acetonitrile solvent, gave excellent conversion (upto 83%) with 100% selectivity to ethyl pyruvate at room temperature. However, the heterogeneous catalyst, V<span style="font-size: 13.5px; line-height: 0; position: relative; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">2<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">O<span style="font-size: 13.5px; line-height: 0; position: relative; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">5<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;"> exhibited very high activity for oxidative dehydrogenation of ethyl lactate only at higher temperature (80 °C). At higher temperature, significant TBHP decomposition was observed if all TBHP was added in one lot. In case of ethyl lactate dehydrogenation using V<span style="font-size: 13.5px; line-height: 0; position: relative; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">2<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">O<span style="font-size: 13.5px; line-height: 0; position: relative; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">5<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;"> catalyst at 80 °C with two equivalents TBHP, 60% ethyl lactate conversion with 100% TBHP conversions were observed after 5 h when all TBHP was added initially in the reaction mixture. However, the ethyl lactate conversion at 80 °C, after 5 h increased to 72% when the same amount of TBHP was added batch wise over a period of 4 h, indicating improved conversion of TBHP to ethyl pyruvate. The heterogeneous catalyst, V<span style="font-size: 13.5px; line-height: 0; position: relative; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">2<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">O<span style="font-size: 13.5px; line-height: 0; position: relative; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">5<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;"> exhibited up to 98% conversion with 100% ethyl pyruvate selectivity at 80 °C after 10 h with 3 equivalent TBHP added batch wise. The homogeneous catalyst could not be reused while V<span style="font-size: 13.5px; line-height: 0; position: relative; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">2<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">O<span style="font-size: 13.5px; line-height: 0; position: relative; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">5<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;"> could be successfully recycled five times without catalytic performances loss. Oxidation proceeds by radical mechanism, as proved by experiment with radical scavenger.

Waste to wealth: a Case study of papaya peel - Pathak, Pranav D. (Waste and Biomass Valorization, 2019)
Papaya is a popular fruit consumed worldwide and well-known for its food and nutritional values. It is used in food industries for the production of jams, jellies, etc. As a result, these industries generate huge amounts of papaya peel (PP) and seeds as by-products, which are typically considered a waste, and thus discarded. However, our current investigation indicates that PP is a valuable source of bioactive compounds, which can be converted into many value-added products. In this article, we review the physicochemical composition and valorization of PP. PP can be utilized to obtain many value-added products by fermentation (e.g., biofuels, adsorbents, dietary fibers, biomedicine, biomaterials). The biorefinery approach for PP will definitely increase the value of this waste by producing an array of value-added products and achieving zero waste generation.
Keywords: Bioactive compounds; Biorefinery; Papaya peel; Valorization; Value-added products

Whole proteome analysis of GA(3) response at panicle stage in Grape (Vitis vinifera) CV. Thompson seedless - Maske, Smita; Upadhyay, Anuradha; Jogaiha, Satisha; Patil, Sucheta S.; Kadoo, Narendra Y.; Gupta, Vidya S. (Journal of Plant Growth Regulation, 2019)
Rachis elongation is a crucial process in producing good quality table grapes. In compact clustered grape variety like Thompson Seedless, treating the flower panicles with a mild dose of GA(3) results in loose clusters. We sprayed GA(3) on Thompson Seedless panicles immediately after emergence, and the samples were collected at 6 h and 24 h after application. Whole proteome analysis revealed significant differential expression of 530 proteins of the total 1288 expressed proteins at two time-points. GO term enrichment analysis revealed enrichment of GO terms related to translation, biosynthetic processes, and photosynthesis in GA(3)-treated samples. As the process of rachis elongation requires enhanced carbon metabolism and accumulation of sugars through the expansion of phloem area, we attribute this to the overexpression of several proteins involved in these processes. Significantly highly expressed proteins also belonged to biological processes like the generation of precursor metabolites, cellular protein metabolic processes, response to abiotic stimulus, and protein metabolic processes. This study might be the first of its kind in deciphering the contribution of a different group of proteins during rachis elongation as an early response to GA(3) application in seedless grapes. These results provide quality information on various physiological and biochemical changes occurring during early stages of rachis elongation.
Keywords: Bunch architecture; Gibberellic acid; Proteome; Rachis elongation; Vitis vinifera

Why the thin film form of a photocatalyst is better than the particulate form for direct solar-to-hydrogen conversion: a poor man's approach - Nalajala, Naresh; Patra, Kshirodra Kumar; Bharad, Pradnya A.; Gopinath, Chinnakonda S. (RSC Advances, 2019)
We demonstrated an easy method to improve the efficiency of photocatalysts by an order of magnitude by maximizing light absorption and charge carrier diffusion. Degussa titania (P25) and Pd/P25 composite photocatalyst thin films coated over regular glass plates were prepared and evaluated for solar hydrogen production in direct sunlight with aqueous methanol. It is worth noting that only UV light present in direct sunlight (similar to 4%) was absorbed by the catalysts. The hydrogen production activities of catalysts were compared for thin film and particulate forms at 1 and 25 mg levels. The hydrogen yield values suggested that 1 mg thin film form of Pd/P25 provided 11-12 times higher activity than 25 mg powder form. Comparable light absorption throughout the entire thickness of photocatalyst device and better contact of nanostructures that enabled the charge diffusion and charge utilization at redox sites are the reasons for high efficiency. While solar cells require charge carriers to diffuse through long distances of microns, they are utilized locally in an ensemble of particles (of nanometres) for hydrogen generation in photocatalyst thin films; this concept was used effectively in the present work.

2-D to 3-D conversion of WO3 nanostructures using structure directing agent for enhanced NO2 gas sensing performance - Beknalkar, S. A.; Patil, V. L.; Harale, N. S.; Suryawanshi, M. P.; Patil, A. P.; Patil, V. B.; Kim, J. H.; Patil, P. S. (Sensors and Actuators A-Physical, 2020)
An exotic 3-D tungsten oxide (WO3) microflower was synthesized via low-cost and environmental-friendly hydrothermal strategy. The effect of structure-directing agent on the formation of 3-D microflowers from a 2-D nanosheets of WO3 and its gas sensing behavior are investigated. The assynthesized WO3 powder was used in morphological, structural and phase studies by X-ray diffraction (XRD), scanning electron microscopy (SEM), FT-Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The WO3 samples were found to be polycrystalline with monoclinic crystal structure. The SEM micrographs revealed the formation of 3-D microflowers made up of two-dimensional (2-D) multi-directional dendritic nanoplates. The potassium hydroxide (KOH) acts as a structure-directing agent in the formation of 3-D microflowers of WO3 sample. To further understand the formation of 3-D microflowers of WO3 sample, concentration-dependent experiments were carried out by varying KOH concentration and the formation mechanism was investigated. The synthesized WO3 microstructures were subjected to detailed gas sensing tests for different gases at an optimized temperature. A selective, sensitive gas response was obtained for WO3 gas sensor. The lower detection limit is about 1 ppm at 150 degrees C working temperature for an optimized WO3 gas sensor. The gas sensing results indicate that the 3-D microflower-like WO3 nanostructures are highly promising for applications as gas sensors. (C) 2020 Published by Elsevier B.V.
Keywords: Microflowers; NO2 detection; WO3

3 d transition metal-catalyzed hydrogenation of nitriles and alkynes - Sharma, Dipesh M.; Punji, Benudhar (Chemistry-An Asian Journal, 2020)
Selective hydrogenation of nitriles and alkynes is crucial considering the vast applications of reduced products in industries and in the synthesis of bioactive compounds. Particularly, the late 3d transition metal catalysts (manganese, iron, cobalt, nickel and copper) have shown promising activity for the hydrogenation of nitriles to primary amines, secondary amines and imines. Similarly, semihydrogenation of alkynes to E- and Z-alkenes by 3d metals is adequately successful both via the transfer hydrogenation and by using molecular hydrogen. The emergence of 3d transition metals in the selective synthesis of industrially relevant amines, imines and alkenes makes this protocol more attractive. Herein, we provide a concise overview on the late 3d transition metal-catalyzed hydrogenation of nitriles to amines and imines as well as semihydrogenation of alkynes to alkenes.
Keywords: 3d transition metal; Alkynes; Hydrogenation; nitriles; Semihydrogenation

Access to diverse germylenes and a six-membered dialane with a flexible beta-diketiminate - Pahar, Sanjukta; Swamy, V. S. V. S. N.; Das, Tamal; Gonnade, Rajesh G.; Vanka, Kumar; Sen, Sakya S. (Chemical Communications, 2020)
A nacnac-based tridentate ligand containing a picolyl group (L) was employed to isolate chlorogermylene (1). The reaction of1with another equivalent of GeCl2 center dot dioxane surprisingly gave pyridylpyrrolide-based chlorogermylene (2)viaC-N bond cleavage and C-C coupling, while with AlCl3, it afforded a transmetalated product,4. The reaction of L with AlH3 center dot NMe2Et led to an unusual cyclohexane type six-membered dialane heterocycle (5).

AIE emission of SDS capped diphenylanthracene nanoparticles for selective recognition and estimation of Al(3+)ion in aqueous medium based on enhancement effect and analytical application - Suryawanshi, Sonali B.; Deshmukh, Gunvant R.; Bodake, Anita J.; Patil, Shivajirao R. (Macromolecular Symposia, 2020)
The sodium dodecyl sulfate capped 9,10 Diphenylanthracene nanoparticles is prepared by using reprecipitation method. The average particle size of NPs obtained from DLS examination is 67 nm. The aqueous suspension of NPs exhibits red shifted aggregation induces enhanced emission. The zeta potential value-42.9 mV indicates stability of NPs and generation of expected negative surface charge over the NPs to attract and adsorb cations from the solution on the surface. The cation recognition test based on fluorescence shows that the presence of Al(3+)ion significantly enhances the fluorescence of NPs. Furthermore, the proposed system is successfully applied for the detection of Al(3+)ion from environmental water samples and Digene table available in the market. The advantage of developed analytical method is lower value of LOD and even in presence of interfering ion Mg(2+)the Al(3+)is estimated with no need of their separation prior to analysis.
Keywords: 10-Diphenyl anthracene nanoparticles; aggregation induced enhanced emission; Al(3+)detection; fluorescence enhancement; SDS capped 9

Amphiphilic mannose-6-phosphate glycopolypeptide-based bioactive and responsive self-assembled nanostructures for controlled and targeted lysosomal cargo delivery - Mondal, Basudeb; Pandey, Bhawana; Parekh, Nimisha; Panda, Sidharth; Dutta, Tahiti; Padhy, Abinash; Sen Gupta, Sayam (Biomaterials Science, 2020)
Receptors of carbohydrate mannose-6-phosphate (M6P) are overexpressed in specific cancer cells (such as breast cancer) and are also involved in the trafficking of mannose-6-phosphate labeled proteins exclusively onto lysosomes via cell surface M6P receptor (CI-MPR) mediated endocytosis. Herein, for the first time, mannose-6-phosphate glycopolypeptide ((M6P)GP)-based bioactive and stimuli-responsive nanocarriers are reported. They are selectively taken up via receptor-mediated endocytosis, and trafficked to lysosomes where they are subsequently degraded by pH or enzymes, leading to the release of the cargo inside the lysosomes. Two different amphiphilic M6P block copolymers (M6P)GP(15)-(PPO44)-P-A and (M6P)GP(15)-(PCL25)(2) were synthesized by click reaction of the alkyne end-functionalized (M6P)GP(15) with pH-responsive biocompatible azide end-functionalized acetal PPO and azide end-functionalized branched PCL, respectively. In water, the amphiphilic M6P-glycopolypeptide block copolymers self-assembled into micellar nanostructures, as was evidenced by DLS, TEM, AFM, and fluorescence spectroscopy techniques. These micellar systems were competent to encapsulate the hydrophobic dye rhodamine-B-octadecyl ester, which was used as the model drug. They were stable at physiological pH but were found to disassemble at acidic pH (for (M6P)GP(15)-(PPO44)-P-A) or in the presence of esterase (for (M6P)GP(15)-(PCL25)(2)). These (M6P)GP based micellar nanoparticles can selectively target lysosomes in cancerous cells such as MCF-7 and MDA-MB-231. Finally, we demonstrate the clathrin-mediated endocytic pathway of the native FL-(M6P)GP polymer and RBOE loaded (M6P)GP micellar-nanocarriers, and selective trafficking of MCF-7 and MDA-MB-231 breast cancer cell lysosomes, demonstrating their potential applicability toward receptor-mediated lysosomal cargo delivery.

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.

Anticancer potential of AgNPs synthesized using acinetobacter sp. and curcuma aromatica against HeLa cell lines: a comparative study - Nadhe, Shradhda B.; Tawre, Madhumita S.; Agrawal, Sonia; Chopade, Balu A.; Sarkar, Dhiman; Pardesi, Karishma (Journal of Trace Elements in Medicine and Biology, 2020)
Background: Biogenic nanoparticles are gaining attention due to their low toxicity and numerous biomedical applications. Present study aimed to compare the potential anticancer activity of two biogenic silver nanoparticles (bAgNPs and pAgNPs) against human cervical cancer cell lines (HeLa). Methods: bAgNPs were synthesized using Acinetobacter sp. whereas pAgNPs were synthesized using aqueous root extract of Curcuma aromatica. Effect of these nanoparticles on HeLa cells viability was studied using MTT assay and colony formation assay. Anticancer potential was determined using fluorescence microscopy and flow cytometry studies. Bio-compatibility studies were performed against peripheral blood mononuclear cells (PBMCs). Results: Both the nanoparticles showed 50 % viability of peripheral blood mononuclear cells (PBMCs) when used at high concentration (200 mu g/mL). IC50 for bAgNPs and pAgNPs against HeLa cells were 17.4 and 14 mu g/mL respectively. Colony formation ability of Hela cells was reduced on treatment with both nanoparticles. Acridine orange and ethidium bromide staining demonstrated that bAgNPs were cytostatic whereas pAgNPs were apoptotic. JC-1 dye staining revealed that the mitochondrial membrane potential was affected on treatment with pAgNPs while it remained unchanged on bAgNPs treatment. Flow cytometry confirmed cell cycle arrest in HeLa cells on treatment with nanoparticles further leading to apoptosis in case of pAgNPs. About 77 and 58 % HeLa cells were found in subG1 phase on treatment with bAgNPs and pAgNPs respectively. bAgNPs showed cytostatic effect on HeLa cells arresting the cell growth in subG1 phase, whereas, pAgNPs triggered death of HeLa cells through mitochondrial membrane potential impairment and apoptosis. Conclusion: Overall, bAgNPs and pAgNPs could be safe and showed potential to be used as anticancer nanoantibiotics against human cervical cancer cells.
Keywords: Acinetobacter sp.; AgNPs; Anticancer; Curcuma aromatica; HeLa cells; PBMCs

Bacterial biofilm formation using PCL/curcumin electrospun fibers and its potential use for biotechnological applications - Pompa-Monroy, Daniella Alejandra; Figueroa-Marchant, Paulina Guadalupe; Dastager, Syed G.; Thorat, Meghana Namdeo; Iglesias, Ana Leticia; Miranda-Soto, Valentin; Perez-Gonzalez, Graciela Lizeth; Villarreal-Gomez, Luis Jesus (Materials, 2020)
Electrospun nanofibers are used for many applications due to their large surface area, mechanical properties, and bioactivity. Bacterial biofilms are the cause of numerous problems in biomedical devices and in the food industry. On the other hand, these bacterial biofilms can produce interesting metabolites. Hence, the objective of this study is to evaluate the efficiency of poly (x190;- caprolactone)/Curcumin (PCL/CUR) nanofibers to promote bacterial biofilm formation. These scaffolds were characterized by scanning electron microscopy (SEM), which showed homogeneous fibers with diameters between 441-557 nm; thermogravimetric analysis and differential scanning calorimetry (TGA and DSC) demonstrated high temperature resilience with degradation temperatures over >350 degrees C; FTIR and H-1-NMR serve as evidence of CUR incorporation in the PCL fibers. PCL/CUR scaffolds successfully promoted the formation of Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa biofilms. These results will be valuable in the study of controlled harvesting of pathogenic biofilms as well as in metabolites production for biotechnological purposes.
Keywords: Bacteria; curcumin; electrospinning; Escherichia coli; Pseudomona aeruginosa; Staphylococcus aureus

Biofilm formation to inhibition: role of zinc oxide-based nanoparticles - Mahamuni-Badiger, Pranjali P.; Patil, Pooja M.; Badiger, Manohar V.; Patel, Pratikshkumar R.; Thorat-Gadgil, Bhagyashi S.; Pandit, Abhay; Bohara, Raghvendra A. (Materials Science & Engineering C-Materials for Biological Applications, 2020)
Zinc oxide nanoparticles have received much attention worldwide as they possess unique properties like varied morphology, large surface area to volume ratio, potent antibacterial activity, and biocompatibility. Biofilm contains homogenous or heterogeneous microorganisms that remain enclosed in a matrix of an extracellular polymeric substance on biotic or abiotic surfaces. Bacterial biofilm formed on medical devices such as central venous catheters, urinary catheters, prosthetic joints, cardiovascular implantable devices, dental implants, contact lenses, intrauterine contraceptive devices and breast implants cause persistent infections. Such biofilm-associated infections in medical implants cause serious problems for public health and affect the function of medical implants. So, there is an urgent need for the use of an antimicrobial agent that will inhibit biofilm, including such antibiotic-resistant bacterial strains as bacteria, to develop multiple drug-resistances resulting in failure of the antibiotic's action. The antimicrobial agent used should be ideal in terms of biocompatibility, antimicrobial activity, stability at different environmental conditions, with less sensitivity to the development of resistance towards micro-organisms, safe for in vivo and in vitro use, and remain non-hazardous to the environment, etc. The first objective of the review discusses the insights into the formation of biofilm on a medical device with the current strategies to inhibit. The second purpose is to review the recent progress in ZnO- based nanostructure including composites for antibacterial and anti-biofilm activities. This will offer a new opportunity for the application of Zinc oxide-based material in the prevention of biofilm on the medical devices.
Keywords: antibacterial activity; Antibiofilm agent; Biocompatibility; Biofilm; Nanocomposites; ZnO nanoparticles

Bioinspired synthesis of multifunctional silver nanoparticles for enhanced antimicrobial and catalytic applications with tailored SPR properties - Parit, S. B.; Karade, V. C.; Patil, R. B.; Pawar, V. N.; Dhavale, R. P.; Tawre, M.; Pardesi, K.; Jadhav, U. U.; Dawkar, V. V.; Tanpure, R. S.; Kim, J. H.; Jadhav, J. P.; et al. (Materials Today Chemistry, 2020)
In the developing nanotechnology world, numerous attempts have been made to prepare the nobel metallic nanoparticles (NPs), which can improve their applicability in diverse fields. In the present work, the biosynthesis of silver (Ag) NPs has been successfully achieved through the medicinal plant extract (PE) of G. resinifera and effectively used for the catalytic and antibacterial applications. The size dependant tuneable surface plasmon resonance (SPR) properties attained through altering precursor concentrations. The X-ray and selected area diffraction pattern for Ag NPs revealed the high crystalline nature of pure Ag NPs with dominant (111) phase. The high-resolution TEM images show the nonspherical shape of NPs shifting from spherical, hexagonal to triangular, with wide particle size distribution ranging from 13 to 44 nm. Accordingly, the dual-band SPR spectrum is situated in the UV-Vis spectra validating the non-spherical shape of Ag NPs. The functional group present on the Ag NPs surface was analysed by FT-IR confirms the capping and reducing ability of methanolic PE G. resinifera. Further, the mechanism of antimicrobial activity studied using electron microscope showed the morphological changes with destructed cell walls of E. coli NCIM 2931 and S. aureus NCIM 5021 cells, when they treated with Ag NPs. The Ag NPs were more effective against S. aureus and E. coli with MIC 128 mu g/ml as compared to P. aeruginosa NCIM 5029 with MIC 256 mu g/ml. Apart from this, the reduction of toxic organic pollutant 4-NP to 4-AP within 20 min reveals the excellent catalytic activity of Ag NPs with rate constant k = 15.69 s(-1). (C) 2020 Elsevier Ltd. All rights reserved.
Keywords: Ag NPs; Antibacterial; Catalytic activity; Gardenia resinifera; surface plasmon resonance

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] .

Bis(silanetellurone) with C-H center dot center dot center dot Te Interaction - Ghosh, Moushakhi; Panwaria, Prakash; Tothadi, Srinu; Das, Aloke; Khan, Shabana (Inorganic Chemistry, 2020)
Herein, we report the synthesis of a series of bis(silanechalcogenones) [Ch = Te (2), S (3), or Se (4)] using an N-heterocyclic silylene-based SiCSi pincer ligand (1). 2 is the first example of a bis(silanetellurone) derivative. The bonding patterns of 2-4 were extensively studied by natural bond orbital, quantum theory of atoms in molecules, and noncovalent interaction index analyses, and these exhibit weak C-H center dot center dot center dot Ch interaction. The analogous reaction of 1 with trimethyl N-oxide produced a novel bis(cyclosiloxane) derivative (5). All of the complexes are duly characterized by single-crystal X-ray diffraction studies, multinuclear nuclear magnetic resonance (H-1, C-13, and Si-29) spectroscopy, and high-resolution mass spectrometry.

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

Carbon quantum dots functionalized agarose gel matrix for in solution detection of nonylphenol - Singh, S.; Nigam, P.; Pednekar, A.; Mukherjee, S.; Mishra, A. (Environmental Technology, 2020)
Nonylphenol, an endocrine disrupter, is widely released to the aquatic environment, which is accumulative and extremely toxic to aquatic organisms. Here, we report a simple and cost-effective large-scale green synthesis of water-soluble highly fluorescent carbon quantum dots (CQDs) from marine biowaste (offshore washed algae) which gets quenched strongly in the presence of nonylphenol. These CQDs were around 20-40 nm in size and exhibit fluorescence constantly at 360 nm. The XRD profile depicted the interlayer spacing in the particle as 0.284 nm with a humped peak around 14 degrees showing the amorphous nature of the CQDs. FTIR spectra showed the stretching vibration of the hydroxyl groups (OH), asymmetric and symmetric stretching vibrations of the carboxylate anions (COO-). The fluorescence quantum yield of the CQDs is up to 68% and nonyl phenol detection limit is less than 0.1 µM. Furthermore, the CQDs were found to be stable at a wide pH range which makes it a suitable nonylphenol sensor for a variety of environmental samples. We functionalized these CQDs on an agarose gel matrix to develop a convenient sensor for the rapid detection of nonylphenol.
Keywords: Carbon quantum dots; endocrine disrupter; marine algae; nonylphenol; pollutant

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

Chapter 18 - Advances in agrochemical remediation using nanoparticles - Abin Sebastian; Ashwini Nangia; Majeti Narasimha Vara Prasad (Agrochemicals Detection, Treatment and Remediation, 2020)
Agrochemical pollution is a serious threat to environmental safety. Exposure to agrochemicals had deleterious health effects such as nervous system damage and cancer. Biological magnification of persistent agrochemicals also occurred. Hence, remediation approaches for agrochemical pollution must be a holistic approach, including environment and crop produces. The advent of nanotechnology helped to formulate highly efficient methods for the remediation of agrochemicals. High reactive surface area and very small packing space requirements made usage of nanoparticles as a popular agent in agrochemical remediation. Growing interests in surface-engineered nanoparticles promise complete removal of agrochemicals from the environment. Nanosorbents immobilized agrochemicals in the soil and helped microbial degradation of these compounds. However, many of the agrochemicals are persistent, and hence complete removal of these residues practice via photocatalysis. Photocatalytic degradation of persistent agrochemicals using bimetallic nanocomposites widely adopted. Large-scale environmental remediation of agrochemicals in soil, water, and agriculture products achieved via nanoparticles-based agrochemical cleaning systems such as thin-film fixed-bed reactors and nano-phytoremediation.
Keywords: agrochemical cleaning systems; nanosorbents; Pesticides; Photocatalysis; surface engineering

Characterisation of hyper tolerant Bacillus firmus L-148 for arsenic oxidation - Bagade, Aditi; Nandre, Vinod; Paul, Dhiraj; Patil, Yugendra; Sharma, Nisha; Giri, Ashok; Kodam, Kisan (Environmental Pollution, 2020)
Groundwater arsenic pollution causes millions of deaths worldwide. Long term natural and anthropogenic activities have increased arsenic levels in groundwater causing higher threats of arsenic exposure. Arsenic hyper-tolerant Firmicute Bacillus firmus L-148 was isolated from arsenic limiting Lonar lake soil, which tolerated more than 3 M arsenic and could oxidize 75 mM arsenite [As(III)] in 14 days. It oxidized As(III) in presence of heavy metals and had unusual pH optima at 9.2. B. firmus L-148 was studied at the biochemical, protein, genomic and transcript level for understanding its arsenic oxidizing machinery. The proteomic and transcript analysis exhibited the presence of ars and aio operon and supported the inducible nature of ars operon. Robust, hyper-tolerant, fast As(III) oxidizing, least nutrient requiring and multi-metal resistance qualities of the strain were used in microcosm studies for bioremediation. Artificial groundwater mimicking microcosm with 75 mM As(III) was developed. Modulation of carbon source, iron and multi metals affected growth and As(III) oxidation rate. The As(III) oxidation was recorded to be 77% in 15 days in presence of sodium acetate and Fe ions. This microcosm study can be explored for bioremediation of arsenic contaminated water and followed by precipitation using other methods. (C) 2020 Elsevier Ltd. All rights reserved.
Keywords: Arsenic hyper-tolerance; Lonar lake; Microcosm studies; Multi-metal resistance; Next generation sequencing

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

Chemoselective ring closure of 4-(3-Methyl-2-oxo-2,5-dihydro-1H-pyrrol-1-yl)butanal leading to pandalizine A - Yadav, Mahesh B.; Pandhade, Kailas R.; Argade, Narshinha P. (ACS Omega, 2020)
Starting from methylmaleic anhydride, a facile total synthesis of pandalizine A alkaloid is described via the regioselective reduction of methylmaleimide and acid-catalyzed enolization of 4-(3-methyl-2-oxo-2,5-dihydro-1H-pyrrol-1-yl)butanal followed by chemoselective intramolecular dehydrative cyclization as the key steps. It is noteworthy that the analogous model system with an additional beta-methyl group followed an alternative chemoselective intermolecular aldol condensation pathway.

CO2 hydrogenation to formate by palladium nanoparticles supported on N-incorporated periodic mesoporous organosilica - Betsy, K. J.; Lazar, Anish; Pavithran, Anjuna; Vinod, C. P. (ACS Sustainable Chemistry & Engineering, 2020)
Development of a heterogeneous catalyst capable of selective transformation of CO2 to valuable products still remains a challenge. In this article, we account for the surfactant-directed synthesis of a new framework-incorporated nitrogen-containing periodic mesoporous organosilica nanosphere (NPMO). A thoroughly characterized N-incorporated hybrid PMO was utilized as a platform for stabilizing well-dispersed and easily accessible Pd nanoparticles (Pd-NPMO) without using any stabilizing agents or expensive dendrimers. Further, this bifunctional hybrid catalyst has been demonstrated to heterogeneously catalyze aqueous phase CO2 hydrogenation (CO2/H-2 ratio 1:3) for the direct synthesis of formate under 4 MPa pressure and at 100 degrees C. To validate the superior performance of the Pd-NPMO catalyst, we compared the activity with Pd-SBA-15 catalysts, and the results showed a 10-fold increase in turnover frequency of 108 h(-1) using Pd on NPMO which envisaged the crucial role of nitrogen sites in this catalyst to boost the CO2 valorization to formate.
Keywords: CO2 hydrogenation; Formic acid synthesis; Hybrid silica; Pd nanoparticles; PMO

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

Comparative proteomics unravels the differences in salt stress response of own-rooted and 110R-grafted thompson seedless grapevines - Patil, Sucheta; Shinde, Manisha; Prashant, Ramya; Kadoo, Narendra; Upadhyay, Anuradha; Gupta, Vidya (Journal of Proteome Research, 2020)
Thompson Seedless, a commonly grown table grape variety, is sensitive to salinity when grown on its own roots, and therefore, it is frequently grafted onto salinity-tolerant wild grapevine rootstocks. Rising soil salinity is a growing concern in irrigated agricultural systems. The accumulation of salts near the root zone severely hampers plant growth, leading to a decrease in the productive lifespan of grapevine and causing heavy yield losses to the farmer. In the present study, we investigated the differences in response to salinity between own-rooted Thompson Seedless (TSOR) and 110R-grafted Thompson Seedless (TS110R) grapevines, wherein 110R is reported to be a salt-tolerant rootstock. The grapevines were subjected to salt stress by treating them with a 150 mM NaCl solution. The stress-induced changes in protein abundance were investigated using a label-free shotgun proteomics approach at three time points viz. 6 h, 48 h, and 7 days of salt treatment. A total of 2793 proteins were identified, of which 246 were differentially abundant at various time-points in TSOR and TS110R vines. The abundance of proteins involved in several biological processes such as photosynthesis, amino acid metabolism, translation, chlorophyll biosynthesis, and generation of precursor metabolites was significantly affected by salt stress in both the vines but at different stages of stress. The results revealed that TSOR vines responded fervently to salt stress, while TS110R vines adopted a preventive approach. The findings of this study add to the knowledge of salinity response in woody and grafted plants and hence open the scope for further studies on salt stress-specific differences induced by grafting.
Keywords: 110R rootstock; gene ontology; grafting; label-free proteomics; salt stress; Vitis vinifera

Conjunctive photoluminescence enhancement through plasmonic and photonic band-gap pathways in a chiral self-assembled system - Baral, Marlin; Krishna Prasad, S.; Bhat, Sachin A.; Nayak, Rashmi A.; Yelamaggad, C. V. (ChemPhotoChem, 2020)
We describe two parallel pathways for enhancing the intrinsic photoluminescence of an organic emitter dispersed in a liquid crystal (LC) medium. The pathways have independent origins: (i) Metal enhanced fluorescence (MEF) incorporating gold nanoparticles having an organic shell of pro-mesogenic cholesterol esters; and (ii) Matching the photonic band gap (PBG) due to the helical structure in a self-assembled chiral system with the excitation wavelength. This unprecedented combination of both pathways achieves a level of photoluminescence exceeding the sum of the contribution from the individual methods. This conjunctive protocol results in an overall enhancement by a factor of 37 between the emitter dispersed in a non-chiral LC and that appealing to both MEF and PBG pathways. Circular polarized luminescence measurements also show that this protocol helps in effective discrimination of chiral light achieving a large dissymmetry factor whose magnitude (+0.33) is comparable to the highest recorded to date. Electric field switching between two states is also shown to result in appreciable fluorescence modulation. Being generic in nature the protocol employed can be adapted to a variety of situations with the large magnitude as well the modulation level suitable for applications such as biosensors, various analyte detection, and other photonic devices.
Keywords: chirality; circularly polarized luminescence; liquid crystals; photonic band-gap; plasmonics

Construction of unique SCF3-containing building blocks via allylic alkylation of Morita-Baylis-Hillman adducts - Halder, Priyanka; Pol, Mahesh D.; Ahire, Milind M.; Mhaske, Santosh B. (Organic & Biomolecular Chemistry, 2020)
Lewis base-catalyzed allylic alkylation of Morita-Baylis-Hillman adducts with alpha-SCF3 ketones has been demonstrated. The developed strategy provides efficient access to a series of highly functionalized scaffolds featuring trifluoromethanesufinyl motif on a stereogenic carbon.

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

Copper-catalyzed direct arylation of indoles and related (hetero)arenes: a ligandless and solvent-free approach - Pandey, Dilip K.; Shabade, Anand B.; Punji, Benudhar (Advanced Synthesis & Catalysis, 2020)
A ligandless and solvent-free copper-catalyzed method for the regioselective C-H bond arylation of indoles and related heteroarenes is reported. The use of CuCl efficiently catalyzes the direct coupling of diverse heteroarenes with aryl iodides via chelation-assistance. This reaction could tolerate sensitive and structurally diverse functionalities, including halides, ethers, thioethers, amines, indolyl, pyrrolyl and carbazolyl groups. The directing group, 2-pyridinyl can be smoothly removed to generate C-2 arylated free-NH indoles, and the arylated indoles can further be functionalized into Tryptamine derivatives. Preliminary mechanistic study revealed a radical pathway for the arylation reaction.
Keywords: Arylation; C-H activation; Chelation-assistance; Copper; Indole; Solvent-free

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

Cyanosilylation by compounds with main-group elements: an odyssey - Pahar, Sanjukta; Kundu, Gargi; Sen, Sakya S. (ACS Omega, 2020)
The past few decades have seen remarkable headways in the structural and reaction chemistry of compounds with heavier main-group elements. In recent years, there is an ongoing effort to derive catalytic chemistry involving main-group compounds, driven by their lower costs and higher terrestrial abundances. Here, a survey on the state-of-the-art in the development of cyanosilylation methodology by compounds with heavier main-group elements has been given. Once dominated by transition metals, the field has matured to embrace the majority of the main-group elements including aluminum, silicon, and calcium. Of particular focus will be how the mechanism of cyanosilylation involving compounds with main-group elements differs from those of transition metals.

Design, expression, and evaluation of novel multiepitope chimeric antigen of Wuchereria bancrofti for the diagnosis of lymphatic filariasis - A structure-based strategy - Yasin, Nazeer; Laxmanappa, Hoti Sugerappa; Muddapur, Uday M.; Cheruvathur, Jennifer; Prakash, S. M. Uday; Thulasiram, Hirekodathakallu Venkataramaiah (International Immunopharmacology, 2020)
The Global Program for Elimination Lymphatic Filariasis (GPELF) is in an advanced stage and requires tools for diagnosing infection, assessing transmission and certification. This study was aimed at developing an antibody-based assay using a chiemric antigen containing multi-B-cell epitopes from antigens highly expressed in different stages of Wuchereria bancrofti to detect LF infection and its transmission. The antigen was express cloned and two indirect ELISA based (IgG1 & IgG4 based) antibody assays were developed using the recombinant antigen. The chimeric antigen displayed 1 and 3-fold reactivity with IgG1 and IgG4 antibodies, respectively in microfilaraial (mf) positive sera when compared to that in sera samples of Non-endemic normal sera (NEN) (O.D, 0.13 +/- 0.20 and 0.18 +/- 0.07), thus differentiating infected from uninfected individuals. In IgG1 and IgG4 antibody assays, the multiepitope antigen also showed reactivity (O.D, 0.27 +/- 0.18 and 0.16 +/- 0.03) in a small proportion (18 and 30, respectively out of 156) endemic normal individuals and in IgG1 antibody in a few (4) chronic patients (CP). The antigen did not react with IgG1 or IgG4 antibodies in the sera samples of malaria, scrub typhus, dengue, hookworm, and roundworm helminth cases (0.139 +/- 0.018, 0.144 +/- 0.007 0.17804 +/- 0.007 and 0.162 +/- 0.006), thus showing its high specificity. The sensitivity (%) and specificity (%) of the multi-epitope antigen-based IgG1 and IgG4 antibody assays are 100, 98.1 and 100, 99.52, respectively. Thus, the recombinant multiepitope antigen appears to have good potential in detecting active LF infection and in assessing its transmission in endemic communities.
Keywords: Filariasis; Multi-epitope antigen; Serodiagnosis; Transmission

Development of a smart scaffold for sequential cancer chemotherapy and tissue engineering - Sengupta, Poulomi; Agrawal, Vinay; Bhagavatula L. V. Prasad (ACS Omega, 2020)
The fabrication of a dual-functional drug-containing porous polymeric scaffold by layer-by-layer surface modification involving citrate-stabilized gold nanoparticles and cisplatin molecules is being reported. These scaffolds were characterized by electron microscopy and X-ray photoelectron spectroscopy. The capability of the scaffolds to release hydrated cisplatin in a slow and sustained manner over two days is established. Most importantly, the scaffolds turn nontoxic and cell-friendly after drug release, thus allowing the noncancerous fibroblast cells to adhere and proliferate (from 5000 cells to 16,000 cells in 6 days), becoming a potential solution toward an effective drug-carrying scaffold for volume-filling applications. The scaffold-mediated cancer cell killing and fibroblast cell proliferation were confirmed by fluorescence microscopy imaging, flow cytometry, and cell proliferation assays. We surmise that such a dual-purpose (drug-delivery and volume-filler) scaffold could help avoid the multiple surgical interventions needed for tumor surgery and cosmetic corrections. To the best of our knowledge, this is the first example of scaffolds with such a dual functionality which gets manifested in a sequential manner.

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.

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

Discovery of potential multi-target-directed ligands by targeting host-specific SARS-CoV-2 structurally conserved main protease - Joshi, Rakesh S.; Jagdale, Shounak S.; Bansode, Sneha B.; Shankar, S. Shiva; Tellis, Meenakshi B.; Pandya, Vaibhav Kumar; Chugh, Anita; Giri, Ashok P.; Kulkarni, Mahesh J. (Journal of Biomolecular Structure & Dynamics, 2020)
Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) infection has resulted in the current COVID-19 pandemic. Worldwide this disease has infected over 2.5 million individuals with a mortality rate ranging from 5 to 10%. There are several efforts going on in the drug discovery to control the SARS-CoV-2 viral infection. The main protease (M-Pro) plays a critical role in viral replication and maturation, thus can serve as the primary drug target. To understand the structural evolution of M-Pro, we have performed phylogenetic and Sequence Similarity Network analysis, that depicted divergence of Coronaviridae M-Pro in five clusters specific to viral hosts. This clustering was corroborated with the comparison of M-Pro structures. Furthermore, it has been observed that backbone and binding site conformations are conserved despite variation in some of the residues. These attributes can be exploited to repurpose available viral protease inhibitors against SARS-CoV-2 M-Pro. In agreement with this, we performed screening of similar to 7100 molecules including active ingredients present in the Ayurvedic anti-tussive medicines, anti-viral phytochemicals and synthetic anti-virals against SARS-CoV-2 M-Pro as the primary target. We identified several natural molecules like delta-viniferin, myricitrin, taiwanhomoflavone A, lactucopicrin 15-oxalate, nympholide A, afzelin, biorobin, hesperidin and phyllaemblicin B that strongly binds to SARS-CoV-2 M-Pro. Intrestingly, these molecules also showed strong binding with other potential targets of SARS-CoV-2 infection like viral receptor human angiotensin-converting enzyme 2 (hACE-2) and RNA dependent RNA polymerase (RdRp). We anticipate that our approach for identification of multi-target-directed ligand will provide new avenues for drug discovery against SARS-CoV-2 infection. Communicated by Ramaswamy H. Sarma
Keywords: Coronavirus; COVID-19; hACE-2; MPro; multi-target-directed ligand; protease inhibitor; RdRp; SARS-CoV-2 virus

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

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

Early metastable assembly during the stress-induced formation of worm-like amyloid fibrils of nucleic acid binding domains of TDP-43 - Pillai, Meenakshi; Jha, Santosh Kumar (Biochemistry, 2020)
TDP-43 protein travels between the cytosol and the nucleus to perform its nucleic acid binding functions through its two tandem RNA recognition motif domains (TDP-43(tRRM)). When exposed to various environmental stresses, it forms abnormal aggregates in the cytosol of neurons, which are the hallmarks of amyotrophic lateral sclerosis and other TDP-43 proteinopathies. However, the nature of early structural changes upon stress sensing and the consequent steps during the course of aggregation are not well understood. In this study, we show that under low-pH conditions, mimicking starvation stress, TDP-43(tRRm) undergoes a conformational opening reaction linked to the protonation of buried ionizable residues and grows into a metastable oligomeric assembly (called the ``low-pH form'' or the ``L form''). In the L form, the protein molecules have disrupted tertiary structure, solvent-exposed hydrophobic patches, and mobile side chains but the native-like secondary structure remains intact. The L form structure is held by weak interactions and has a steep dependence on ionic strength. In the presence of as little as 15 mM KCl, it fully misfolds and further oligomerizes to form a beta-sheet rich ``beta form'' in at least two distinct steps. The beta form has an ordered, stable structure that resembles worm-like amyloid fibrils. The unstructured regions of the protein gain structure during L (sic) beta conversion. Our results suggest that TDP-43(tRRm) could function as a stress sensor and support a recent model in which stress sensing during neurodegeneration occurs by assembly of proteins into metastable assemblies that are precursors to the solid aggregates.

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

Electrochemical evaluation of the stability and capacity of r-GO-wrapped copper antimony chalcogenide anode for Li-ion battery - Yadav, Poonam; Sharma, Neha; Patrike, Apurva; Sabri, Ylias M.; Jones, Lathe A.; Shelke, V. Manjusha (ChemElectroChem, 2020)
Poor cycling stability and capacity fade are primary concerns for next-generation anode materials for Li-ion batteries. In non-carbonaceous anode materials, alloying with Li leads to volume increase that affects practical applications, and increase in particle size, amorphization and reduced conductivity can all lead to a loss of performance. In this work, binary antimony sulfide (Sb2S3) and ternary copper antimony sulfide (CuSbS2) are synthesized by a convenient solvothermal process. These materials are used to study the Li-active/inactive concept, by incorporating Cu into Sb(2)S(3)forming CuSbS(2)wherein Cu is Li inactive whereas Sb is Li active. By direct comparison, we have shown that incorporating Cu into binary antimony sulfide (Sb2S3) resulting into ternary copper antimony sulfide (CuSbS2) addresses the problem of poor conductivity and capacity loss, as Cu provides conductivity leading to enhanced charge transfer and prevents Sb particle aggregation while charge-discharge by exhibiting spectator or diluent ion effect. The better performance of CuSbS(2)is associated with the better Li(+)ion diffusion in the CuSbS2(D=8.97x10(-15) cm(2) s(-1)) compared to Sb2S3(D=2.76x10(-15) cm(2) s(-1)) and lower series resistance of CuSbS2(R=4.70x10(5) omega) compared to Sb2S3(R=5.81x10(8) omega). We have also investigated the composite with the addition of rGO. The CuSbS2-rGO delivered a reversible capacity of 672 mAh g(-1)after 1000 cycles at 200 mA g(-1)which has shown best performance.
Keywords: Batteries; chalcogenides; Diffusion coefficient; lithium; Ternary sulfides

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

Electronic structure parameter of nuclear magnetic quadrupole moment interaction in metal monofluorides - Talukdar, Kaushik; Nayak, Malaya K.; Vaval, Nayana; Pal, Sourav (Journal of Chemical Physics, 2020)
The electronic structure parameter (W-M) of the nuclear magnetic quadrupole moment (MQM) interaction in numerous open-shell metal monofluorides (viz., MgF, CaF, SrF, BaF, RaF, and PbF) is computed in the fully relativistic coupled-cluster framework. The electron-correlation effects are found to be very important for the precise calculation of W-M in the studied molecular systems. The molecular MQM interaction parameter scales nearly as Z(2) in the alkaline earth metal monofluorides, where Z is the nuclear charge of metal. Our study identifies (RaF)-Ra-223 as a good candidate for the experimental search of the nuclear MQM, which can help unravel the physics beyond the standard model in the hadron sector of matter.

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

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

Elucidating the effect of CaF 2 on structure, biocompatibility and antibacterial properties of S53P4 glass - Prasad, Sakthi; Ganisetti, Sudheer; Jana, Anuradha; Kant, Shashi; Sinha, P. K.; Tripathy, Sucheta; Illath, Kavya; Ajithkumar, T. G.; Annapurna, K.; Allu, Amarnath R.; Biswas, Kaushik (Journal of Alloys and Compounds, 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;">The present work focuses on the synthesis and structural elucidation of fluoride containing bioactive glasses in the system (in mol%) given by (53.86) SiO<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;"> – (22.65) Na<span style="font-size: 13.5px; line-height: 0; position: relative; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">2<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">O – (21.77-x) CaO – (1.72) P<span style="font-size: 13.5px; line-height: 0; position: relative; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">2<span style="color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-size: 18px; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">O<span style="font-size: 13.5px; line-height: 0; position: relative; bottom: -0.25em; color: rgb(46, 46, 46); font-family: NexusSerif, Georgia, "Times New Roman", Times, STIXGeneral, "Cambria Math", "Lucida Sans Unicode", "Microsoft Sans Serif", "Segoe UI Symbol", "Arial Unicode MS", serif; font-style: normal; font-variant-ligatures: normal; font-variant-caps: normal; font-weight: 400;">5<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;"> – x CaF<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;">, where, x = 0, 5.44, 10.885 and 16.33. The role of the incorporated fluoride and its distribution within the glass were interpreted and analyzed using Molecular dynamics (MD) simulations and the results were compared with the modified random network (MRN) model. The interpretations from the model have been verified using the MAS-NMR spectroscopy technique. According to this model, fluoride containing bioactive glasses have been proposed to consist of silicate rich network regions and modifier cation – fluoride rich inter-network regions. The interface region was found to consist of non-bridging oxygen species (NBO) and phosphate cations which are either isolated orthophosphates (<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;">Q<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;">0<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;">P<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;">) or bridged with silicates in the form of pyrophosphate (<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;">Q<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;">1<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;">P<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;">) units forming Si–O–P bonds. The gradual substitution of CaF<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;"> for CaO in the base glass resulted in an increase in the silicate network connectivity with a reduction in the NBOs and lead to an increase in the association of modifier cations with fluoride ions. However, fluoride ions were found to show a marginal preference to associate with Na<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;"> cations leading to a decrease in the association of Na<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;"> ions with orthophosphate and silicate units. These overall structural findings were correlated with the <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 vitro<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;"> ion dissolution behaviour of the bioactive glasses as well as with the thermal properties. The glasses were tested for their <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 vitro<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;"> cell viability towards mouse osteoblast type (MC3T3) cells in which fluoride containing bioactive glasses did not show any toxicity and exhibited better cell proliferation. The antibacterial efficacy of the fluoride containing glasses was tested at various concentrations (5, 10 and 20 mg/ml) in <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;">E.coli<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;"> bacterial inoculum in which bactericidal action was evidenced.
Keywords: Fluoride bioactive glasses; In vitro apatite formation and bactericidal action; MAS-NMR spectroscopy; MD simulations

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 titers and productivity of rCHO clones with a combination of an optimized fed-batch process and ER-stress adaptation - Chandrawanshi, Vikas; Kulkarni, Rohan; Prabhu, Anuja; Mehra, Sarika (Journal of Biotechnology, 2020)
To increase the productivity of rCHO cells, many cell engineering approaches have been demonstrated that over-express or knockout a specific gene to achieve increased titers. In this work, we present an alternate approach, based on the concept of evolutionary adaptation, to achieve cells with higher titers. rCHO cells, producing a monoclonal antibody, are adapted to ER-stress, by continuous culturing under increasing concentration of tunicamycin. A sustained higher productivity of at-least 2-fold was achieved in all the clones, in a concentration-dependent manner. Similarly, a 1.5-2 fold increase in final titers was also achieved in the batch culture. Based on metabolic analysis of the adapted cells, a fed-batch process was designed where significantly higher titersare achieved as compared to control. Metabolic flux analysis is employed in addition with gene expression analysis of key genes to understand the basis of increased performance of the adapted cells. Overall, this work illustrates how process modifications and cellular adaptation can be used in synergy to drive up product titers.
Keywords: Adaptive laboratory evolution; CHO cells; ER-stress; Fed-batch; Increased productivity and titers; Recombinant protein production; UPR pathway

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

Expeditious and solvent-free nickel-catalyzed c-h arylation of arenes and indoles (vol 10, pg 2242, 2017) - Jagtap, Rahul A.; Soni, Vineeta; Punji, Benudhar (ChemSusChem, 2020)
Keywords: Arylation; C-H activation; heterocycles; Homogeneous catalysis; Nickel

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

Fluoride release and fluoride-recharging ability of three different sealants - Patil, Sneha; Kontham, Ujwal R.; Kontham, Rakesh K.; Patil, Smita S.; Kamble, Sanjay P. (Journal of Indian Society of Pedodontics and Preventive Dentistry, 2020)
Background: We aimed to determine the fluoride release and fluoride-recharging ability of a sealant containing surface pre-reacted glass (S-PRG) ionomer filler particles (BeautiSealant) with a fluoride-releasing resin sealant (Helioseal F), and a glass-ionomer sealant (Fuji VII). Materials: And: Methodology: Forty-eight disc-shaped specimens of each material were immersed in deionized water to determine the fluoride release utilizing a fluoride ion-selective electrode. After 21 days, 8 specimens were soaked in 0.22% Sodium Fluoride solution for 2 min; 8 specimens were coated with 1.23% Acidulated Phosphate Fluoride (APF) gel for 4 min, and the fluoride-recharging ability was evaluated for 40 days. Data were analyzed using one way-ANOVA and Bonferroni post hoc tests. Results: Total fluoride release over the 21-day period was: Fuji VII > BeautiSealant > Helioseal F, (P = 0.000). After refluoridation of the specimens with 0.22% Sodium Fluoride solution, the cumulative fluoride release during the 40-day period for each material was: BeautiSealant > Fuji VII > Helioseal (P = 0.000). After exposure to 1.23% APF gel, the cumulative fluoride release during the 40-day period for each material was: BeautiSealant > Fuji VII > Helioseal F (P = 0.000). Conclusion: Glass ionomer-based sealants (Fuji VII) exhibited higher initial fluoride release whilst the surface pre-reacted glass-ionomer filler containing sealant (BeautiSealant) demonstrated superior fluoride recharging properties.

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

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

Gold and hypervalent iodine(iii): liaisons over a decade for electrophilic functional group transfer reactions - Banerjee, Somsuvra; Bhoyare, Vivek W.; Patil, Nitin T. (Chemical Communications, 2020)
Over the last two decades, hypervalent iodine(iii) reagents have evolved from being `bonding curiosities' to mainstream reagents in organic synthesis, in particular, electrophilic functional group transfer reactions. In this context, gold catalysts have not only emerged as a unique toolbox to facilitate such reactions (especially alkynylations) but also opened new possibilities with their different modes of reactivities for other functional group transfer reactions (acetoxylations and arylations). This feature article critically summarizes hitherto all such Au-catalyzed electrophilic functional group transfer reactions with hypervalent iodine(iii) reagents, emphasizing their mechanistic aspects.

Gold-catalyzed alkynylative meyer-schuster rearrangement - Banerjee, Somsuvra; Ambegave, Shivhar B.; Mule, Ravindra D.; Senthilkumar, Beeran; Patil, Nitin T. (Organic Letters, 2020)
By applying the ``interplay'' mode, which consolidates two key reactivity modes of gold catalysis, namely pi-activation mode and cross-coupling mode, the first alkynylative Meyer-Schuster rearrangement is designed and successfully implemented. The current protocol gives straightforward access to enynones, a highly valuable building block, from easily available propargyl alcohol feedstocks. Control experiments suggest an Au(III) catalyst triggers the Meyer-Schuster rearrangement, whereas monitoring the reaction with ESI-HRMS provided strong evidence in favor of a key alkynylgold(III) intermediate which supports the proposed ``interplay'' scenario.

Graphene-MnO2 composite supercapacitor material accomplished tactically using liquid-liquid and solid-liquid interface reaction techniques - Patil, Sagar H.; Gaikwad, Aarti P.; Waghmode, Babasaheb J.; Sathaye, Shivaram D.; Patil, Kashinath R. (New Journal of Chemistry, 2020)
A novel methodology is described to grow architectures of 3-dimensional graphene nanosheet (GNS)-manganese oxide (MnO2) composite materials to be used in supercapacitors. The in situ growth of the three-dimensional MnO2 fiber-network over the surface of graphene layers is achieved at the solid-liquid interface. The composite electrode shows good electron and charge transfer, rapid plus reversible faradaic reactions and excellent cyclic ability in electrochemical studies. The electrochemical properties of the as-prepared GNS-MnO2/FTO electrode material were assessed by cyclic voltammetry and galvanostatic charge/discharge tests. The specific capacitance of GNS-MnO2 reaches 683 F g(-1) at a current density of 2.2 A g(-1) and shows excellent cycle stability, retaining 96.9% of its initial capacitance up to 5000 cycles. A coulomb efficiency of about 99% displayed by the GNS-MnO2/FTO electrode is an excellent performance for a desired supercapacitor material. Herein, the charge storage mechanism in 3-dimensional graphene nanosheet (GNS)-manganese oxide (MnO2) composite is discussed in detail. Furthermore, at an elevated current density of similar to 10.86 A g(-1), a power density of similar to 6.235 kW kg(-1) is achieved, maintaining an energy density of similar to 7.99 kW h kg(-1); thus, it demonstrates promising potential as an electrode material for supercapacitor application.

Highly enantioselective synthesis of sitagliptin - Khopade, V. Kishor; Sen, Anirban; Birajdar, Rajkumar S.; Paulbudhe, Uday P.; Kavale, Dattatry S.; Shinde, Prashant S.; Mhaske, Santosh B.; Chikkali, Samir H. (Asian Journal of Organic Chemistry, 2020)
A highly enantioselective synthesis of sitagliptin, a potent DPP-4 inhibitor, is reported. Explicitly identified chiral FerroLANE ligands in the presence of rhodium catalyze the asymmetric hydrogenation of an enamine to yield sitagliptin with excellent enantioselectivity (98% ee). The process was scaled up to 5 g and the final product was isolated as a phosphate salt with >99% ee.
Keywords: asymmetric hydrogenation; catalysis; FerroLANE ligands; Rhodium; sitagliptin

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

Hydrophobic interpenetrating polyamide-PDMS membranes for desalination, pesticides removal and enhanced chlorine tolerance - Khairkar, Shyam R.; Pansare, V, Amol; Shedge, Amol A.; Chhatre, Shraddha Y.; Suresh, A. K.; Chakrabarti, Subhananda; Patil, Vishwanath R.; Nagarkar, Amit A. (Chemosphere, 2020)
Hydrophobic membranes for desalination and toxic organic pollutant removal have been fabricated using polyamide - PDMS (polydimethylsiloxane) chemistries in a one-step protocol. The curing of polyamide and PDMS are orthogonal and co-curing both networks imparts hydrophobicity to the thin film composite membranes. The membranes exhibit increased adsorption of pesticides from the feed water along with maintaining excellent salt rejection capability (97% NaCl rejection), thus giving the membranes a multifunctional character. Three toxic pesticides have been used in this study to demonstrate the viability of combining osmosis desalination technology with organic matter adsorption. The membranes also show excellent resistance to fouling by toxic pesticides (85% salt rejection vs 67% for commercial membranes in the presence of pesticides) and significantly improved chlorine tolerance (93.8% salt rejection vs 86.5% for commercial membranes after 20 h of exposure to sodium hypochlorite solution). (C) 2020 Elsevier Ltd. All rights reserved.
Keywords: PDMS (Polydimethylsiloxane); Pesticide rejection; Salt rejection; Water purification membranes

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

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

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

Insights of Bipolaris sorokinianasecretome-anin silicoapproach - Pathak, Gauri M.; Gurjar, Gayatri S.; Kadoo, Narendra Y. (Biologia, 2020)
The plant pathogen,Bipolaris sorokiniana(teleomorph:Cochliobolus sativus), is of global concern as it attacks many economically important cereals and grasses. During the infection process, phytopathogenic fungi are known to secrete a variety of proteins collectively known as the secretome, analyzing which can help in deciphering the mechanism of fungal pathogenesis. In this study, we performedin silicosecretome analysis ofC. sativusstrain ND90Pr using established secretome prediction pipeline involving software tools such as SignalP, TargetP, TMHMM, big-PI Fungal Predictor, ProtComp, and WoLF PSORT. Using these software and other prediction criteria, we identified 196 probable secretory proteins from theB. sorokinianaproteome. Characterization of the predicted secretome revealed proteins that may have probable functions in degradation of the plant cell wall, lipids, proteins, and nucleic acids, as well as in pathogenesis and metabolism. Further, the PHI-base analysis identified 38 proteins having a possible role in pathogenicity and virulence. This study helped to predict the composition of the secretome ofB. sorokinianaand extrapolate its role in plant infection and pathogen survival. It may provide clues for developing new control strategies targeting the vital fungal secretory proteins.
Keywords: Cochliobolus sativus; pathogenesis; Phytopathogenic fungi; Secretory proteins; Virulence

Iron-catalyzed C(sp(2))-H alkylation of indolines and benzo[h]quinoline with unactivated alkyl chlorides through chelation assistance - Jagtap, Rahul A.; Samal, Pragnya Paramita; Vinod, C. P.; Krishnamurty, Sailaja; Punji, Benudhar (ACS Catalysis, 2020)
Regioselective C-H bond alkylation of indolines and benzo[h]quinoline with a wide range of unactivated and highly demanded primary and secondary alkyl chlorides is accomplished using a low-cost iron catalyst. This reaction tolerates diverse functionalities, such as C(sp(2))-Cl, fluoro, alkenyl, silyl, ether, thioether, pyrrolyl, and carbazolyl groups including cyclic and acyclic alkyls as well as alkyl-bearing fatty-alcohol and polycyclic-steroid moieties. The demonstrated iron-catalyzed protocol proceeded via either a five-membered or a six-membered metallacycle. Intriguingly, the C-7-alkylated indolines can be readily functionalized into free-NH indolines/indoles and tryptamine derivatives. A detailed mechanistic investigation highlights the participation of an active Fe(I) catalyst and the involvement of a halogen-atom transfer process via a single-electron-based mechanism. Deuterium labeling and kinetics analysis indicate that the C-H metalation of indoline is the probable turnover-limiting step. Overall, the experimental and theoretical studies supported an Fe(I)/Fe(III) pathway for the alkylation reaction comprising the two-step, one-electron oxidative addition of alkyl chloride.
Keywords: alkyl chlorides; Alkylation; C-H activation; chelation assistance; indolines; iron

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.

Lipid-dependent conformational landscape of the ErbB2 growth factor receptor dimers - Gopal, Srinivasa M.; Pawar, Aiswarya B.; Wassenaar, Tsjerk A.; Sengupta, Durba (Chemistry and Physics of Lipids, 2020)
Altered lipid metabolism has been linked to cancer development and progression. Several roles have been attributed to the increased saturation and length of lipid acyl tails observed in tumors, but its effect on signaling receptors is still emerging. In this work, we have analyzed the lipid dependence of the ErbB2 growth factor receptor dimerization that plays an important role in the pathogenesis of breast cancer. We have performed coarse-grain ensemble molecular dynamics simulations to comprehensively sample the ErbB2 monomer-dimer association. Our results indicate a dynamic dimer state with a complex conformational landscape that is modulated with increasing lipid tail length. We resolve the native N-terminal ``active'' and C-terminal ``inactive'' conformations in all membrane compositions. However, the relative population of the N-terminal and C-terminal conformers is dependent on length of the saturated lipid tails. In short-tail membranes, additional non-specific dimers are observed which are reduced or absent in long-tailed bilayers. Our results indicate that the relative population as well as the structure of the dimer state is modulated by membrane composition. We have correlated these differences to local perturbations of the membrane around the receptor. Our work is an important step in characterizing ErbB dimers in healthy and diseased states and emphasize the importance of sampling lipid dynamics in understanding receptor association.
Keywords: ErbB2 dimer; Lipid effects; Martini coarse-grained simulations; Membrane protein structure; Transmembrane association

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

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

MnBr2-catalyzed direct and site-selective alkylation of indoles and benzo[h]quinoline - Jagtap, Rahul A.; Verma, Suryadev K.; Punji, Benudhar (Organic Letters, 2020)
Manganese-catalyzed regioselective C-H alkylation of indoles and benzo[h]quinoline with a variety of unactivated alkyl iodides is reported. Unlike other Mn-catalyzed C-H functionalization, this protocol does not require a Grignard reagent base and employs a simple and inexpensive MnBr2 as a catalyst. This method tolerates diverse functionalities, including fluoro, chloro, bromo, iodo, alkenyl, alkynyl, pyrrolyl, and carbazolyl groups. The alkylation proceeds through a single-electron transfer pathway comprising reversible C-H manganesation and involving an alkyl radical intermediate.

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

NADP-dependent glutamate dehydrogenases in a dimorphic zygomycete Benjaminiella poitrasii: purification, characterization and their evaluation as an antifungal drug target - Pathan, Ejaj K.; Kulkarni, Anand M.; Prasanna, Nallaballe V. L.; Ramana, V, Chepuri; Deshpande, V, Mukund (Biochimica Et Biophysica Acta-General Subjects, 2020)
Background: It has been reported that the genes coding for NADP-dependent glutamate dehydrogenases (NADP-GDHs) showed a cause-effect relationship with Yeast-Hypha (Y-H) reversible transition in a zygomycete Benjaminiella poitrasii. As Y-H transition is significant in human pathogenic fungi for their survival and proliferation in the host, the NADP-GDHs can be explored as antifungal drug targets. Methods: The yeast-form specific BpNADPGDH I and hyphal-form specific BpNADPGDH II of B. poitrasii were purified by heterologous expression in E. coll. BL-21 cells and characterized. The structural analogs of L-glutamate, dimethyl esters of isophthalic acid (DMIP) and its derivatives were designed, synthesized and screened for inhibition of NADP-GDH activity as well as Y-H transition in B. poitrasii, and also in human pathogenic Candida albicans strains. Results: The BpNADPGDH I and BpNADPGDH II were found to be homo-hexameric proteins with native molecular mass of 282 kDa and 298 kDa, respectively and subunit molecular weights of 47 kDa and 49 kDa, respectively. Besides the distinct kinetic properties, BpNADPGDH I and BpNADPGDH II were found to be regulated by cAMP-dependent- and Calmodulin (CaM) dependent- protein kinases, respectively. The DMIP compounds showed a more pronounced effect on H-form specific BpNADPGDH II and inhibited Y-H transition as well as growth in B. poitrasii and C. albicans strains. Conclusion: The present study will be useful to design and develop antifungal drugs against dimorphic human pathogens using glutamate dehydrogenase as a target. Significance: Glutamate dehydrogenases can be explored as a target against human pathogenic fungi.
Keywords: Antifungal compound; Benjaminiella poitrasii; Candida albicans; Dimethyl esters and amides of isophthalic acid; dimorphism; Enzyme inhibition; NADP-glutamate dehydrogenases

Nanocomposite of functional silver metal containing curcumin biomolecule model systems: Protein BSA bioavailability - Shedge, Amol A.; Pansare, Shubham V.; Khairkar, Shyam R.; Chhatre, Shraddha Y.; Chakrabarti, S.; Nagarkar, Amit A.; Pansare, Amol V.; Patil, Vishwanath R. (Journal of Inorganic Biochemistry, 2020)
Curcumin, a constituent of Curcuma longa L-Zingiberaceae is used in traditional Indian and worldwide medicine and shows anticancer and antioxidant properties. Curcumin has numerous biological and pharmacological ac-tivities but due to its hydrophobic nature, the major drawback is poor absorption and rapid elimination, rendering curcumin with the tag of a poor biomaterial. Hence, there is a need to develop functional metal containing curcumin model systems (FMCCMS) as a metallo-biomolecule to enhance the bioavailability of curcumin. We designed the interaction of silver metal ion with curcumin to form curcumin-silver nanocomposite (CURC-AgNCP) via ultrasonic synthetic route. Formations of FMCCMS were characterized by spectroscopic techniques. The crystalline face-centered cubic pattern and particle size of the nanocomposite was evaluated using X-ray diffraction and high-resolution transmission electron microscopy. The bonding of silver metal to curcumin was confirmed by X-ray photon spectroscopy. Interaction of the nanocomposite with bovine serum albumin (BSA) protein was performed using excitation, emission, and circular dichroism spectroscopy. In binding interaction of BSA, the negative value of Delta S degrees (-358.04 J mol(-1) K-1) and Delta H degrees (-129.42 KJ mol(-1)) demonstrates the hydrophilic nature of the nanocomposite. The binding distance r evaluated according to the Forster resonance energy transfer theory and was 4.69 nm for CURC-AgNCP, which suggested non-radiative transfer of energy between CURC-AgNCP and BSA. The role of FMCCMS metallo-biomolecule CURC-AgNCP in medicine for cancer activity can have immense importance and hence we performed Sulphorhodamine B based in-vitro cytotoxicity assay on human breast cancer Michigan Cancer Foundation-7 cell line.
Keywords: Ag-based CURC biomaterials; Breast cancer; Metal in medicine; Metallobiomolecules; Nanocomposite

Negative ion resonance states: the fock-space coupled-cluster way - Basumallick, Suhita; Sajeev, Y.; Pal, Sourav; Vaval, Nayana (Journal of Physical Chemistry A, 2020)
The negative ion resonance states, which are electron-molecule metastable compound states, play the most important role in free-electron controlled molecular reactions and low-energy free-electron-induced DNA damage. Their electronic structure is often only poorly described but crucial to an understanding of their reaction dynamics. One of the most important challenges to current electronic structure theory is the computation of negative ion resonance states. As a major step forward, coupled-cluster theories, which are well-known for their ability to produce the best approximate bound state electronic eigen solutions, are upgraded to offer the most accurate and effective approximations for negative ion resonance states. The existing Fock-space coupled-cluster (FSCC) and the equation-of-motion coupled-cluster (EOM-CC) approaches that compute bound states are redesigned for the direct and simultaneous determination of both the kinetic energy of the free electron at which the electron-molecule compound states are resonantly formed and the corresponding autodetachment decay rate of the electron from the metastable compound state. This Feature Article reviews the computation of negative ion resonances using the FSCC approach and, in passing, provides the highlights of the equivalent EOM-CC approach.

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

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

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

Penicillium janthinellum NCIM1366 shows improved biomass hydrolysis and a larger number of CAZymes with higher induction levels over Trichoderma reesei RUT-C30 - Sreeja-Raju, Athiraraj; Christopher, Meera; Kooloth-Valappil, Prajeesh; Kuni-Parambil, Rajasree; Gokhale, Digambar Vittal; Sankar, Meena; Abraham, Amith; Pandey, Ashok; Sukumaran, Rajeev K. (Biotechnology for Biofuels, 2020)
Background Major cost of bioethanol is attributed to enzymes employed in biomass hydrolysis. Biomass hydrolyzing enzymes are predominantly produced from the hyper-cellulolytic mutant filamentous fungus Trichoderma reesei RUT-C30. Several decades of research have failed to provide an industrial grade organism other than T. reesei, capable of producing higher titers of an effective synergistic biomass hydrolyzing enzyme cocktail. Penicillium janthinellum NCIM1366 was reported as a cellulase hyper producer and a potential alternative to T. reesei, but a comparison of their hydrolytic performance was seldom attempted. Results Hydrolysis of acid or alkali-pretreated rice straw using cellulase enzyme preparations from P. janthinellum and T. reesei indicated 37 and 43% higher glucose release, respectively, with P. janthinellum enzymes. A comparison of these fungi with respect to their secreted enzymes indicated that the crude enzyme preparation from P. janthinellum showed 28% higher overall cellulase activity. It also had an exceptional tenfold higher beta-glucosidase activity compared to that of T. reesei, leading to a lower cellobiose accumulation and thus alleviating the feedback inhibition. P. janthinellum secreted more number of proteins to the extracellular medium whose total concentration was 1.8-fold higher than T. reesei. Secretome analyses of the two fungi revealed higher number of CAZymes and a higher relative abundance of cellulases upon cellulose induction in the fungus. Conclusions The results revealed the ability of P. janthinellum for efficient biomass degradation through hyper cellulase production, and it outperformed the established industrial cellulase producer T. reesei in the hydrolysis experiments. A higher level of induction, larger number of secreted CAZymes and a high relative proportion of BGL to cellulases indicate the possible reasons for its performance advantage in biomass hydrolysis.
Keywords: Bioethanol; CAZymes; Cellulase; Penicillium janthinellum; Secretome; Trichoderma reesei

Phase- and morphology-controlled synthesis of tunable plasmonic MoO3-x nanomaterials for ultrasensitive surface-enhanced raman spectroscopy detection - Patil, Manoj Krishnat; Gaikwad, Supriya Hanmant; Mukherjee, Shatabdi Porel (Journal of Physical Chemistry C, 2020)
The enhancement of the surface-enhanced Raman scattering (SERS) property of the plasmonic metal oxide semiconductor nanostructures by controlling their phase, shape, size, and oxygen vacancy to detect trace amounts of organics is of significant interest. In this study, a simple surfactant-free hydrothermal strategy was proposed to fabricate crystalline h-MoO3-x and alpha-MoO3-x nanomaterials with tunable plasmonic properties. Herein, the crystal phase, morphology, and oxygen vacancy of MoO3-x nanostructures were precisely controlled under suitable synthetic conditions. The plasmonic properties of the as-synthesized h-MoO3-x and alpha-MoO3-x micro-/nanostructures were controlled by adjusting the residual volume in the autoclaving chamber. In addition, the plasmonic MoO3-x exhibited SERS activity with a detection limit as low as 1.0 x 10(-9) M and the maximum enhancement factor (EF) up to 6.99 x 10(5) for h-MoO3-x, while for alpha-MoO3-x, the detection limit was 1.0 x 10(-7) M with the corresponding EF up to 8.51 x 10(3), comparable with plasmonic noble metal nanomaterials without a ``hot spot''.

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

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.

Possible role of glycation in the regulation of amyloid beta precursor protein processing leading to amyloid beta accumulation - Patil, Gouri V.; Joshi, Rakesh S.; Kazi, Rubina S.; Kulsange, Shabda E.; Kulkarni, Mahesh J. (Medical Hypotheses, 2020)
Alzheimer's disease (AD) is one of the most common forms of neurodegenerative diseases amongst the aged population. The disease is multifactorial, and diabetes has been considered as one of the major risk factors for the development of AD. Chronic hyperglycemic condition in diabetes promotes non-enzymatic protein modification by glucose termed as glycation, which affects protein structure and function. Previous studies have shown that many of the enzymes, including proteases, are affected by glycation. Conversely, glycated proteins are known to become resistant to protease action. In these hypotheses, we have extended these two concepts to the regulation of amyloid-beta protein precursor (A beta PP) by secretases leading to amyloid-beta (Af3) accumulation. The first hypothesis deals with the glycation of alpha-secretases leading to its reduced activity, while in the second hypothesis, A beta PP glycation may prevent a-secretases action, rendering its processing by beta secretase. As diabetes is a risk factor for the development of AD, either or both these pathways may operate, leading to the manifestation of AD.
Keywords: Alpha-secretase; Alzheimer `s disease; Amyloid-beta; Amyloid-beta protein precursor; Beta-secretase; Diabetes; glucose; Glycation; Type-3 diabetes

Potential of myo-inositol as a starting material for natural product synthesis - Shashidhar, Mysore; Patil, Nivedita (Journal of the Indian Chemical Society, 2020)
Phosphorylated derivatives of myo-inositol are involved in various cellular processes and they are crucial for the survival of cells. Discoveries related to these biological aspects revived the interest in the chemistry of inositols, since derivatives and analogs of phosphoinositols were required as molecular tools for the delineation of the myo-inositol cycle in eukaryotic cells. Extensive research on the chemistry of inositols in the last 3-4 decades encouraged organic chemists to explore the use of myo-inositol, the most abundantly available inositol, as a starting material for the synthesis of natural products. This article is an attempt to review the progress in this area of synthetic chemistry and identify aspects that need to be addressed to increase the potential of myo-inositol as a starting material for natural product synthesis.

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

Recent advances in plant nanobionics and nanobiosensors for toxicology applications - Ansari, Mohammad Hasan Dad; Lavhale, Santosh; Kalunke, Raviraj M.; Srivastava, Prabhakar L.; Pandit, Vaibhav; Gade, Subodh; Yadav, Sanjay; Laux, Peter; Luch, Andreas; Gemmati, Donato; Zamboni, Paolo; Singh, Ajay Vikram (Current Nanoscience, 2020)
Emerging applications in the field of nanotechnology are able to solve a gamut of problems surrounding the applications of agroecosystems and food technology. Nano Engineered Material (NEM) based nanosensors are important tools for monitoring plant signaling pathways and metabolism that arc nondestructive, minimally invasive, and can provide real-time analysis of biotic and abiotic threats for better plant health. These sensors can measure chemical flux even at the single molecule level. Therefore, plant health could be monitored through nutrient management, disease assessment, plant hormones level, environmental pollution, etc. This review provides a comprehensive account of the current trends and practices for the proposed NEM related research and its (i) structural aspect, (ii) experimental design and performance as well as (iii) mechanisms of field application in agriculture and food system. This review also discusses the possibility of integration of data from NEM based nanosensors in current and emerging trends of precision agriculture, urban farming, and plant nanobionics to adopt a sustainable approach in agriculture,
Keywords: agro-ecosystems; engineered nanomaterials; nanobionics; Nanosensors; nanotechnology; nanotoxicology

Relativistic coupled-cluster study of BaF in search of CP violation - Talukdar, Kaushik; Nayak, Malaya K.; Vaval, Nayana; Pal, Sourav (Journal of Physics B-Atomic Molecular and Optical Physics, 2020)
BaF is one of the potential candidates for the experimental search of the electric dipole moment of the electron (eEDM). The NL-eEDM collaboration is building a new experimental set up to measure the eEDM using the BaF molecule (The NL-eEDM collaboration, 2018 Eur. Phys. J. D 72: 197). To analyze the results of such an experiment, one would require the accurate value of the molecular P, T-odd interaction parameters that cannot be measured from any experiment. In this work, we report the precise value of the P, T-odd interaction parameters of the BaF molecule obtained from the four-component relativistic coupled-cluster calculations. We also calculate the hyperfine structure (HFS) constants of the same molecule to assess the reliability of the reported molecular parameters. The calculated HFS constants show good agreement with the available experimental values. Further, the systematic effects of electron-correlation along with the roles of inner-core electrons and the virtual energy functions in the calculation of the studied properties of BaF are investigated.
Keywords: electric dipole moment of the electron; electron-correlation; Relativistic effects

Relativistic double-ionization equation-of-motion coupled-cluster method: application to low-lying doubly ionized states - Pathak, Himadri; Sasmal, Sudip; Talukdar, Kaushik; Nayak, Malaya K.; Veval, Nayana; Pal, Sourav (Journal of Chemical Physics, 2020)
This article deals with the extension of the relativistic double-ionization equation-of-motion coupled-cluster (DI-EOMCC) method [H. Pathak et al. Phys. Rev. A 90, 010501(R) (2014)] for the molecular systems. The Dirac-Coulomb Hamiltonian with four-component spinors is considered to take care of the relativistic effects. The implemented method is employed to compute a few low-lying doubly ionized states of noble gas atoms (Ar, Kr, Xe, and Rn) and Cl-2, Br-2, HBr, and HI. Additionally, we presented results with two intermediate schemes in the four-component relativistic DI-EOMCC framework to understand the role of electron correlation. The computed double ionization spectra for the atomic systems are compared with the values from the non-relativistic DI-EOMCC method with spin-orbit coupling [Z. Wang et al. J. Chem. Phys. 142, 144109 (2015)] and the values from the National Institute of Science and Technology (NIST) database. Our atomic results are found to be in good agreement with the NIST values. Furthermore, the obtained results for the molecular systems agree well with the available experimental values.

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

Role of cholesterol-mediated effects in GPCR heterodimers - Prasanna, Xavier; Mohole, Madhura; Chattopadhyay, Amitabha; Sengupta, Durba (Chemistry and Physics of Lipids, 2020)
G protein-coupled receptors (GPCRs) are transmembrane receptors that mediate a large number of cellular responses. The organization of GPCRs into dimers and higher-order oligomers is known to allow a larger repertoire of downstream signaling events. In this context, a crosstalk between the adenosine and dopamine receptors has been reported, indicating the presence of heterodimers that are functionally relevant. In this paper, we explored the effect of membrane cholesterol on the adenosine(2A) (A(2A)) and dopamine D-3 (D-3) receptors using coarse-grain molecular dynamics simulations. We analyzed cholesterol interaction sites on the A(2A) receptor and were able to reproduce the sites indicated by crystallography and previous atomistic simulations. We predict novel cholesterol interaction sites on the D-3 receptor that could be important in the reported cholesterol sensitivity in receptor function. Further, we analyzed the formation of heterodimers between the two receptors. Our results suggest that membrane cholesterol modulates the relative population of several co-existing heterodimer conformations. Both direct receptor-cholesterol interaction and indirect membrane effects contribute toward the modulation of heterodimer conformations. These results constitute one of the first examples of modulation of GPCR hetero-dimerization by membrane cholesterol, and could prove to be useful in designing better therapeutic strategies.
Keywords: Adenosine(2A) receptor; Cholesterol; Dopamine D-3 receptor; G protein-coupled receptors; Heterodimer; MARTINI coarse-grain simulation

Role of electron correlation in the P, T-odd effects of CdH: a relativistic coupled-cluster investigation - Talukdar, Kaushik; Nayak, Malaya K.; Vaval, Nayana; Pal, Sourav (Physical Review A, 2020)
We investigate the parity (P) and time-reversal (T) symmetry violating effects in the CdH molecule and perform the relativistic coupled-cluster calculation of the molecular parameters-E-eff, W-s, and W-M-related to the electric dipole moment of electron (eEDM) interaction, the scalar-pseudoscalar (S-PS) nucleus-electron neutral current coupling, and the nuclear magnetic quadrupole moment (MQM) interaction with electrons, respectively. We also compute the molecular dipole moment and the magnetic hyperfine structure coupling constant of CdH. The values of E-eff, W-s, and W-M obtained by us in the said molecule are 12.2 GV/cm, 14.0 kHz, and 0.82 x 10(33) Hz/e cm(2), respectively, within an uncertainty of 10%. Furthermore, we study the trend of electron-correlation in the computed properties of CdH and that of the P, T-odd parameters in the group-12 monohydrides (i.e., ZnH, CdH, and HgH).

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

Scalable synthesis of 3-Ethyl-4-methyl-1,5-dihydro-2H-pyrrol-2-one: an important building block of the antidiabetic drug glimepiride - Chavan, Subhash P.; Pawar, Ambaji A.; Patil, Niteen B.; Kadam, Appasaheb L.; Shinde, Shrikrishna S. (Synthesis-Stuttgart, 2020)
A four-step, practical, and easily scalable synthesis of 3-ethyl-4-methyl-1,5-dihydro-2H-pyrrol-2-one, an important building block of the antidiabetic drug glimepiride, has been accomplished. Key features are the synthesis of 3-methyl-4-hydroxy-2-butenolide in water and triflic acid mediated N-benzyl lactam N-deprotection. The main advantages of this process are the scalable synthetic route and decreased number of reaction steps, which paves the way for the industrial-scale synthesis of 3-ethyl-4-methyl-1,5-dihydro-2H-pyrrol-2-one.
Keywords: antidiabetic drug; Butenolide; glimepiride; lactams; scalable synthesis

Shape resonance of sulphur dioxide anion excited states using the CAP-CIP-FSMRCCSD method - Basumallick, Suhita; Bhattacharya, Sumantra; Jana, Irina; Vaval, Nayana; Pal, Sourav (Molecular Physics, 2020)
We have studied the shape resonance of excited states of sulphur dioxide (SO2) anion by using the correlated independent particle Fock space multi-reference coupled cluster (CAP-CIP-FSMRCCSD) method augmented by complex absorption potential. These resonant states have been trapped experimentally in recent years by electron collision. In particular, we have investigated e(-)-SO2 scattering and computed the negative-ion resonance states of the anion responsible for the two resonances around 4.45 and 6.56 eV and compared the results with the existing experimental observations. From the computational results using the CAP-CIP-FSMRCCSD method, it has been observed that both the resonances near 4.45 and 6.56 eV result from A(1) symmetries. [GRAPHICS] .
Keywords: CAP augmented correlated independent particle (CAP-CIP-FSMRCCSD); complex absorption potential (CAP); coupled cluster; Fock space multireference coupled cluster (FSMRCCSD); shape resonance

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

Simultaneous determination of anthraquinone, flavonoids, and phenolic antidiabetic compounds from cassia auriculata seeds by validated UHPLC based MS/MS method - Girme, Aboli; Saste, Ganesh; Chinchansure, Ashish; Joshi, Swati; Kunkulol, Rahul; Hingorani, Lal; Patwardhan, Bhushan (Mass Spectrometry Letters, 2020)
A systematic isolation and characterization study for Cassia auriculata (CA) seeds resulted in identifying antidiabetic compounds 1,3,8-trihydroxyanthraquinone and quercetin, quercetin-3-O-rutinoside, gallic acid, caffeic acid, ferulic acid, and ellagic acid. The ultra-high-performance liquid chromatography based triple quadrupole mass spectrometry methodology was developed and validated for simultaneous identification and confirmation of these compounds from CA seeds. Multiple reaction monitoring (MRM) based quantification method was developed with MRM optimizer software for MS1 and MS2 mass analysis. The method was optimized on precursor ions and product ions with the ion ratio of each compound. The calibration curves of seven bioactive analytes showed excellent linearity (r2 ≥ 0.99). The quantitation results found precise (RSD, < 10 %) with good recoveries (84.58 to 101.42%). The matrix effect and extraction recoveries were found within the range (91.66 to 102.11%) for the CA seeds. This is the first MS/MS-based methodology applied to quantifying seven antidiabetic compounds in CA seeds and its extract for quality control purposes.

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)

Solvent-less solid state synthesis of dispersible metal and semiconducting metal sulfide nanocrystals (vol 6, pg 12006, 2018) - Bera, Abhijit; Busupalli, Balanagulu; Prasad, Bhagavatula L. V. (ACS Sustainable Chemistry & Engineering, 2020)

Spectroscopic evidences for the size dependent generation of pd species responsible for the low temperature CO oxidation activity on Pd-SBA-15 nanocatalyst - Soni, Yogita; Pradhan, Sumanta; Bamnia, Mahesh K.; Yadav, A. K.; Jha, S. N.; Bhattacharyya, D.; Khan, Tuhin Suvra; Haider, M. A.; Vinod, C. P. (Applied Catalysis B-Environmental, 2020)
A comprehensive size dependent CO oxidation activity has been demonstrated for Pd-SBA-15 catalysts with Pd NPs of varying sizes such as 1-2, 4-6 and 7-10 nm. Pd-SBA-15 catalyst with smallest sized NPs (Pd-S-N) has been synthesized by modified deposition precipitation method recently developed in our lab. Pd-S-N catalyst (reduced at 400 degrees C) demonstrated CO oxidation activity with lower light off temperature (50 degrees C), clearly one of the best reported for a Pd-silica system. A detailed XPS and in-situ DRIFTS analyses further supported by XAS and DFT calculations reveal the presence of easily decomposable highvalent Pd-oxide on co-ordinatively unsaturated Pd sites (Pdcus). Weak binding of CO on Pdcus sites in small Pd NPs leaving sites for oxygen activation is attributed to the low temperature activity of Pd-S-N for CO oxidation.
Keywords: CO oxidation; high-valent Pd species; Pd nanoparticles; SBA-15; under coordinated Pd atoms

Sphingomyelin effects in caveolin-1 mediated membrane curvature published as part of the journal of physical chemistry virtual special issue ``computational and experimental advances in biomembranes'' - Krishna, Anjali; Prakash, Shikha; Sengupta, Durba (Journal of Physical Chemistry B, 2020)
The caveolin-1 (cav-1) protein is an integral component of caveolae and has been reported to colocalize with cholesterol and sphingomyelin-rich curved membrane domains. Here, we analyze the molecular interactions between cav-1 and sphingomyelin containing bilayers using a series of coarse-grain simulations, focusing on lipid clustering and membrane curvature. We considered a palmitoylated-cav-1 construct interacting with phospholipid/cholesterol membranes with asymmetrically distributed sphingomyelin, varying between 5 and 15% in total. We observe that cav-1 binds to the intracellular leaflet and induces a small positive curvature in the leaflet to which it is bound and an opposing negative curvature in the extracellular leaflet. Both cholesterol and sphingomyelin are observed to cluster in cav-1 bound membranes, mainly in the extracellular leaflet. Due to their negative spontaneous curvature, clustering of cholesterol and sphingomyelin facilitates membrane curvature such that the extent of either cholesterol or sphingomyelin clustering is dependent on the curvature induced. Our results suggest that cav-1 binding induces concentration-dependent curvature effects in sphingomyelin-rich membranes. Overall, our work is an important step in understanding the molecular basis of curvature and lipid clustering in cav1 bound cellular membranes.

Stepwise nucleophilic substitution to access saturated N-heterocyclic carbene haloboranes with boron-methyl bonds - Kundu, Gargi; Pahar, Sanjukta; Tothadi, Srinu; Sen, Sakya S. (Organometallics, 2020)
Compounds of boranes with N-heterocyclic carbenes are known, yet little attention has been paid to NHC compounds of boron bearing methyl and halogen moieties together. The reason can be attributed to the hazardous methyldichloroborane (MeBCl2), which ignites in air. We describe here convenient solution-phase access to SIDipp.MeBCl2 (SIDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) (3) by a salt metathesis reaction of SIDipp.BCl3 (2) with MeLi. Replacement of the chlorine atoms of 3 with stepwise addition of AgOTf led to the formation of SIDipp.MeBCl(OTf) (4) and SIDipp.MeB(OTf)2 (5). In the case of 4, all of the substituents on the boron atom are different. Subsequently, we extended our synthetic approach to the amidinate system and prepared PhC(NtBu)2B(Me)Cl (7) from the reaction of PhC(NtBu)2BCl2 (6) with MeLi.

Stimuli-responsive biodegradable polyurethane nano-constructs as a potential triggered drug delivery vehicle for cancer therapy - Gajbhiye, Kavita R.; Chaudhari, Bhushan P.; Pokharkar, Varsha B.; Pawar, Atmaram; Gajbhiye, Virendra (International Journal of Pharmaceutics, 2020)
Polyurethanes (PUs) constitute an essential class of stimuli-responsive and biodegradable material, which has significantly contributed to the advancement of polymers utilization in the biomedical field. The bio-erodible PUs construct an active corridor for facilitating drug into tumor cells, which has significantly impacted the progression of nano-micellar delivery systems. The self-assembled colloidal PUs pose distinctive features such as enhancing the solubility of hydrophobic chemotherapeutics, rapid cellular uptake, triggered erosion and drug release, bio-stimulus sensitivity, improvement in the targeting and proficiency of bioactive. Cationic PUs can easily be condensed with genetic material to form polyplexes and have shown excellent transfection efficiency for potential gene therapy against various cancers. Their modifiable chemistry offers a tool to impart the desired multifunctionality such as biocompatibility, sensitivity to pH, redox, temperature, enzyme, etc. and ligand conjugation for active targeting. These diverse exceptional properties make them excellent nano-carrier for a variety of bioactive, including chemotherapeutic drugs, DNA, RNA, and diagnostic moieties to the target tissue or cells. The PUs based nano-devices have certainly uncovered the path to achieve ideal systems for controlled personalized therapy. The literature discussed in this review shed light on the research innovations carried out in the last ten years for the development of multifunctional PUs for triggered delivery of bioactive to treat various cancers.
Keywords: Cancer nanomedicine; GSH; micelles; Polyurathanes; redox; Stimuli-responsive

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

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

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, 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, molecular, functional and immunological characterization of Wuchereria bancrofti-galectin - Yasin, Nazeer; Laxmanappa, Hoti Sugerappa; Muddapur, Uday M.; Cheruvathur, Jennifer; Prakash, S. M. Udaya; Thulasiram, Hirekodathakallu Venkataramaiah (International Journal of Biological Macromolecules, 2020)
Galectins regulate growth and differentiation of immune cells and inflammation through their carbohydrate-binding function in humans, while also play a role in parasite survival. This study focused on the galectin of lymphatic filarial parasite Wuchereria bancrofti (Wb-Gal). The multiple sequence alignment with other galectins showed that the Wb-Gal belonged to galactoside binding lectin family, particularly tandem repeat type galectin-9. A homology model of Wb-Gal was developed in the I-TASser server using high similarity 3D structures with a quality score of 89.5. Molecular docking and dynamics studies revealed that the CCRD and NCRD of Wb-Gal bind with galactose and lactose. Further, Wb-Gal was cloned into the pET28 vector, expressed in E. coli Rosetta strain and purified by affinity chromatography. In the hemagglutination assays, the rWb-Gal bound to lactose, galactose, and glucose. Indirect Enzyme-Linked Immunosorbent Assay (ELISA) using different clinical filarial sera showed that the IgG and IgM response was against Wb-Gal x very high in all filarial clinical groups, whereas the IgA and IgG2 response was minimum to negligible. There was an enhanced response of IgG1 and IgG4 antibodies in Microfilaremics (MF) cases compared to Chronic Pathology (CP) and Endemic Normal (EN) individuals. Interestingly, the IgE response was comparatively higher in EN than MF and CP. These studies show that Wb-Gal is a member of the lectin family of proteins binding to different carbohydrates and may have an important role in the pathophysiology of filarial infection which needs to be investigated in greater detail. (C) 2020 Elsevier B.V. All rights reserved.
Keywords: Filariasis; Hemagglutination assay; Immunomodulation; Wuchereria bancrofti galectin

Study of interfacial adhesion between nickel-titanium shape memory alloy and a polymer matrix by laser surface pattern - Samal, Sneha; Tyc, Ondrej; Heller, Ludek; Sittner, Petr; Malik, Monika; Poddar, Pankaj; Catauro, Michelina; Blanco, Ignazio (Applied Sciences-Basel, 2020)
The aim of this article is to investigate the interfacial adhesion of Ni-Ti shape memory alloy with a polymer matrix of Poly (methyl methacrylate) (PMMA). The surface pattern on Ni-Ti plates was channeled by a solid state laser machine. The laser machine allows for creating channels on the Ni-Ti surface for infiltration of the PMMA matrix, which could be attached as an intra-surface locking pattern to the Ni-Ti surface. The influence of the PMMA matrix on the surface of the NiTi plate was evaluated by thermomechanical analysis (TMA) and dynamic mechanical analysis (DMA). The surface characterization was carried out by an optical microscope on the PMMA/NiTi composite after mechanical testing. During mechanical testing, the polymer displays the multiple cracks in the longitudinal direction that result in slipping and fracture. TMA and DMA analyses were performed on the Ni-Ti- and PMMA-coated Ni-Ti ribbon to observe elasticity and the storage modulus for both samples. Better adhesion than 80 % was observed in the Ni-Ti surface, in the laser surface pattern, in comparison to the free plain surface. However, the polymer acts as mechanical backing that caused a reduction in the shape-memory properties of the composite material.
Keywords: adhesion; mechanical properties; NiTi composites; NiTi plate; PMMA; Polymer; surface features

Study of the phase-evolution mechanism of an Fe-Se system at the nanoscale: optimization of synthesis conditions for the isolation of pure phases and their controlled growth - Ghalawat, Monika; Poddar, Pankaj (Langmuir, 2020)
The iron selenide (Fe-Se) family of nanoparticles (FexSey-where x/y ranges from 1:2 to 1:1) has been fabricated by a thermal decomposition method. The control over solution chemistry has been developed by intensively investigating the effect of reaction parameters by means of wide-angle X-ray scattering, leading to the rich insights into the phase-evolution mechanism of the Fe-Se system. The phase transformation followed the FeSe2 -> Fe3Se4 -> Fe7Se8 -> FeSe sequence in the temperature range of 110-300 degrees C. The deep mechanistic insight helped in the identification of optimized conditions needed to crystallize the individual phase of the Fe-Se system as well as control of the morphology, crystalline phase purity, and thermal stability of the obtained Fe-Se nanoparticles.

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

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

Synthesis of 2-azabicyclo[m.n.0]-alkanes and their application towards the synthesis of strychnos and stemona classes of alkaloids - Majumder, Binoy; Pandey, Ganesh (European Journal of Organic Chemistry, 2020)
2-Azabicyclo[m.n.0]alkane ring systems, the conceptual precursors towards the synthesis of Strychnos and Stemona classes of alkaloids, were synthesized from tert-butyl 2-(phenylsulfonyl)-7-aza-bicyclo[2.2.1]hept-2-ene-7-carboxylate by alkyl Grignard reaction and intramolecular cyclisation of the in situ generated ring opening product 2. The synthesized cis-hexahydroindole 3 and cis-octahydro-benzo[b]azepine 5 scaffolds were utilized to construct the advanced intermediates 25 and 35, respectively, towards the synthesis of the corresponding Strychnos and Stemona classes of alkaloids.
Keywords: alkaloids; amines; Grignard reaction; Michael addition; Natural products

Synthesis of artemisinic acid derived glycoconjugates and their anticancer studies - Kotammagari, Tharun K.; Paul, Sayantan; Barik, Ganesh K.; Santra, Manas K.; Bhattacharya, Asish K. (Organic & Biomolecular Chemistry, 2020)
Glycoconjugates, due to their diverse functions, are widely regarded as biologically important molecules. Artemisinic acid 1 occurs naturally in the plant Artemisia annua and is considered to be the biogenetic precursor of the antimalarial drug, artemisinin 2. We report herein the design and synthesis of diverse artemisinic acid derived glycoconjugates. We have synthesized 12-O-artemisinic acid-glycoconjugates (7a-k) and 12-N-artemisinic acid-glycoconjugates (8a-k) by utilizing Cu(i)-catalyzed azide-alkyne cycloaddition reactions (Click chemistry) with various synthesized sugar azides (6a-k) in good to excellent yields along with two fluorescently labeled compounds, 12-O-artemisinic acid-glycoconjugate 11 and 12-N-artemisinic acid-glycoconjugate 12, to investigate the mode of action of these compounds in biological systems. All the synthesized artemisinic acid glycoconjugates were assayed for their efficacy against the MCF7 cell line. Our anticancer studies indicated that all the synthesized compounds inhibited the growth of MCF7 cells in a dose dependent manner, barring compounds 4 and 7d. However, these compounds exhibit moderate cytotoxicity, as is evident from their IC50 values.

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

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

Triazine-based organic polymer-catalysed conversion of epoxide to cyclic carbonate under ambient CO2 pressure - Biswas, Tanmoy; Halder, Arjun; Paliwal, Khusboo S.; Mitra, Antarip; Tudu, Gouri; Banerjee, Rahul; Mahalingam, Venkataramanan (Chemistry-An Asian Journal, 2020)
In this work we have achieved epoxide to cyclic carbonate conversion using a metal-free polymeric catalyst under ambient CO2 pressure (1.02 atm) using a balloon setup. The triazine containing polymer (CYA-ANIS) was prepared from cyanuric chloride (CYA-Cl) and o-dianisidine (ANIS) in anhydrous DMF as solvent by refluxing under the N-2 gas environment. The presence of triazine and amine functional groups in the polymer results in the adsorption of CO2 up to 7 cc/g at 273 K. This inspired us to utilize the polymer for the conversion of a series of functionalised epoxides into their corresponding cyclic carbonates in the presence of tetrabutyl ammonium iodide (TBAI) as co-catalyst. The product has wide range of applications like solvent in lithium ion battery, precursor for polycarbonate, etc. The catalyst was efficient for the conversion of different mono and di-epoxides into their corresponding cyclic carbonates under atmospheric pressure in the presence of TBAI as co-catalyst. The study indicates that epoxide attached with electron withdrawing groups (like, CH2Cl, glycidyl ether, etc.) displayed better conversion compared to simple alkane chain attached epoxides. This is mainly due to the stabilization of electron rich intermediates produced during the reaction (e. g. epoxide ring opening or CO2 incorporation into the halo-alkoxide anion). This catalyst mixture was capable to maintain its reactivity up to five cycles without losing its activity. Post catalytic characterization clearly supports the heterogeneous and recyclable nature of the catalyst.
Keywords: CO2 fixation; cyclic carbonates; epoxides; Heterogeneouscatalyst; metal free catalyst; Triazinepolymer

Triethyl phosphite/benzoyl peroxide mediated reductive dealkylation of O-benzoylhydroxylamines: a cascade synthesis of secondary amides - Aegurla, Balakrishna; Mandle, Ram D.; Shinde, Prasad G.; Parit, Ratan S.; Kamble, Sanjay P.; Sudalai, Arumugam; Senthilkumar, Beeran (European Journal of Organic Chemistry, 2020)
A new triethyl phosphite/benzoyl peroxide (BPO) mediated system has been developed for the synthesis of secondary amides with good to excellent yields in a single step. This unprecedented cascade process involves sequential reduction of N-O bond and benzoylation followed by dealkylation of N-C bond ofO-benzoylhydroxylamines (O-BHA). The methodology is versatile as it tolerates a variety of aromatic and aliphaticO-BHA as substrates to access secondary amides.
Keywords: Amides; Cascade reactions; O-Benzoylhydroxylamines; Redox reactions; synthetic methods

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

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

Tweaking palladium electronic structure to attain oxygen reduction activity superior to platinum/C - Sarma, Saurav Ch.; Kaja, Sai Manoj; Mishra, Vidyanshu; Vinod, Chathakudath Prabhakaran; Peter, Sebastian C. (ACS Applied Energy Materials, 2020)
Enhancing oxygen reduction (ORR) activity through alloying is crucial to improve the performance of a fuel-cell catalysts. In this work, we have studied the alloying effects of 4f rare-earth (RE) metals with palladium. The modified catalyst exhibits better activity (E-onset = 1 V and E-1/2 = 0.88 V) and higher selectivity toward H2O (similar to 97%) compared to the state-of-the-art catalysts due to complete dissociation of O-2. Hirshfeld charge analysis and 2D-electron localization function reveal improved adsorbate-adsorbent interaction on the catalyst surface. This work paves a strategy to design highly selective non-Pt-based catalysts for the ORR by controlling electronic structures and surface oxide formation.
Keywords: d-band center; DFT calculation; durability; EuPd; oxygen reduction reaction; YbPd

Ultrahigh molecular weight polyethylene: catalysis, structure, properties, processing and applications - Patel, Ketan; Chikkali, Samir H.; Sivaram, Swaminathan (Progress in Polymer Science, 2020)
Ultrahigh molecular weight polyethylene (UHMWPE) belongs to an emerging class of high-performance specialty polymers with a unique set of properties and applications. The field has witnessed many scientific and technological advances in recent years. However, synthesis of UHMWPE is not a trivial exercise and presents several challenges. This review addresses these fundamental challenges and provides an overview of recent developments in the field of UHMWPE. The nature of catalysts, reaction conditions that favor its formation, their physical properties, methods of processing them into products, and their applications are discussed. Recent developments in formation of UHMWPE in a disentangled state by use of appropriate catalysts and reaction conditions are also discussed. This has elicited considerable interest as a means of enabling melt processing of UHMWPE. This review provides a comprehensive source of information and understanding of the multifaceted aspects of UHMWPE with specific reference to chemistry, catalysis, processes for manufacturing, and an analysis of catalyst structure-polymer property relationships. (C) 2020 Elsevier B.V. All rights reserved.
Keywords: Catalysts for UHMWPE; Disentangled UHMWPE; Entangled UHMWPE; polyethylene (PE); Ultrahigh molecular weight (UHMW) PE

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

Unraveling the role of excess ligand in nanoparticle pattern formation from an evaporatively dewetting nanofluid droplet - Bhattacharjee, Kaustav; Biswas, Korak; Bhagavatula L. V. Prasad (Journal of Physical Chemistry C, 2020)
Nanoparticle (NP) patterning on a solid surface via nanofluid droplet evaporation is one of the most fascinating topics of research. Quite intriguingly, though a dose of excess ligand has been invariably included in all of the experimental studies that resulted in large-area NP patterns, the role of this excess ligand has been addressed inadequately in the modeling studies carried out so far. Addressing this, we have conducted systematic studies by including excess ligand both in our experiments and modeling, and correlated the results with each other. For this, we prepared nearly monodispersed thiol-protected gold nanoparticle dispersion in toluene and added calculated amounts of excess thiol before drop-casting it onto a transmission electron microscopy (TEM) grid. Subsequently, upon solvent evaporation, the patterns formed were imaged using conventional electron microscopy and analyzed with customized image processing tools, to perform statistically significant measurements. Our study demonstrates the ability of soluble excess ligand to induce NP aggregation under nonequilibrium condition, leading to large-area monolayer formation. These experimental results were then rationalized by Monte Carlo simulations, based on a modified coarse-grained two-dimensional (2D) lattice-gas model. We found that excess ligand facilitates NP spinodal phase separation under nonequilibrium conditions, largely governed by the interplay between ligand-solvent and nanoparticle-ligand interactions. Using power spectrum density analysis, we clearly demonstrate that these spatial patterns have fractal surface characteristics due to persistent fractional Brownian motion within subdiffusion limit.

Whole-cell phenotypic screening of medicines for malaria venture pathogen box identifies specific inhibitors of plasmodium falciparum late-stage development and egress - Patra, Alok Tanala; Hingamire, Tejashri; Belekar, Meenakshi A.; Xiong, Aoli; Subramanian, Gowtham; Bozdech, Zbynek; Preiser, Peter; Shanmugam, Dhanasekaran; Chandramohanadas, Rajesh (Antimicrobial Agents and Chemotherapy, 2020)
We report a systematic, cellular phenotype-based antimalarial screening of the Medicines for Malaria Venture Pathogen Box collection, which facilitated the identification of specific blockers of late-stage intraerythrocytic development of Plasmodium falciparum. First, from standard growth inhibition assays, we identified 173 molecules with antimalarial activity (50% effective concentration [EC50] <= 10 mu M), which included 62 additional molecules over previously known antimalarial candidates from the Pathogen Box. We identified 90 molecules with EC50 of <= 1 mu M, which had significant effect on the ring-trophozoite transition, while 9 molecules inhibited the trophozoite-schizont transition and 21 molecules inhibited the schizontring transition (with >= 50% parasites failing to proceed to the next stage) at 1 mu M. We therefore rescreened all 173 molecules and validated hits in microscopy to prioritize 12 hits as selective blockers of the schizont-ring transition. Seven of these molecules inhibited the calcium ionophore-induced egress of Toxoplasma gondii, a related apicomplexan parasite, suggesting that the inhibitors may be acting via a conserved mechanism which could be further exploited for target identification studies. We demonstrate that two molecules, MMV020670 and MMV026356, identified as schizont inhibitors in our screens, induce the fragmentation of DNA in merozoites, thereby impairing their ability to egress and invade. Further mechanistic studies would facilitate the therapeutic exploitation of these molecules as broadly active inhibitors targeting late-stage development and egress of apicomplexan parasites relevant to human health.
Keywords: DNA fragmentation; egress; Medicines for Malaria Venture; MMV; Pathogen Box; phenotypic screening; Plasmodium falciparum; schizonts; stage-specific inhibition

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

Access to enantiomeric organic compounds with potential for synthesis via racemic conglomerates: inositol derivatives as a case in point - Patil, Nivedita T.; Patil, Madhuri T.; Sarkar, Nitai; Gonnade, Rajesh G.; Shashidhar, Mysore S. (Crystal Growth & Design, 2021)
The crystal structure database was used to identify inositol derivatives that could be crystallizing as racemic conglomerates. Among the six racemic inositol derivatives identified, racemic 4-O-tosyl-6-O-benzyl-myo-inositol-1,3,5-orthoformate (A) was found to be a true conglomerate and was resolved on the multigram scale by the preferential crystallization technique. This resolution procedure does not require the use of any enantiomeric resolving agent. The resolved enantiomers of A are useful for the synthesis of natural and unnatural enantiomeric derivatives of inositol, since they carry orthogonal hydroxy protecting groups. Racemic 4-O-methanesulfonyl-myo-inositol-1,3,5-orthoformate (B) on crystallization from common organic solvents generally yielded racemic twin crystals, while in the presence of structural analogs as additives, they yielded true racemic crystals. A comparison of the crystal structures of the true racemate, twinned crystal and crystal of one of the enantiomers of B, revealed the reasons for the formation of polymorphic (twin) crystals. Such instances are relatively rarely encountered but nevertheless shed light on our understanding of polymorphism and twinning of crystals.

Achiral and chiral NNN-pincer nickel complexes with oxazolinyl backbones: application in transfer hydrogenation of ketones - Jagtap, Rahul A.; Ankade, Shidheshwar B.; Gonnade, Rajesh G.; Punji, Benudhar (New Journal of Chemistry, 2021)
We describe the synthesis of new NNN-oxazolinyl-pincer nickel complexes and their application in the transfer hydrogenation of ketones. Achiral NNN-ligands, R `(2)-oxazolinyl-2-C6H4-NH-C(O)CH2NEt2 [((R ` 2-OxNNNEt2))-H; R' = H (3a), R ` = Me (3b)], and chiral ligands, (R)-R `-oxazolinyl-2-C6H4-NH-C(O)CH2NEt2 [(R)-((R `-OxNNNEt2))-H; R ` = Ph (3c), R ` = CH2Ph (3d), R ` = Pr-i (3e), R ` = (CH2Pr)-Pr-i (3f)], were efficiently synthesized. Treatment of these ligands with (DME)NiCl2 afforded the desired amido-pincer nickel complexes, ((R ` 2-OxNNNEt2))NiCl [R ` = H (4a), R ` = Me (4b)] and ((R `-OxNNNEt2))NiCl [R ` = Ph (4c), R ` = CH2Ph (4d), R ` = Pr-i (4e), R ` = (CH2Pr)-Pr-i (4f)], in good yields. All the ligand precursors and nickel complexes were thoroughly characterized by various analytical techniques. The molecular structures of 4a, 4d and 4f were established by X-ray crystallography. The developed nickel complexes were found to be efficient catalysts for the transfer hydrogenation of ketones using (PrOH)-Pr-i as a viable hydrogen source. Enantioselectivity in hydrogenation was not observed with the developed chiral catalysts.

Active nickel hollow nanosphere supported over SiO2 catalyst for reduction of nitro compound - Pawar, Priyanka S.; Lokhande, Aboli A.; Nandanwar, Sachin U.; Niphadkar, Prashant S.; Bokade, Vijay V. (Particulate Science and Technology, 2021)
Nickel hollow nanospheres (Ni HNSs) was prepared by solvothermal method using mixture of ethylenediamine (EN) and ethanol (ET), sodium borohydride as reducing agent and nickel chloride hexahydrate as precursor. The particle size of the Ni HNSs were tuned by varying several parameters including precursor concentrations, reaction temperatures (130-190 degrees C), and ET to EN volume ratios. The particle size and morphology of Ni HNSs were confirmed by dynamic light scattering and transmission electron microscope, respectively. Spherical shape of Ni nanoparticles of 300 nm size having similar to 200 nm hollow space and 50 nm thickness was achieved at optimize condition of 4:6 volume ratio of ET/EN, 150 degrees C temperature, 0.1 M NaBH4 concentration, and 7 h. Ni HNSs supported over SiO2 (Ni HNSs/SiO2) with different loading of Ni HNSs (1-10 wt.%) were prepared by impregnation method. The catalyst was characterized by X-ray diffraction, and inductively coupled plasma - optical emission spectroscopy. The catalytic performance of Ni HNSs/SiO2 was carried out in the reduction of 4-Nitrophenol (4-NP) to 4 - Aminophenol (4-AP). 5 wt.% Ni HNSs/SiO2 exhibited 87% reduction of 4-NP in 25 min and stable up to 6 catalyst cycles due to higher surface area of the catalyst.
Keywords: 4-Aminophenol; 4-nitrophenol; Catalyst; hollow nanospheres; Nanoparticles; Nickel

Advances in C(sp(2))-H/C(sp(2))-H oxidative coupling of (Hetero)arenes using 3d transition metal catalysts - Bansal, Sadhna; Shabade, Anand B.; Punji, Benudhar (Advanced Synthesis & Catalysis, 2021)
C-H/C-H oxidative coupling has emerged as a straightforward and powerful technique for the construction of (hetero)biaryls, with substantial application to drug discovery, agrochemicals, biology, and material sciences. Mainly aryl-aryl, aryl-heteroaryl, and heteroaryl-heteroaryl couplings via double C(sp(2))-H activation using 4d or 5d noble transition metal catalysts have been extensively studied. Considering the earth-abundant and inexpensive nature of 3d transition metals, the sustainable development of C(sp(2))-H/C(sp(2))-H oxidative coupling employing such metal catalysts has gained significant attention. In this review, we present a comprehensive overview of C(sp(2))-H/C(sp(2))-H oxidative coupling of (hetero)arenes catalyzed by 3d transition metals.
Keywords: (hetero)biaryls; 3d transition metal; Biaryls; C-H activation; cross-dehydrogenative coupling