Total synthesis and structural assignment of hexaketide xylarinolb and its C1-epimer - Mullapudi, Venkanna Babu; Ramana, Chepuri V. (Asian Journal of Organic Chemistry, 2016)
The total synthesis of two isomeric hexaketides isolated along with sordarial, which have the proposed relative arabino and ribo configurations, has been executed. A Rh-catalyzed [2+2+2]-alkyne cyclotrimerization has been employed as the key reaction to construct the central dihydroisobenzofuran core. The absolute configuration of the xylarinolB hexaketide has been established as l-arabino. This is the first natural product of this family for which the absolute configuration has been determined, and this can be extended to provide structural details of several of related hexaketides.
Keywords: hexaketides; sordarial; Wilkinson's catalyst; xylarinolB; {[2+2+2]-cyclotrimerization

Total synthesis of integrastatin B enabled by a benzofuran oxidative dearomatization cascade - More, Atul A.; Ramana, Chepuri V. (Organic Letters, 2016)
The first total synthesis of integrastatin B, a potent HIV-1 integrase inhibitor, has been accomplished in seven steps with a 17.9% overall yield employing easily accessible starting compounds. The Oxone-mediated oxidative benzofuran dearomatization cascade has been employed as the key skeletal construct to forge the central tetracyclic nucleus.

Total synthesis of isocladosporin and 3-epi-isocladosporin - Mohapatra, Debendra K.; Maity, Saurabh; Banoth, Shivalal; Gonnade, Rajesh G.; Yadav, J. S. (Tetrahedron Letters, 2016)
A convergent total synthesis of isocladosporin and 3-epi-isocladosporin is reported starting from commercially available homoallyl alcohol in 10 longest linear steps with 28% overall yield. The key steps involved in the synthesis are cross-metathesis, tandem isomerization followed by C-O and C-C bond formation reactions for the synthesis of trans-2,6-disubstituted dihydropyrans developed by us, acylation reaction and Luche reaction. (C) 2015 Elsevier Ltd. All rights reserved.
Keywords: Acylation reaction; Cross-metathesis; Iodocyclization; Isocladosporin 3-epi-Isodadosporin; Luche reduction

Total synthesis of the marine natural product solomonamide B necessitates stereochemical revision - Kashinath, K.; Jachak, Gorakhnath R.; Athawale, Paresh R.; Marelli, Udaya Kiran; Gonnade, Rajesh G.; Reddy, D. Srinivasa (Organic Letters, 2016)
The first total synthesis of the proposed structure of solomonamide B has been achieved. However, the H-1 and C-13 NMR spectral data of the synthesized compound was not exactly matching with that of the natural solomonamide B. This prompted us to revise the originally proposed structure, in particular, the stereochemistry of the nonpeptide part, which was confirmed by its total synthesis. During the course of the synthesis, we have developed an interesting hydroxy group directed Wacker oxidation of internal olefins in a macrocyclic setting.

Tracing the architecture of caffeic acid phenethyl ester cocrystals: studies on crystal structure, solubility, and bioavailability implications - Ketkar, Sameer; Pagire, Sudhir K.; Goud, N. Rajesh; Mahadik, Kakasaheb R.; Nangia, Ashwini; Paradkar, Anant (Crystal Growth & Design, 2016)
Caffeic acid phenethyl ester (CAPE) is a polyphenolic active compound present in popular apiproduct, "propolis", obtained from beehives, Though it has broad therapeutic capability, the bioavailability of CAPE is limited due to poor solubility. In this study, we report novel cocrystals of CAPE engineered using coformers such as caffeine (CAP), isonicotinamide (INIC), and nicotinamide (NIC) with enhanced solubility and bioavailability of CAPE. The cocrystals were prepared by microwave-assisted cocrystallization and characterized using PXRD, DSC, and Raman spectroscopy. PXRD and DSC confirm the successful formation and phase purity of CAPE-CAF, CAPE-INIC, and CAPE-NIC cocrystals. Raman spectra of CAPE cocrystals complement these results in confirming the formation of novel crystalline phases. CAPE-NIC cocrystal was further subjected X-ray crystallography to understand its molecular arrangement and hydrogen bonding in the crystal structure. The CAPE-NIC cocrystal structure is found to be stabilized by a rare 1,2-benzenediol-amide heterosynthon. Cocrystallization of CAPE with NIC improved its aqueous solubility and pharmacokinetic profile, thereby demonstrating a 2.76-fold escalation in bioavailability.

Tuning emission responses of a triphenylamine derivative in host-guest complexes and an unusual dynamic inclusion phenomenon - Gangopadhyay, Monalisa; Mandal, Amal K.; Maity, Arunava; Ravindranathan, Sapna; Rajamohanan, Pattuparambil R.; Das, Amitava (Journal of Organic Chemistry, 2016)
A newly synthesized triphenylamine derivative (1Cl(3)) shows significant differences in inclusion complex formation with two different macrocyclic hosts, cucurbit[7]uril (CB[7]) and beta-cyclodextrin (beta-CD). Detailed investigations by NMR spectroscopy reveal that CB[7] forms a 1:3 host-guest complex ([1 center dot 3{CB[7]}]Cl-3) in which three arms of 1Cl(3) are bound to three host molecules. On the other hand, beta-CD forms a dynamic 1:1 inclusion complex ([1 center dotbeta-CD]Cl-3) by binding to only one of the three arms of 1Cl(3) at a given time. The formation of a 1:1 host-guest complex with beta-CD and 1:3 host-guest complex with CB[7] was also confirmed from the results of the isothermal titration calorimetric studies. Interestingly, 1Cl(3) exhibits a rare dual emission property in solution at room temperature with the lower and higher energy bands arising from a locally excited state and an intramolecular charge-transfer transition, respectively. The difference in inclusion complex formation behavior of 1Cl(3) with the two macrocyclic hosts results in the stabilization of different emission states in the two inclusion complexes. The fundamental difference in the electrostatic surface potentials, cavity polarities, and shapes of the two macrocyclic hosts could account for the formation of the different inclusion complexes with distinct luminescence responses.

Ultrahydrophobic fluorous metal-organic framework derived recyclable composite as apromising platform to tackle marine oil spills - Mukherjee, Soumya; Kansara, Ankit M.; Saha, Debasis; Gonnade, Rajesh; Mullangi, Dinesh; Manna, Biplab; Desai, Aamod V.; Thorat, Shridhar H.; Singh, Puyam S.; Mukherjee, Arnab; Ghosh, Sujit K. (Chemistry-A European Journal, 2016)
Derived from a strategically chosen hexafluorinated dicarboxylate linker aimed at the designed synthesis of a superhydrophobic metal-organic framework (MOF), the fluorine-rich nanospace of a water-stable MOF (UHMOF-100) exhibits excellent water-repellent features. It registered the highest water contact angle (approximate to 176 degrees) in the MOF domain, marking the first example of an ultrahydrophobic MOF. Various experimental and theoretical studies reinforce its distinc-tive water-repellent characteristics, and the conjugation of superoleophilicity and unparalleled hydrophobicity of a MOF material has been coherently exploited to achieve real-time oil/water separation in recyclable membrane form, with significant absorption capacity performance. This is also the first report of an oil/water separating fluorinated ultrahydrophobic MOF-based membrane material, with potential promise for tackling marine oil spillages.

Urinary proteome alterations in HER2 enriched breast cancer revealed by multipronged quantitative proteomics - Gajbhiye, Akshada; Dabhi, Raju; Taunk, Khushman; Vannuruswamy, Garikapati; RoyChoudhury, Sourav; Adhav, Ragini; Seal, Shubhendu; Mane, Anupama; Bayatigeri, Santhakumari; Santra, Manas K.; Chaudhury, Koel; Rapole, Srikanth (Proteomics, 2016)
Globally, breast cancer is the second most common cancer among women. Although biomarker discoveries through various proteomic approaches of tissue and serum samples have been studied in breast cancer, urinary proteome alterations in breast cancer are least studied. Urine being a noninvasive biofluid and a significant source of proteins, it has the potential in early diagnosis of breast cancer. This study used complementary quantitative gel-based and gel-free proteomic approaches to find a panel of urinary protein markers that could discriminate HER2 enriched (HE) subtype breast cancer from the healthy controls. A total of 183 differentially expressed proteins were identified using three complementary approaches, namely 2D-DIGE, iTRAQ, and sequential window acquisition of all theoretical mass spectra. The differentially expressed proteins were subjected to various bioinformatics analyses for deciphering the biological context of these proteins using protein analysis through evolutionary relationships, database for annotation, visualization and integrated discovery, and STRING. Multivariate statistical analysis was undertaken to identify the set of most significant proteins, which could discriminate HE breast cancer from healthy controls. Immunoblotting and MRM-based validation in a separate cohort testified a panel of 21 proteins such as zinc-alpha2-glycoprotein, A2GL, retinol-binding protein 4, annexin A1, SAP3, SRC8, gelsolin, kininogen 1, CO9, clusterin, ceruloplasmin, and alpha 1-antitrypsin could be a panel of candidate markers that could discriminate HE breast cancer from healthy controls.
Keywords: 2D-DIGE; Biomedicine; Breast cancer; HER2 enriched; SWATH; Urinary biomarkers

Utilization of banana peel for the removal of benzoic and salicylic acid from aqueous solutions and its potential reuse - Pathak, Pranav D.; Mandavgane, Sachin A.; Kulkarni, Bhaskar D. (Desalination and Water Treatment, 2016)
We report on the adsorptive removal of benzoic acid (BA) and salicylic acid (SA) using banana peel (BP), an abundantly available agricultural waste material, for the first time. BP was characterized by proximate analysis, FT-IR, scanning electron microscopy, BET surface area, and XRF. The number of basic sites on BP (4.9mmolg(-1)) is relatively more than acidic sites (0.75mmolg(-1)). The Langmuir uptake capacity values obtained are 6.62mgg(-1) for BA and 9.80mgg(-1) for SA. A mechanism for binding acid molecule to the BP surface is proposed.
Keywords: Adsorption; Banana peel; Benzoic acids; Salicylic acid; Wastewater treatment

Valorization of banana peel: a biorefinery approach - Pathak, Pranav D.; Mandavgane, Sachin A.; Kulkarni, Bhaskar D. (Reviews in Chemical Engineering, 2016)
Banana peel (BP) is an agrowaste produced in large volumes annually, especially by food-processing industries; however, its disposal is of significant concern. However, recent research suggests that BP is a valuable source of bioactive compounds, which can be converted into value-added products. This article reviews the conversion process of value-added products from BP and provides an outline on the chemical composition of BP and its possible applications. In addition, we also discuss the - utilization of BP as a substrate to produce animal feed, biofertilizer, dietary fibers, clean energy, industrial enzymes, as well as its use in the synthesis of nanomaterials. Based on the research conducted so far, it is obvious that BP has a wide variety of applications, and thus, developing a biorefinery approach to adequately utilize BP will help realize its economic benefits to the fullest. Based on the valorization of BP, a scheme for BP biorefinery has been proposed. A material balance for BP biorefinery for 1-ton bone-dry BP is presented and our results show that 432 kg of protein or 170 kg of citric acid, 170 kg of pectin, 325 m(3) of ethanol, and 220 m(3) of methane can be produced.

Virtual screening techniques to probe the antimalarial activity of some traditionally used phytochemicals - Shibi, Indira G.; Aswathy, Lilly; Jisha, Radhakrishnan S.; Masand, Vijay H.; Gajbhiye, Jayant M. (Combinatorial Chemistry & High Throughput Screening, 2016)
Malaria parasites show resistance to most of the antimalarial drugs and hence developing antimalarials which can act on multitargets rather than a single target will be a promising strategy of drug design. Here we report a new approach by which virtual screening of 292 unique phytochemicals present in 72 traditionally important herbs is used for finding out inhibitors of plasmepsin-2 and falcipain-2 for antimalarial activity against P. falciparum. Initial screenings of the selected molecules by Random Forest algorithm model of Weka using the bioassay datasets AID 504850 and AID 2302 screened 120 out of the total 292 phytochemicals to be active against the targets. Toxtree scan cautioned 21 compounds to be either carcinogenic or mutagenic and were thus removed for further analysis. Out of the remaining 99 compounds, only 46 compounds offered drug-likeness as per the `rule of five' criteria. Out of ten antimalarial drug targets, only two target proteins such as 3BPF and 3PNR of falcipain-2 and 1PFZ and 2BJU of plasmepsin-2 are selected as targets. The potential binding of the selected 46 compounds to the active sites of these four targets was analyzed using MOE software. The docked conformations and the interactions with the binding pocket residues of the target proteins were understood by `Ligplot' analysis. It has been found that 8 compounds are dual inhibitors of falcipain-2 and plasmepsin-2, with the best binding energies. Compound 117 (6aR, 12aS)-12a-Hydroxy-9-methoxy-2,3-dimethylenedioxy-8-prenylrotenone (Usaratenoid C) present in the plant Millettia usaramensis showed maximum molecular docking score.
Keywords: ADME; malaria; Molecular docking; molecular operating environment; Plasmodium falciparum; virtual screening; weka

Achmatowicz reaction: A versatile tool in bioactive natural products synthesis - Mahajan, Pankaj S.; Humne, Vivek T.; Mhaske, Santosh B. (Current Organic Chemistry, 2017)
Achmatowicz reaction has emerged as an efficient tool in organic synthesis since its discovery in 1971 by Achmatowicz Jr. The original protocol went through several advantageous variations. Biocatalytic and metal catalyzed versions of this reaction are some of the significant achievements, which further enhanced its effectiveness. The pyranone product of the Achmatowicz reaction is a versatile building block for the synthesis of bioactive scaffolds, drugs and natural products. The present review covers the application of the Achmatowicz reaction in the synthesis of natural products and bioactive molecules reported from 1971 to date. It has been divided into seven sections on the basis of the core structures of the natural products synthesized utilizing the Achmatowicz reaction. We believe that this comprehensive review will attract many more organic chemists to explore its utility in organic synthesis, especially in the synthesis of bioactive natural products as well as drugs in their efficient and atom economical synthesis.
Keywords: Achmatowicz reaction; carbohydrates; Furanols; Natural products; pyranones; Total synthesis

Alternatively packed dry molten globule-like intermediate in the native state ensemble of a multidomain protein - Mishra, Prajna; Jha, Santosh Kumar (Journal of Physical Chemistry B, 2017)
It has been difficult to quantify the degree of side-chain conformational heterogeneity in the native (N) state ensemble of proteins and the relative energetic contributions of the side-chain packing and the hydrophobic effect in protein stability. Here, we show using multiple site specific spectroscopic probes and tools of thermodynamics that the N state ensemble of a multidomain protein contains an equilibrium intermediate (I) whose interdomain region resembles a dry molten globule. In the I state, a tryptophan residue in the interdomain region is alternatively packed, but its secondary structure and intradomain packing are N-like. The I state also has a larger interdomain distance, but the domain-domain interface is dry and molten. Our results indicate that hydrophobic desolvation and side-chain packing are decoupled during protein folding and that interdomain packing interactions have an important energetic contribution in protein stability. Dynamic interconversion between alternatively packed N-like states could be important for multiple allosteric and ligand binding functions of this protein.

Assessing therapeutic potential of molecules: molecular property diagnostic suite for tuberculosis - Gaur, A. S.; Bhardwaj, A.; Sharma, A.; John, L.; Vivek, M. R.; Tripathi, N.; Bharatam, P. V.; Kumar, R.; Janardhan, S.; Mori, A.; Banerji, A.; Lynn, A. M.; et al. (Journal of Chemical Sciences, 2017)
Abstract: Molecular Property Diagnostic Suite (MPDS TB) is a web tool (http://mpds.osdd.net) designed to assist the in silico drug discovery attempts towards Mycobacterium tuberculosis (Mtb). MPDS TB tool has nine modules which are classified into data library (1–3), data processing (4–5) and data analysis (6–9). Module 1 is a repository of literature and related information available on the Mtb. Module 2 deals with the protein target analysis of the chosen disease area. Module 3 is the compound library consisting of 110.31 million unique molecules generated from public domain databases and custom designed search tools. Module 4 contains tools for chemical file format conversions and 2D to 3D coordinate conversions. Module 5 helps in calculating the molecular descriptors. Module 6 specifically handles QSAR model development tools using descriptors generated in the Module 5. Module 7 integrates the AutoDock Vina algorithm for docking, while module 8 provides screening filters. Module 9 provides the necessary visualization tools for both small and large molecules. The workflow-based open source web portal, MPDS TB 1.0.1 can be a potential enabler for scientists engaged in drug discovery in general and in anti-TB research in particular. Graphical Abstract: SYNOPSIS: A web-based MPDS TB Galaxy tool is developed for assessing therapeutic potential of molecules. MPDS TB is categorized into Data Library, Data Processing and Data Analysis. It can be a potential enabler for scientists engaged in drug discovery in general and in anti-TB research in particular. [Figure not available: see fulltext.] © 2017, Indian Academy of Sciences.
Keywords: chemical analysis; Chemoinformatics; computational chemistry; Diagnosis; Drug discovery portal; Information analysis; Libraries; Molecular graphics; Molecules; Neglected diseases; Open science; Portals; tuberculosis; Web-based technology; Websites

Band alignment and charge transfer pathway in three phase anatase-rutile-brookite TiO2 nanotubes: an efficient photocatalyst for water splitting - Preethi, L. K.; Mathews, Tom; Nand, Mangla; Jha, S. N.; Chinnakonda, Gopinath S.; Dash, Sitaram (Applied Catalysis B-Environmental, 2017)
The study reports electrochemical synthesis, phase evolution and hydrogen generation efficiency of anatase, anatase-rutile and anatase-rutile-brookite (ARB) TiO2 nanotubes for the first time. The SEM and TEM micrographs confirm the tubular morphology of the samples. The presence of anatase, rutile and brookite phases in a single nanotube is confirmed from high resolution TEM analysis. The water splitting efficiency of the three systems are studied under one sun illumination. It is observed that the anatase-rutile-brookite TiO2 nanotubes are highly efficient compared to anatase-rutile or anatase TiO2 nanotubes. The hydrogen generated by ARB composites, after four hours of one sun illumination, is found to be nearly twice that of anatase TiO2 nanotubes and 1.6 times that of anatase-rutile TiO2 nanotubes. The results suggest that the ARB in single nanotube having two junction interfaces, highly facilitate interparticle charge transfer compared to single junction anatase-rutile or bare anatase TiO2 nanotubes. From the deconvolution of PL spectra and the synchrotron radiation assisted valence band edge analysis, the band diagram for the anatase-rutile-brookite phase is constructed. The charge separation and its transfer pathway for efficient photo-assisted water splitting are delineated. This opens a new route for the simple synthesis and study of tri-phase TiO2 for efficient photocatalytic water splitting compared to the widely studied two phase TiO2. (C) 2017 Published by Elsevier B.V.
Keywords: Anatase-Rutile-Brookite; Hydrogen generation; nanotubes; Photocatalysis; photoluminescence; Valence band edge

Base-free and catalyst-free synthesis of functionalized dihydrobenzoxazoles via vinylogous carbonate to carbamate rearrangement - Das, Tamal Kanti; Mondal, Santigopal; Gonnade, Rajesh G.; Biju, Akkattu T. (Organic Letters, 2017)
An unexpected, catalyst-free, and base-free intramolecular cyclization of N-aryloxyacrylate aldimines, under thermal conditions leading to the synthesis of functionalized dihydrobenzoxazoles, is reported. The reaction features a unique rearrangement of vinylogous carbonates to vinylogous carbamates resulting in a new carbon–oxygen and carbon–nitrogen bond construction. The reaction tolerates a broad range of functional groups and the desired products are formed in moderate to good yields.

Binding selectivity of vitamin K3 based chemosensors towards nickel(II) and copper(II) metal ions - Patil, Amit; Lande, Dipali N.; Nalkar, Archana; (Gejji, Shridhar P.; Chakrovorty, Debamitra; Gonnade, Rajesh; Moniz, Tania; Rangel, Maria; Pereira, Eulalia; Salunke-Gawali, Sunita (Journal of molecular Structure, 2017)
The vitamin K3 derivatives 2-methyl-3-[(pyridin-2-ylmethyl)-amino]-1,4-naphthoquinone (M-1), 2-methyl-3-[(pyridin-2-ylethyl)-amino]-1,4-naphthoquinone (M-2), 2-methyl-3-((2-(thiophen-2-yl) methyl)amino)naphthalene-1,4-dione (M-3) and 2-methyl-3-((2-(thiophen-2-yl)ethyl)amino)naphthalene-1,4-dione (M-4) have been synthesized, characterized and studied for their chemosensor abilities towards transition metal ions. Crystal structures of M-1 to M-4 revealed a variety of N-H center dot center dot O, C-H center dot center dot center dot O, C-H center dot center dot center dot pi and pi center dot center dot center dot pi interactions. Minor variations in such interactions by chemical stimuli such as metal ions, results in change in color that can be visualized by naked eyes. It has been shown that electronic structure and H-1 NMR, vibrational as well as electronic spectra from the density functional theory agree well with the experiments. The metal ion binding in ethanol, ethanol-water and in mild base triethylamine brings forth recognizing ability of M-1 toward Ni2+ whereas M-2 exhibits large sensing ability for Cu2+ ion. Interestingly M-1 display varying metal ion binding specificity in different solvents with the association constant in ethanol being 11,786 M-1 for Ni2+ compared to 9462 M-1 for the Cu2+. A reversal in preferential binding of M-2 with the respective association constants being 4190 M-1 and 6370 M-1 is discernible. (C) 2017 Elsevier B.V. All rights reserved.
Keywords: Aminonaphthoquinone Molecular-structures; Anthraquinone; Aqueous-solution; Chemosensor; Crystal-structures; Cu(II); Derivatives; DFT; Fluorometric Chemosensors; hydrogen bonding; Naphthoquinone; pi-pi stacking; Recognition; sensors

Biocompatible superhydrophobic coating material for biomedical applications - Mahadik, Satish A.; Pedraza, F.; Mahadik, Sarika S.; Relekar, Brahmanand P.; Thorat, Sagar S. (Journal of Sol-Gel Science and Technology, 2017)
Biomaterials and wettability have played a crucial role in the biocompatibility with a host matrix of body fluid and cells. We discuss designing superhydrophobic biomaterials for novel applications such as temporally implant, contact lenses, controlled drug release coatings, coating on medical instruments, etc. Such Superhydrophobic coating surfaces were created with the simple dip coating method by single step base catalyst sol-gel method. Methyltriethoxysilane/trimethoxymethylsilane-based deposition at different dip periods introduces interesting properties in the region, including superhydrophobicity, biocompatibility and transparency. This works reveal the impact of interaction bone marrow mesenchymal stem cells and surface free energy on the biocompatibility of superhydrophobic biomaterial.

Biosurfactant surfactin as a kinetic promoter for methane hydrate formation - Bhattacharjee, Gaurav; Barmecha, Vivek; Pradhan, Darshan; Naik, Rajesh; Zare, Kirti; Mawlankar, Rahul R.; Dastager, Syed Gulam; Kushwaha, Omkar Singh; Kumar, Rajnish (Energy Procedia, 2017)
In the present study, the effect of the biosurfactant Surfactin on methane hydrate formation kinetics was studied. Initially, several marine derived species were screened for the presence of Surfactin. The polymerase chain reaction technique was used as the preliminary screening step for Surfactin which was then followed up by a couple of different assays to provide conclusive evidence of the same. Based on these tests, the D-9 bacterial strain was identified as a producer of Surfactin. Once the presence of Surfactin had been proven, its effect on methane hydrate formation kinetics was investigated upon by carrying out hydrate formation experiments in a stirred tank reactor. The cell free supernatant containing Surfactin was itself used as the hydrate forming solution without any further processing. It was found that the presence of Surfactin in the system greatly enhances hydrate formation kinetics as compared to pure water. In fact the kinetics in presence of Surfactin also surpassed that obtained with 1 wt% SDS, the most commonly used synthetic kinetic hydrate promoter. This basic study can pave the way for more sophisticated research on the use of biosurfactants as kinetic promoters with a view on rapid methane hydrate formation kinetics for applications such as methane separation, storage and transport.

Biosynthesis of glycomonoterpenes to attenuate quorum sensing associated virulence in bacteria - Patil, Amrita; Joshi-Navre, Kasturi; Mukherji, Ruchira; Prabhune, Asmita (Biotechnology and Applied Biochemistry, 2017)
The acquisition of multidrug resistance in bacteria has become a bigger threat of late, mainly due to the bacterial signaling phenomenon, quorum sensing (QS). QS, among a population of bacteria, initiates the formation of biofilms and offers myriad advantages to bacteria. Burgeoning antibiotic resistance in biofilm-producing bacteria has motivated efforts toward finding new alternatives to these traditional antimicrobials. In the present study, we report the increased solubility and additional quorum quenching as well as biofilm disruption activity of glyco-derivatives of monoterpenes (citral and citronellal). Glycomonoterpenes of citral and citronellal were synthesized via conjugation of the monoterpenes with glucose by the non-pathogenic yeast Candida bombicola (ATCC 22214). Structural elucidation of newly synthesized glycomonoterpenes showed that one synthesized using citronellal contains three major lactonic forms with molecular weight 492.43, 473.47, and 330.39 Da whereas the one produced using citral has an acidic form with molecular weight 389.33 and 346.23 Da. The glycomonoterpenes were able to individually inhibit QS, mediated through various medium-chain and long-chain N-acyl homoserine lactones (AHLs). These new compounds are interesting additions to the known range of quorum sensing inhibitors (QSIs) and could be further explored for potential clinical applications.

Biotechnological interventions to modulate terpenoid indole alkaloid pathway in catharanthus roseus using in vitro tools and approaches - Verma, P.; Khan, S. A.; Parasharami, V.; Mathur, A. K. (Catharanthus Roseus: Current Research and Future Prospects, 2017)
Catharanthus roseus plant is valued for harboring more than 130 bioactive terpenoid indole alkaloids (TIAs) including the two of its leaf derived bisindole alkaloids-vinblastine and vincristine which are indispensible constituents of antineoplastic drugs used in metastatic malignancy associated with acute lymphoblastic leukaemia's and Hodgkin's/Non-Hodgkin's lymphomas. The extremely low in planta occurrence of TIAs in C. roseus plants resulting in high commercial demand and exorbitant price have brought this herb in focus of an intense scientific scrutiny in last 30 years. Research efforts have so far advanced in two major directions: towards understanding the enzymology and genetic regulation of the concerned metabolic pathway(s) leading to TIAs biosynthesis in plant and, secondly, exploring the possibility of developing cell/tissue culture based platforms for in vitro TIAs production to meet the industry's demand. Designing plants, free from such metabolic constraints, can be a possible approach to enhance the production of plant based medicines. This subject of plant metabolic engineering is gaining lot of attention these days. Pathway manipulation using the modern tools of genetic engineering to over-express a limiting enzyme or to suppress the expression of an enzyme using a shared substrate of a branched pathway are attractive options of metabolic engineering for diverting the metabolic flux towards the synthesis of a desired end product. Knowledge, thus gained, indicates that TIAs biogenetic route is characterized by extensive metabolic cross-talk and shuttling of at least 35 intermediates synthesized via 30 enzymatic reactions occurring in four different types of tissues (epidermis, internal phloem parenchyma, idioblasts and leticifers) and five different sub-cellular compartments (cytosol, vacuole, thyllakoid membrane, nucleus and endoplasmic reticulum). The complexity is further compounded by extremely high level of recalcitrancy of C. roseus plant for regeneration and Agrobacterium- mediated genetic transformation for pathway engineering. As a consequence, all genetic modulation efforts so far made in C. roseus are confined to cell suspension and transformed hairy root cultures that lack the required level of cyto- and tissue- differentiation essential for the expression of entire TIAs pathway genes and enzymes. A perusal of published work in C. roseus clearly suggests that inspite of several pathway manipulation/engineering attempts, the level of TIAs production in cell/tissue/hairy root cultures of this herb could never be enhanced to the level of expectations. The enzymatic, developmental and environmental rigidity/complexi- ties associated with the biosynthetic pathway of these alkaloids have often been cited as possible reasons for these disappointing outcomes Therefore, three major areas of investigation are in focused attention of Catharanthus researchers' the world over are: (1) how to select or design the starting cells or tissue(s) to realize the full potential of applying metabolic engineering tools for up-regulating the TIAs pathway in them; (2) how to overcome the strong recalcitrancy of Catharanthus plant tissues for de novo organogenesis and in vitro plant regeneration for whole plant-level expression of a transgene coding either for a limiting pathway enzyme or a transcription factor that can control the global expression of several pathway genes and, (3) how to overcome the inability of non-differentiated cell cultures to execute those pathway steps that are expressed only in specialized tissues/cells of C. roseus plants. Various biotechnological approaches and generation of novel tissue types have been discussed in the present chapter for the modulation and increased TIAs flux in C. Roseus.

Bronsted acid catalyzed enantioselective pericyclic reactions - Sleet, Christopher E.; Tambar, Uttam K.; Maity, Pradip (Tetrahedron, 2017)
Pericyclic reactions can be challenging processes to render asymmetric, due to the concerted and non polar nature of the transition states. Several examples have been reported in which a suitable catalyst binds to a heteroatom-containing substituent in the substrate and accelerates the reaction rate. The requirement of coordinating functionalized substrates has limited the generality of such asymmetric transformations. Multifunctional Bronsted acids are promising catalysts that represent a new paradigm in asymmetric pericyclic reactions. These chiral catalysts rely on multiple non-covalent interactions in the transition state for asymmetric induction, which has been utilized to activate more general substrate classes. In this review, we will cover recent advances in Bronsted acid catalyzed pericyclic reactions and discuss the impact of catalyst design on the expansion of substrate scope for highly enantioselective processes. (C) 2017 Elsevier Ltd. All rights reserved.

Calixarene based nanocomposite materials for high performance supercapacitor electrode - Waghmode, Babasaheb J.; Soni, Roby; Patil, Kashinath Rangu; Malkhede, Dipalee D. (New Journal of Chemistry, 2017)
A functionalised calixarene {4-Sulphatocalix [6] arene Hydrate (SC6)} stabilises MoS2/partially reduced graphene oxide (rGO) nanosheet. Such stabilised SC6-rGO/SC6-MoS2 and SC6 doped polyaniline (PANI) together forms a nanocomposite hybrid material for supercapacitor electrode. It was fabricated by an in situ polymerization method. Transmission electron microscopy (TEM) results suggest that PANI nanostructures grow homogeneously onto the surfaces of SC6 functionalised MoS2. Calixarene acts as a dopant for PANI as well as a stabiliser for the 2D nanosheets of rGO/MoS2. The characterisation of composites together with basic components was done by using various techniques namely, solid-state FT-IRspectroscopy, X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The electrochemical performance was analysed by cyclic voltammetry (CV), galvanostatic charge/discharge and electrochemical impedance spectrometry (EIS). It was found that the SC6 functionalised MoS2 and SC6 doped PANI formed a uniform nanocomposite. The synthesised composites show high specific capacitance (691 F/g) and good cycling stability during the charge-discharge process when used as supercapacitor electrodes. The improvement in electrochemical performance of composites is assigned to synergistic effect of SC6 stabilised MoS2 and doped PANI. Our investigation highlighted the importance of use of calixarene in composites for above stated supercapacitor performance. The role of calixarene in the present study opens a way for the application of alike materials in the composite supercapacitors for energy storage applications.

Camptothecin-producing endophytic bacteria from pyrenacantha volubilis hook. (Icacinaceae): a possible role of a plasmid in the production of camptothecin - Soujanya, K. N.; Siva, R.; Kumara, P. Mohana; Srimany, Amitava; Ravikanth, G.; Mulani, F. A.; Aarthy, T.; Thulasiram, H. V.; Santhoshkumar, T. R.; Nataraja, Karaba N.; Shaanker, R. Uma (Phytomedicine, 2017)
Background: Camptothecin (CPT), a quinoline alkaloid, is a potent inhibitor of eukaryotic topoisomerase I. Because of this property, several derivatives of CPT are used as chemotherapeutic agents. CPT is produced by several plant species belonging to the Asterid clade as well as by a number of endophytic fungal associates of these plants. In this study, we report the production of CPT by four bacterial endophytes and show the possible role of a plasmid in the biosynthesis of CPT. Methods: Endophytic bacteria were isolated from leaves, stems and fruits of Pyrenacantha volubilis Hook. (Icacinanceae). The bacterial isolates were purified and analyzed for production of CPT by ESI-MS/MS and NMR analysis. Bacterial identity was established based on the morphology and 16s rRNA sequence analysis. Crude extracts of the bacterial endophytes were evaluated for their cytotoxicity using colon cancer cell lines. The role of plasmid in the production of CPT was studied by purging the plasmid, using acriflavine, as well as reconstituting the bacteria with the plasmid. Results: Four bacterial isolates, Bacillus sp. (KP125955 and KP125956), Bacillus subtilis (KY741853) and Bacillus amyloliquefaciens (KY741854) were found to produce CPT in culture. Both based on ESI-MS/MS and NMR analysis, the identity of CPT was found to be similar to that produced by the host plant. The CPT was biologically active as evident by its cytotoxicity against colon cancer cell line. The production of CPT by the endophyte (Bacillus subtilis, KY741853) attenuated with sub-culture. A likely role of a plasmid in the production of CPT was established. A 5 kbp plasmid was recovered from the bacteria. Bacterial isolate cured of plasmid failed to produce CPT. Conclusion: Our study implies a possible role of a plasmid in the production of CPT by the endophytic bacteria and opens up further work to unravel the exact mechanisms that might be involved.

Carbonylation of glycerol with urea to glycerol carbonate over supported Zn catalysts - Kondawar, S. E.; Mane, R. B.; Vasishta, A.; More, S. B.; Dhengale, S. D.; Rode, C. V. (Applied Petrochemical Research, 2017)
Glycerol carbonylation with urea is a very feasible option to produce glycerol carbonate with a net result of CO2 fixation through urea synthesis. The prerequisite of an efficient catalyst for this reaction is to possess both acid and basic sites together. Several acidic supports were screened for ZnO catalyst in this work and Zn/MCM-41 was found to exhibit the best activity and almost complete selectivity to glycerol carbonate (GC). Although, non-catalytic glycerol carbonylation resulted in GC formation but glycerol conversion achieved was twice with Zn/MCM-41 as a catalyst. Further to that increase in Zn loading from 2 to 5% resulted in increase in glycerol conversion from 63 to 82%. The prepared catalysts were characterized by XRD, NH3 and CO2-TPD and effects of reaction parameters such as catalyst loading, glycerol to urea mole ratio and temperature on glycerol conversion and GC selectivity in batch mode of operation were also studied. Time on stream activity of 5% Zn/MCM-41 catalyst for continuous carbonylation of glycerol was also studied for ~100 h with an average conversion of ~55% and complete selectivity to GC. This indicated five times lower productivity of GC per h due to lower residence time than that in a batch operation as compared to that of a continuous operation. Activation energy estimated from the Arrhenius plot was found to be 39.82 kJ mol−1 suggesting that the reaction is kinetically controlled. A reaction pathway mediated by acid and basic sites of the Zn/MCM-41 catalyst is also proposed.
Keywords: Acid–base ratio; Continuous process; Glycerol carbonate; Glycerol-urea carbonylation; reaction pathway; Supported Zn; Zn loading

Catalytic ozonation of clofibric acid over copper-based catalysts: in situ ATR-IR studies - Sable, Shailesh S.; Ghute, P. P.; Fakhrnasova, D.; Mane, R. B.; Rode, Chandrashekhar V.; Medina, F.; Contreras, S. (Applied Catalysis B-Environmental, 2017)
The current study describes the catalytic ozonation of clofibric acid (CFA) under ambient conditions using copper oxide catalysts synthesized by different methods. The objective of this study is to provide novel catalysts and reaction mechanism for the degradation of emerging pharmaceutical compounds in aqueous solution. Among the various Cu catalysts screened in this study, the Cut-Ali oxide catalyst showed an excellent activity and stability in the degradation and mineralization of CFA. In situ attenuated total reflection IR (ATR-IR) spectroscopy was used to examine the interaction of ozone with the active sites of the catalyst in presence of water and to investigate the possible catalytic mechanism. The presence of Lewis acid sites in the Cut-Ali catalyst increased the amount of chemisorbed water enhancing stronger interaction of ozone to form surface activated species, resulting in higher catalytic activity. The results obtained from in-situ ATR-IR study indicate that surface hydroxyl groups and Lewis acid sites are responsible for promoting the generation of hydroxyl radicals (OHS) from aqueous ozone. (C) 2017 Elsevier B.V. All rights reserved.

Chiral discrimination through h-1 nmr and luminescence spectroscopy: dynamic processes and solid strip for chiral recognition - Gangopadhyay, Monalisa; Maity, Arunava; Dey, Ananta; Rajamohanan, P. R.; Ravindranathan, Sapna; Das, Amitava (Chemistry-A European Journal, 2017)
The appropriate choice of the host molecules with well-defined optical activity (S-H/R-H) helps in the differentiation between two secondary ammonium ion-derivative guest molecules with different optical activities (R-G/S-G) based on the fluorescence resonance energy transfer (FRET)based luminescence responses. Crown ether-based host molecules with opposite chiral configurations (R-H, S-H) have been derived from 1,1'-bi-2-naphthol (BINOL) derivatives that have axially chiral biaryl centers. These chiral crown ethers form host-guest complexes (i.e., [2] pseudoro-taxanes) with chiral secondary ammonium ion derivatives (R-G, S-G). NMR spectroscopic studies show that the complexes are in a dynamic equilibrium in solution. Results of the H-1 NMR and fluorescence spectroscopic studies indicate a head-on orientation of the host and guest in the [2] pseudorotaxanes. The difference in the efficiency in the FRET-based responses between anthracene and the BINOL derivatives allow efficient chiral discrimination of the guests. Isothermal titration calorimetry and NMR investigations reveal that inclusion complexes between hosts and guests of the same chirality (R-H center dot R-G, S-H center dot S-G) are more stable relative to those of opposite chirality (R-H center dot S-G, S-H center dot R-G). However, FRET-based energy-transfer efficiency is higher for R-H center dot S-G and S-H center dot R-G complexes. NMR spectroscopic studies show that the relative orientation of the guest in the host cavity is significantly different when the host binds a guest of the same or opposite chirality; furthermore, the latter is more favorable for FRET, thus enabling discrimination between enantiomers. Interestingly, chiral discrimination of guest ions could also be achieved by using silica surfaces modified with chiral host molecules.

Chitosan intercalated metal organic gel as a green precursor of fe entrenched and fe distributed N-doped mesoporous graphitic carbon for oxygen reduction reaction - Shijina, Kottarathil; Illathvalappil, Rajith; Kurungot, Sreekumar; Nair, Balagopal N.; Mohamed, A. Peer; Yamaguchi, Takeo; Anilkumar, Gopinathan M.; Hareesh, U. S.; Sailaja, G. S. (Chemistryselect, 2017)
Herein, we present Metal-Organic Gel intercalated with chitosan, a `green'' precursor for the synthesis of intrinsic N-doped Fe entrenched (CHI-TMA-Fe-CW) and Fe distributed mesoporous graphitic carbon structures (CHI-TMA-Fe-CW-M1) with appreciable Oxygen Reduction Reaction (ORR) activity in alkaline medium. Modulation of the synthetic protocol as a function of reaction kinetics and gelation time while maintaining identical pyrolysis conditions (900 degrees C, flowing N-2 atmosphere) improves the microstructure, surface area and Fe distribution of the graphitic structures (CHI-TMA-Fe-CW-M1). CHI-TMA-Fe-CW has a Fe entrenched graphitic nanocapsule like morphology while Fe distributed mesoporous graphitic carbon sheets, with a specific surface area value of 565 m(2) g(-1) obtained by modulating the synthesis chemistry in CHI-TMA-Fe-CW-M1. The higher percentage of graphitic N in CHI-TMA-Fe-CW-M1 apparent from the XPS data validate that the modified synthetic method favours creation of more graphitic N sites contributing for better catalytic performance. CHI-TMA-Fe-CW-M1 catalyst exhibited comparable electrocatalytic activity with that of the commercially available Pt/C via an efficient four-electron-dominant ORR pathway with a positive onset potential value of 0.925 V vs RHE. Good durability of CHI-TMA-Fe-CW-M1 after 5000 cycles further confirm the prospects of MOG-chitosan and the feasibility to be used as a potential catalyst for ORR.
Keywords: electrocatalyst; fuel cell; Metal-Organic-Gel; oxygen reduction reaction

CHO Cells Adapted to Inorganic Phosphate Limitation Show Higher Growth and Higher Pyruvate Carboxylase Flux in Phosphate Replete Conditions - Maralingannavar, Vishwanathgouda;; Parmar, Dharmeshkumar; Pant, Tejal; Gadgil, Chetan; Panchagnula, Venkateswarlu; Gadgil, Mugdha (Biotechnology progress, 2017)
Inorganic phosphate (P-i) is an essential ion involved in diverse cellular processes including metabolism. Changes in cellular metabolism upon long term adaptation to P-i limitation have been reported in E. coli. Given the essential role of P-i, adaptation to P-i limitation may also result in metabolic changes in animal cells. In this study, we have adapted CHO cells producing recombinant IgG to limiting P-i conditions for 75 days. Not surprisingly, adapted cells showed better survival under P-i limitation. Here, we report the finding that such cells also showed better growth characteristics compared to control in batch culture replete with P-i ( higher peak density and integral viable cell density), accompanied by a lower specific oxygen uptake rate and cytochrome oxidase activity towards the end of exponential phase. Surprisingly, the adapted cells grew to a lower peak density under glucose limitation. This suggests long term P-i limitation may lead to selection for an altered metabolism with higher dependence on glucose availability for biomass assimilation compared to control. Steady state U-C-13 glucose labeling experiments suggest that adapted cells have a higher pyruvate carboxylase flux. Consistent with this observation, supplementation with aspartate abolished the peak density difference whereas supplementation with serine did not abolish the difference. This supports the hypothesis that cell growth in the adapted culture might be higher due to a higher pyruvate carboxylase flux. Decreased fitness under carbon limitation and mutations in the sucABCD operon has been previously reported in E. coli upon long term adaptation to P-i limitation, suggestive of a similarity in cellular response among such diverse species. (C) 2017 American Institute of Chemical Engineers

Cisplatin-induced self-assembly of graphene oxide sheets into spherical nanoparticles for damaging sub-cellular DNA - Nandi, Aditi; Mallick, Abhik; More, Piyush; Sengupta, Poulomi; Ballav, Nirmalya; Basu, Sudipta (Chemical Communications, 2017)
This report describes the hitherto unobserved cisplatin induced self-assembly of 2D-graphene oxide sheets into 3D-spherical nano-scale particles. These nanoparticles can encompass dual DNA damaging drugs simultaneously. A combination of confocal microscopy, gel electrophoresis and flow cytometry studies clearly demonstrated that these novel nanoparticles can internalize into cancer cells by endocytosis, localize into lysosomes, and damage DNA, leading to apoptosis. Cell viability assays indicated that these nanoparticles were more cytotoxic towards cancer cells compared to healthy cells.

Colloidal nanocomposite of TiN and N-doped few-layer graphene for plasmonics and electrocatalysis - Shanker, G. Shiva; Markad, Ganesh B.; Jagadeeswararao, Metikoti; Bansode, Umesh; Nag, Angshuman (ACS Energy Letters, 2017)
A combination of high carrier density, high surface area, solution processability, and low cost is desired in a material for electrocatalytic applications, including H-2 evolution and a counter electrode of a solar cell. Also, plasmonic-based applications in biological systems can be derived from such material. In this regard, a colloidal nanocomposite of TiN and N-doped few-layer graphene (TiN NFG) is synthesized from molecular precursors. TiN nano crystals (NCs) provide free electrons for electrical conductivity and plasmonics, whereas NFG is responsible for charge transport, high surface area, and colloidal stability. Colloidal TiN NFG nano composites exhibit a localized surface plasmon resonance band at around 700 nm. Coatings of the nanocomposite form a counter electrode for efficient (8.9%) dye-sensitized solar cells. Furthermore, the nanocomposite acts as an efficient electrocatalyst for hydrogen evolution reaction, exhibiting an overpotential similar to 161 mV at a current density of 10 mA/cm(2).

Colossal photo-conductive gain in low temperature processed TiO2 films and their application in quantum dot solar cells - Mandal, Debranjan; Goswami, Prasenjit N.; Rath, Arup K. (Applied Physics Letters, 2017)
Colloidal quantum dot (QD) solar cells have seen remarkable progress in recent past to reach the certified efficiency of 10.6%. Anatase titanium oxide (TiO2) is a widely studied n-type widow layer for the collection of photogenerated electrons in QD solar cells. Requirement of high temperature (similar to 500 degrees C) processing steps proved to be disadvantageous for its applications in flexible solar cells and roll to roll processing, and it also has adverse commercial implications. Here, we report that solar light exposure to low temperature processed (80 degrees C-150 degrees C) TiO2 and niobium doped TiO2 films leads to unprecedented enhancement in their electron densities and electron mobilities, which enables them to be used as efficient n-type layers in quantum dot solar cells. Such photoinduced high conducting states in these films show gradual decay over hours after the light bias is taken off and can be retrieved under solar illumination. On the contrary, TiO2 films processed at 500 degrees C show marginal photo induced enhancements in their characteristics. In bilayer configuration with PbS QDs, photovoltaic devices based on low temperature processed TiO2 films show improved performance over high temperature processed TiO2 films. The stability of photovoltaic devices also improved in low temperature processed TiO2 films under ambient working conditions. Published by AIP Publishing.

Comparative analysis of extractive and pressure swing distillation for separation of THF-water separation - Ghuge, Pravin D.; Mali, Nilesh A.; Joshi, Sunil S. (Computers & Chemical Engineering, 2017)
In the present work, extractive and pressure-swing distillation methods are analyzed in detail through steady state ASPEN Plus simulations to propose the most economic method for separation of equimolar mixture of THF-Water. Various solvents were evaluated and DMSO was identified as the most appropriate solvent, as it gave minimum Total Annual Cost (TAC) for desired purity. In case of pressure swing distillation, various pressure ranges were explored to achieve minimum TAC. Configurations for extractive and pressure swing distillation with heat integration were also worked out. The optimum designs of extractive and pressure swing distillation with and without heat integration were compared on a common basis of feed conditions and purity constraints. Results indicate that TAC of extractive distillation with heat integration is 5.2% less than that of PSD with partial heat integration. (C) 2017 Elsevier Ltd. All rights reserved.

Compositional dependence of electrical conduction in solution grown Zn1-xCrxSe thin films: a correlation - Deshmukh, S. L.; Pingale, P. C.; Chavan, G. T.; Pawar, S. T.; Prakshale, V. M.; Kamble, S. S.; Jadkar, S. R.; Chaure, N. B.; Gopinath, C. S.; Maldar, N. N.; Deshmukh, L. P. (Journal of Materials Science: Materials in Electronics, 2017)
Zinc selenide (ZnSe) has a typical band gap of 2.7 eV suitable for window application and can easily be synthesized using a liquid phase chemical bath deposition. An attempt is made to tune its band gap and other characteristics to cope with a maxima of the solar spectrum by deliberate addition of Cr3+. ZnSe and Zn1-xCrxSe (0 <= x <= 0.35) thin films were obtained under the controlled deposition conditions (temperature = 70 A degrees C, time = 210 min, pH = 10, etc). The compositional analysis showed Zn2+ replacement by Cr3+. The X-ray photoelectron spectroscopy revealed chemical states of the constituents Zn, Cr and Se as 2(+), 3(+) and 2(-) respectively. The electrical conductivity and thermo-power measurements in the 300-550 K temperature range showed semiconducting nature of the material and that the electrical conduction is of the n-type. The electrical conductivity is found to be increased continuously up to x = 0.05 and then decreased for further increase in x. The Hall-probe measurements also confirmed n-type conduction. The average Hall coefficient for pure ZnSe is -1.03 x 10(7) cm(3)/C whereas, it is -4.55 x 10(6) cm(3)/C for a sample with x = 0.35.

Computational strategies to explore antimalarial thiazine alkaloid lead compounds based on an australian marine sponge plakortis lita - Lilly, Aswathy; Jisha, R. S.; Masand, Vijay H.; Gajbhiye, Jayant M.; Shibi, Indira G. (Journal of biomolecular Structure & Dynamics, 2017)
In this work, an attempt was made to propose new leads based on the natural scaffold Thiaplakortone-A active against malaria. The 2D QSAR studies suggested that three descriptors correlate with the anti-malarial activity with an R2 value of 0.814. Robustness, reliability and predictive power of the model were tested by internal validation, external validation, Y-scrambling and Applicability domain analysis. HQSAR studies were carried out as an additional tool to find the sub-structural fingerprints. The CoMFA and CoMSIA models gave Q2 values of 0.813 and 0.647, and R2ncv values of 0.994 and 0.984, respectively. Using the 2D-QSAR equation, the activity values of the seven modified compounds were calculated and it was found that three molecules showed good anti-malarial activity. Molecular docking of the 42 Thiaplakortone-A derivatives with P. falciparum calcium-dependent protein kinase 1 (PfCDPK1) was carried out to find out protein-ligand interactions. Data mining of the bioassay dataset AID: 504850 using the classifier based on Random Forest (RF) of Weka suggested that all of the eight molecules selected and three out of the seven virtual molecules were anti-malarial active. Both the virtual molecules and drug molecules were docked with CYP3A4, indicating that the virtual molecules could metabolize easily. Toxicity studies using Osiris shows that three molecules showed no toxic characters.

Computational survey of ligand properties on iron(III)-iron(II) redox potential: exploring natural attenuation of nitroaromatic compounds - Rizvi, Masood Ahmad; Mane, Manoj; Khuroo, Mohammad Akbar; Peerzada, Ghulam Mustafa (Monatshefte Fur Chemie, 2017)
This study is a computational investigation of the ligand effect on the redox potential of iron redox couple aimed at screening these systems for novel applications. The influence of common and naturally available organic compounds with diverse ligand characteristics (nature of donor site, chelation, pre-organization, degree of back acceptance) on the redox potential of iron(III)-iron(II) redox couple has been theoretically calculated using an appropriate level of density functional theory (DFT). The DFT calculated redox potentials of iron complexes are explored to supplement, corroborate, and predict the experimental behavior of the studied systems towards environmental reduction of nitroaromatic compounds to corresponding anilines. The comparative avidity of iron complexes with cysteine derivatives for the reduction of nitroaromatic compounds has been theoretically explored and based on structure-activity relationship; new iron complexes with a range of reactivity and enhanced ability towards nitroaromatic reduction have been predicted.
Keywords: Catechol derivatives; computational chemistry; Density functional theory; Iron complexes; Ligand effect on redox potential; Natural attenuation; Nitroaromatic compounds

Continuous flow telescopic oxidation of alcohols via generation of chlorine and hypochlorite - Sharma, Y.; Moolya, S.; Joshi, Ramesh A.; Kulkarni, Amol A. (Reaction Chemistry & Engineering, 2017)
A 3-step continuous flow oxidation of alcohols is demonstrated with continuous generation of chlorine as the first step followed by its use for the flow synthesis of high strength sodium hypochlorite. The solution is subsequently used for oxidation of alcohols in the presence of a catalytic amount of the nitroxyl radical “TEMPO”, which inhibits oxidation at the aldehyde stage. Selective oxidations of eight different alcohols were demonstrated. To achieve identical yields, the aromatic alcohols containing electron withdrawing groups needed a longer residence time than aliphatic alcohols.

Controlling necking in extrusion film casting using polymer nanocomposites - Rokade, Dhammaraj; Azad, Lal B.; Poddar, Suparna; Mishra, Satyendra; Pol, Harshawardhan V.; Shukla, Rishab (Journal of Macromolecular Science Part B-Physics, 2017)
The research described was concerned with the effect of layered-silicate-based organically modified nanoclay fillers on controlling the extent of necking in a polymer melt extrusion film casting (EFC) process. We show that a linear polythylene resin (such as a linear low-density polyethylene-LLDPE) filled with a very low percentage of well-dispersed (or intercalated) nanoclay displays an enhanced resistance to the necking phenomenon. In general, melt-compounded nanoclay-filled LLDPE resin formulations displayed a higher final film width (less necking), thus a lower final film thickness (greater draw down for the same draw ratio), and cooled down faster when compared to the base LLDPE resin. Incorporation of nanoclay filler in the mainly linear chain LLDPE resin led to significant modification of the melt rheological properties that, in turn, affected the melt processability of these formulations. Primarily, the intercalated nanoclay-filled LLDPE formulations displayed the presence of strain-hardening in unaxial extensional rheology. Additionally, the presence of well-dispersed nanoclay in the LLDPE resin led to a display of prominent extrudate swell indicating the presence of melt elasticity in such formulations. The presence of melt elasticity, as shown by shear rheology and strain-hardening, observed by uniaxial extensional rheology, contributed to the LLDPE nanoclay formulations displaying an enhanced resistance to necking for these films. It can be concluded that linear chain polymers susceptible to necking in an EFC process can be made more resistant to such necking by using nanoclay fillers at very low levels of loading.

Copper oxide supported on three-dimensional ammonia-doped porous reduced graphene oxide prepared through electrophoretic deposition for non-enzymatic glucose sensing - Maaoui, H.; Singh, S. K.; Teodorescu, F.; Coffinier, Y.; Barras, A.; Chtourou, R.; Kurungot, S.; Szunerits, S.; Boukherroub, R. (Electrochimica Acta, 2017)
The paper reports on the preparation of N-doped porous reduced graphene oxide/copper oxide (ammonia-doped-prGO/CuO) nanocomposite on gold electrodes using electrophoretic deposition (EPD) from an ethanolic suspension of ammonia-doped-prGO and Cu(ClO4)(2) by applying a DC voltage. The ammonia-doped-prGO/CuO nanocomposite film thickness is controlled by varying the deposition time. Morphological analysis using scanning electron microscopy (SEM) showed the formation of a 3 dimensional structure with CuO nanoparticles being homogeneously embedded in the graphene layer. Xray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Raman analysis revealed that the deposited copper was in its oxidized form, mainly CuO. The Au/ammonia-doped-prGO/CuO electrode was successfully applied for non-enzymatic amperometric detection of glucose. Under optimized conditions, the electrode exhibited a sensitivity of 1210 mu mM(-1) cm(-2) with a detection limit of 0.25 p,M (S/N =3) over a wide concentration range (0.25 mu M to 6 mM) at an applied potential of +0.50 V vs. Ag/AgCl. The electrode material displayed good stability, excellent selectivity, and accurate measurement in healthy and diabetic human serum samples.

Cross-coupling reactions of aryldiazonium salts with allylsilanes under merged gold/visible-light photoredox catalysis - Akram, Manjur O.; Mali, Pramod S.; Patil, Nitin T. (Organic Letters, 2017)
A method for the cross-coupling reactions of aryldiazonium salts with trialkylallylsilanes via merged gold/photoredox catalysis is described. The reaction is proposed to proceed through a photoredox-promoted generation of an electrophilic arylgold(III) intermediate that undergoes transmetalation with allyltrimethylsilane to form allylarenes.

Cucurbit[7]uril induced formation of fret-enabled unilamellar lipid vesicles - Kushwaha, Shilpi; Maity, Arunava; Gangopadhyay, Monalisa; Ravindranathan, Sapna; Rajamohanan, Pattuparambil R.; Das, Amitava (Langmuir, 2017)
A unique fluorescence resonance energy transfer (FRET) process is found to be operational in a unilamellar lipid self-assembly in the aqueous phase. A newly synthesized naphthyl based long chain lipid derivative [N-(naphthalene-1-ylmethyl)tetradecane-1-ammonium chloride, 14NA(+)] forms various self-assembled architectures in the aqueous phase. Controlled changes in lipid concentration lead to a transition of the self-assemblies from micelles to vesicles to rods. In the presence of cucurbit[7]uril (CB7), 14NA(+) forms a host-guest [2]pseudorotaxane complex (CB7(sic)14NA(+)) and secondary interactions lead to the formation of a lipid bilayer with hydrophobic pockets situated in between the layers. The change in the structure of 14NA(+) assemblies, interaction with CB7 and formation of supramolecular assemblies of CB7(sic)14NA(+) were examined using light scattering, spectroscopic, and microscopic techniques. Entrapment of a luminescent dye, anthracene within the hydrophobic bilayer of the supramolecular assembly CB7(sic)14NA(+) favors a modified luminescent response due to an efficient FRET process. Further, the FRET process could be controlled by thermal and chemical stimuli that induce transformation of unilamellar vesicles.

Cyclization mechanism of phomopsene synthase: mass spectrometry based analysis of various site-specifically labeled terpenes - Shinde, Sandip S.; Minami, Atsushi; Chen, Zhi; Tokiwano, Tetsuo; Toyomasu, Tomonobu; Kato, Nobuo; Sassa, Takeshi; Oikawa, Hideaki (Journal of Antibiotics, 2017)
Elucidation of the cyclization mechanism catalyzed by terpene synthases is important for the rational engineering of terpene cyclases. We developed a chemoenzymatic method for the synthesis of systematically deuterium-labeled geranylgeranyl diphosphate ( GGPP), starting from site-specifically deuterium-labeled isopentenyl diphosphates (IPPs) using IPP isomerase and three prenyltransferases. We examined the cyclization mechanism of tetracyclic diterpene phomopsene with phomopsene synthase. A detailed EI-MS analysis of phomopsene labeled at various positions allowed us to propose the structures corresponding to the most intense peaks, and thus elucidate a cyclization mechanism involving double 1,2-alkyl shifts and a 1,2-hydride shift via a dolabelladien-15-yl cation. Our study demonstrated that this newly developed method is highly sensitive and provides sufficient information for a reliable assignment of the structures of fragmented ions.

Degradation of metaldehyde in water by nanoparticle catalysts and powdered activated carbon - Li, Zhuojun; Kim, Jong Kyu; Chaudhari, Vrushali; Mayadevi, Suseeladevi; Campos, Luiza C. (Environmental Science and Pollution Research, 2017)
Metaldehyde, an organic pesticide widely used in the UK, has been detected in drinking water in the UK with a low concentration (< 1 mu g L-1) which is still above the European and UK standard requirements. This paper investigates the efficiency of four materials: powdered activated carbon (PAC) and carbon-doped titanium dioxide nanocatalyst with different concentrations of carbon (C-1.5, C-40, and C-80) for metaldehyde removal from aqueous solutions by adsorption and oxidation via photocatalysis. PAC was found to be the most effective material which showed almost over 90% removal. Adsorption data were well fitted to the Langmuir isotherm model, giving a q (m) (maximum/saturation adsorption capacity) value of 32.258 mg g(-1) and a K-L (Langmuir constant) value of 2.013 L mg(-1). In terms of kinetic study, adsorption of metaldehyde by PAC fitted well with a pseudo-second-order equation, giving the adsorption rate constant k(2) value of 0.023 g mg(-1) min(-1), implying rapid adsorption. The nanocatalysts were much less effective in oxidising metaldehyde than PAC with the same metaldehyde concentration and 0.2 g L-1 loading concentration of materials under UV light; the maximum removal achieved by carbon-doped titanium dioxide (C-1.5) nanocatalyst was around 15% for a 7.5 ppm metaldehyde solution.

On demand electrochemical release of drugs from porous reduced graphene oxide modified flexible electrodes - Boulahneche, Samia; Jijie, Roxana; Barras, Alexandre; Chekin, Fereshteh; Singh, Santosh K.; Bouckaert, Julie; Medjram, Mohamed Salah; Kurungot, Sreekumar; Boukherroub, Rabah; Szunerits, Sabine (Journal of Materials Chemistry B, 2017)
Despite the advantages of an electrochemical control for drug release, only a handful of electrochemical-based release systems have been developed so far. We report herein on the development of an electrochemically activatable platform for on-demand delivery of drugs. It is based on flexible gold thin film electrodes coated with porous reduced graphene oxide (prGO) nanosheets onto which the drug of interest has been integrated beforehand. Two different drugs are investigated here: ondansetron hydrochloride (ODS), a selective 5-HT3 receptor antagonist used for preventing nausea and vomiting caused by chemotherapy and radiotherapy, and ampicillin (AMP), an antibiotic to prevent and treat a number of bacterial infections such as respiratory tract infections, urinary tract infections, and meningitis. In the case of ODS, application of a negative potential bias of -0.8 V results in a sustained slow ODS release with an ODS flux of 47 mu g cm(-2) h(-1). In the case of AMP, we show that polyethyleneimine modified prGO (prGO/PEI) is an extremely efficient matrix. Upon the application of +0.8 V, 24% of AMP could be released from the electrical interface in a time span of 2 h. The released AMP kept its antibacterial activity as demonstrated by antimicrobial tests. These examples illustrate the major benefits of the developed approach for biomedical applications.

Demonstrating the role of anchoring functionality in interfacial electron transfer dynamics in newly synthesized BODIPY-TiO2 nanostructure composite - Ghosh, Hirendra N.; Das, Amitava; Aute, Sunil; Maity, Partha (New Journal of Chemistry, 2017)
New Bodipy derivatives (Dye 1 and 2) having catechol or resorcinol functionality for anchoring to the nanostructured (NS) TiO2 surfaces have been synthesized. Extended conjugation at one of the two pyrrole rings at the C3 position has helped us in achieving the desired control in tuning the optical and redox properties of the BODIPY based dye molecules. Relative emission quantum yields (em1 = ~52 ± 2% and em2 = 54 ± 2%) are found to be much higher in polar aprotic solvent (acetonitrile), while this are found to be substantially lower for dye 1 in polar protic solvent. Steady state optical absorption studies reveal the formation of a strong charge transfer complex between dye 1 and NS-TiO2, while this interaction is much weaker for dye 2. Transient absorption studies have been carried out for 1/NS-TiO2 and 2/NS-TiO2 systems following excitation with a laser source of 400 nm for understanding the charge transfer dynamics. Results of the transient absorption spectral studies helped in elucidating role of anchoring functionality in influencing the dynamics of the interfacial electron transfer and the charge recombination process in ultrafast time scale.

Determination of triazines and triazoles in grapes using atmospheric pressure matrix-assisted laser desorption/ionization high-resolution mass spectrometry - Mahale, Vishal; Singh, Ajeet; Phadke, Gayatri S.; Ghanate, Avinash D.; Oulkar, Dasharath P.; Banerjee, Kaushik; Panchagnula, Venkateswarlu (Journal of Aoac International, 2017)
A chromatography-free atmospheric pressure matrix-assisted laser desorption/ionization high-resolution mass spectrometry (AP-MALDI HRMS) method is described for the simultaneous and quantitative detection of triazines and triazoles in grapes. The analytes were detected reproducibly with high mass accuracy (mass error within 5 ppm) and further confirmed by collision-induced dissociation fragmentation in tandem MS. The LODs and LOQs for all the analytes were found to be in the nanogram per gram level (15-20 ng/g LOQ). Internal standard normalized high-resolution accurate mass extracted (HR-AM) peak intensities of the detected ions were used to generate the concentration response curves. Linearity (with R-2 values around 0.99) was obtained for these curves within a concentration range of 20-200 ng/g of the individual analytes. The accuracy and precision of the method were further established using QC samples. Validation and performance comparison of the AP-MALDI HRMS method with an existing standard method using LC with :triple quadrupole MS was carried out (evaluating sensitivity, accuracy, precision, and analysis time) using 20 table-grape field samples after QuEChERS extraction.

Diastase induced green synthesis of bilayered reduced graphene oxide and its decoration with gold nanoparticles - Maddinedi, Sireesh Babu; Mandal, Badal Kumar; Patil, Sagar Hindurao; Andhalkar, Vaibhav Vilas; Ranjan, Shivendu; Dasgupta, Nandita (Journal of Photochemistry and Photobiology B-Biology, 2017)
In this paper, we report an enzyme dependent, green one-pot deoxygenation cum decoration method to synthesize diastase-conjugated reduced graphene oxide (DRG) nanosheets, DRG/gold nanoparticles (DRG/Au) composite. The DRG synthesis was completed in 7 h under heating at 90 degrees C on water bath. Selected area electron diffraction (SAED) and Atomic force microscopy (AFM) study has revealed the formation of bilayered reduced graphene oxide sheets. Transmission electron microscopy (TEM) images of DRG/Au composite have shown the uniform decoration of gold nanoparticles (AuNPs) onto the DRG nanosheet surface. Fourier transform infrared spectroscopy (FTIR) and Raman results additionally have shown the functionalization of enzyme molecules onto the DRG nanosheet surface after reduction making it as an effective platform towards the efficient binding of gold nanoparticles. In vitro cytotoxicity studies by MIT assay on A549 and HCT116 cell lines exhibited that the cytotoxicity of the prepared graphene oxide (GO), DRG and DRG/Au is dose dependant. These results have shown that this synthetic method is effective for the production of large scale graphene in a low cost, simple and green method. Since this process avoids the use of hazardous and toxic substances, the produced DRG/Au composites are likely to offer various potential applications in biology and medicine. (C) 2016 Published by Elsevier B.V

Differential accumulation of vimentin fragments in preeclamptic placenta - Mary, Sheon; Kulkarni, Mahesh J.; Mehendale, Savita S.; Joshi, Sadhana R.; Giri, Ashok P. (Cytoskeleton, 2017)
Preeclampsia is a pregnancy complication that is the result of abnormal placentation because of inadequate trophoblast invasion into spiral arteries that prevent normal blood flow to the placenta. We report the alteration in vimentin protein proteolysis in placenta of normotensive and preeclamptic women, which is known to have a role in many physiological functions other than its major function in the structural integrity of the cell. Placental proteome from normotensive (n=25) and preeclamptic pregnancies (n=25) showed eight differentially accumulated protein spots of vimentin (proteolytic fragments) by two-dimensional electrophoresis. Immunoblots of normotensive and preeclamptic placenta revealed a difference in proteolytic processing of vimentin. In particular, lower molecular weight vimentin fragments of 32 and 20 kDa were 3.3 and 2.6-fold (p<0.0001) higher, respectively, in preeclampsia compared with normotensive placenta.

Differential rubisco content and photosynthetic efficiency of rol gene integrated Vinca minor transgenic plant: correlating factors associated with morpho-anatomical changes, gene expression and alkaloid productivity - Verma, Priyanka; Khan, Shamshad Ahmad; Masood, Nusrat; Manika, N.; Sharma, Abhishek; Verma, Neha; Luqman, Suaib; Mathur, Ajay K. (Journal of Plant Physiology, 2017)
Transgenic plants obtained from a hairy root line (PVG) of Vinca minor were characterized in relation to terpenoid indole alkaloids (TIAs) pathway gene expression and vincamine production. The hairy roots formed callus with green nodular protuberances when transferred onto agar-gelled MS medium containing 3.0 mg/l zeatin. These meristematic zones developed into shoot buds on medium with 1.0 mg/l 2, 4-dichlorophenoxyacetic acid and 40 mg/l ascorbic acid. These shoot buds subsequently formed rooted plants when shifted onto a hormone-free MS medium with 6% sucrose. Transgenic nature of the plants was confirmed by the presence of rol genes of the Ri plasmid in them. The transgenic plants (TP) had elongated internodes and a highly proliferating root system. During glass house cultivation TP consistently exhibited slower growth rate, low chlorophyll content (1.02 +/- 0.08 mg/gm fr. wt.), reduced carbon exchange rate (2.67 +/- 0.16 mu mol m(-2) s(-1)), less transpiration rate (2.30 +/- 0.20 mmol m(-2) s(-1)) and poor stomatal conductance (2.21 +/- 0.04 mmol m-2 s(-1)) when compared with non-transgenic population. The activity of rubisco enzyme in the leaves of TP was nearly two folds less in comparison to non-transgenic controls (1.80 milliunits ml(-1) mg protein-1 against 3.61 milliunits ml(-1) mg protein-1, respectively). Anatomically, the TP had a distinct tetarch arrangement of vascular bundles in their stem and roots against a typical ployarched pattern in the non-transgenic plants. Significantly, the transgenic plants accumulated 35% higher amount of total TIAs (3.10 +/- 0.21% dry wt.) along with a 0.03% dry wt. content of its vasodilatory and nootropic alkaloid vincamine in their leaves. Higher productivity of alkaloids in TP was corroborated with more than four (RQ = 4.60 +/- 0.30) and five (RQ = 5.20 +/- 0.70) times over-expression of TIAs pathway genes tryptophan decarboxylase (TDC) and strictosidine synthase (STR) that are responsible for pushing the metabolic flux towards TIAs synthesis in this medicinal herb.

Dihydropyrimidinone-isatin hybrids as novel non-nucleoside HIV-1 reverse transcriptase inhibitors - Devale, T. L.; Parikh, J.; Miniyar, P.; Sharma, P.; Shrivastava, B.; Murumkar, P. (Bioorganic Chemistry, 2017)
A novel series of substituted N-(2-( 2,3-dioxoindolin-1-yl) acetyl)-2-oxo-1,2,3,4-tetrahydropyrimidine-5carboxamide was designed, synthesized and evaluated for in vitro Reverse Transcriptase (RT) inhibitory activity. This series is a combination of peculiar structural features from leading scaffolds of [(2-hydroxye thoxy) methyl]-6-(phenylthio) thymine (HEPT) and oxyindole. In vitro screening led to identification of two hybrids (9c and 9d) possessing higher RT inhibitory activity than the standard rilpivirine. Docking study was performed to study the binding orientations of synthesized hybrids towards RT enzyme.

Direct production of furfural in one-pot fashion from raw biomass using bronsted acidic ionic liquids - Matsagar, Babasaheb M.; Hossain, Shahriar A.; Islam, Tofazzal; Alamri, Hatem R.; Alothman, Zeid A.; Yamauchi, Yusuke; Dhepe, Paresh L.; Wu, Kevin C. W. (Scientific Reports, 2017)
The conversion of raw biomass into C5-sugars and furfural was demonstrated with the one-pot method using Bronsted acidic ionic liquids (BAILs) without any mineral acids or metal halides. Various BAILs were synthesized and characterized using NMR, FT-IR, TGA, and CHNS microanalysis and were used as the catalyst for raw biomass conversion. The remarkably high yield (i.e. 88%) of C5 sugars from bagasse can be obtained using 1-methyl-3(3-sulfopropyl)-imidazolium hydrogen sulfate ([C3SO3HMIM][HSO4]) BAIL catalyst in a water medium. Similarly, the [C3SO3HMIM][HSO4] BAIL also converts the bagasse into furfural with very high yield (73%) in one-pot method using a water/toluene biphasic solvent system.

Diversification of quinazolinones by Pd-catalyzed C(sp(3))-acetoxylation - Garad, Dnyaneshwar N.; Mhaske, Santosh B. (Journal of Organic Chemistry, 2017)
The quinazolinone ring has been exploited as a directing group for C(sp(3))-H functionalization for the first time. The proximal C-gamma(sp3)-H bonds have been oxidized by palladium-catalyzed acetoxylation reaction. Various functional groups on the quinazolinone scaffold were tolerated to provide novel quinazolinone derivatives. The use of base was found to be crucial for the mono selective acetoxylations.

Diversity of natural yeast flora of grapes and its significance in wine making - Deshpande, M.V.; Mane, S.S.; Ghormade, V.; Tupe, S.G. (Yeast Diversity in Human Welfare, 2017)
The biodiversity of yeasts associated with grapes has been studied in different regions of wine producing countries throughout the world. Most of the species associated with the wine environment are similar, while some species are specifically associated with specific regions. Though Saccharomyces cerevisiae is primarily used for fermentation of grape juice, its occurrence is low on grape berries. Non-Saccharomyces yeasts belonging to the genera Torulaspora, Hanseniaspora, Pichia, Candida, Issatchenkia, Metschnikowia etc. are in abundance in grape musts and may dominate the early stages of fermentation. Subsequently, S. cerevisiae proliferates, becomes dominant and completes the wine fermentation. Therefore, yeasts diversity associated with the grapes and must significantly contribute to the quality and varietal character of wine. In present review, the diversity of yeasts associated with vineyard, winery, succession of yeasts during fermentation and their role in wine quality is discussed. The knowledge will be useful to monitor and control the fermentation with respect to quality and spoilage.

Diversity-oriented synthesis of spiroannulated benzofuran-3-one scaffold of leptosphaerin C and congeners via aryne insertion - Dhokale, Ranjeet A.; Mhaske, Santosh B. (Journal of Organic Chemistry, 2017)
A concise synthesis of functionalized cyclohexenone-fused spirobenzofuran-3-ones under mild reaction conditions was developed. The reaction proceeds via insertion of aryne into the C-O bond followed by a regioselective intramolecular conjugate addition. The use of silyl-protected acid was crucial for the transformation. This protocol was successfully applied for the synthesis of leptosphaerin C core and its novel analogues.

Docetaxel-titanate nanotubes enhance radiosensitivity in an androgen-independent prostate cancer model - Mirjolet, C.; Martin, E.; Boudon, J.; Loiseau, A.; Chevrier, S.; Boidot, R.; Oudot, A.; Collin, B.; Joy, P. A.; Millot, N.; Créhange, G. (International Journal of Nanomedicine, 2017)
Around 40% of high-risk prostate cancer patients who undergo radiotherapy (RT) will experience biochemical failure. Chemotherapy, such as docetaxel (DTX), can enhance the efficacy of RT. Multidrug resistance mechanisms often limit drug efficacy by decreasing intracellular concentrations of drugs in tumor cells. It is, therefore, of interest to develop nanocarriers of DTX to maintain the drug inside cancer cells and thus improve treatment efficacy. The purpose of this study was to investigate the use of titanate nanotubes (TiONts) to develop a TiONts-DTX nanocarrier and to evaluate its radiosensitizing in vivo efficacy in a prostate cancer model. In vitro cytotoxic activity of TiONts-DTX was evaluated using an MTS assay. The biodistribution of TiONts-DTX was analyzed in vivo by single-photon emission computed tomography. The benefit of TiONts-DTX associated with RT was evaluated in vivo. Eight groups with seven mice in each were used to evaluate the efficacy of the nanohybrid combined with RT: control with buffer IT injection ± RT, free DXL ± RT, TiONts ± RT and TiONts-DXL ± RT. Mouse behavior, health status and tumor volume were monitored twice a week until the tumor volume reached a maximum of 2,000 mm3. More than 70% of nanohybrids were localized inside the tumor 96 h after administration. Tumor growth was significantly slowed by TiONts-DTX associated with RT, compared with free DTX in the same conditions (P=0.013). These results suggest that TiONts-DTX improved RT efficacy and might enhance local control in high-risk localized prostate cancer.
Keywords: Docetaxel Nanocarrier; nanoparticle; Prostate Cancer; Radiosensitivity; Titanate nanotubes

Domibacillus mangrovi sp nov and domibacillus epiphyticus sp nov., isolated from marine habitats of the central west coast of India - Verma, Ashish; Ojha, Anup Kumar; Dastager, Syed G.; Natarajan, Rameshkumar; Mayilraj, Shanmugam; Krishnamurthi, Srinivasan (International Journal of Systematic and Evolutionary Microbiology, 2017)
While studying culturable bacterial diversity in different marine habitats of the central west coast of India, two novel Gramstain-positive, strictly aerobic, motile, endospore-forming and rod-shaped bacterial strains designated as SAOS 44(T) and SAB 38(T) were isolated from mangrove sediment soil and the surface of a macroalga, respectively. The strains were taxonomically characterized by using a polyphasic approach and genomic methods. The phylogenetic analysis based on 16S rRNA gene sequencing placed the strains firmly in the genus Domibacillus and were most closely related to Domibacillus antri KCTC 33636(T). The predominant fatty acids were iso-C-15 : 0 and anteiso-C-15 : 0. The major polar lipids were diphosphatidylglycerol and phosphatidylglycerol in addition to an aminophosphoglycolipid. MK-6 was the only respiratory quinone. The range of values of digital DNA-DNA hybridization (19.2-24.9 %) and the ortho-average nucleotide identity (74.1-81.4 %) among strains SAOS 44(T), SAB 38(T) and other Domibacillus species clearly supports their status as a distinct and novel species for which the names Domibacillus mangrovi sp. nov. SAOS 44(T) (=DSM 100930(T)=KCTC 33820(T)=MTCC 12571(T)) and Domibacillus epiphyticus sp. nov. SAB 38(T) (=DSM 100929(T)= KCTC 33830(T)=MTCC 12575(T)) are proposed, respectively.

Dry molten globule-like intermediate during the base-induced unfolding of a multidomain protein - Acharya, Nirbhik; Mishra, Prajna; Jha, Santosh Kumar (Physical Chemistry Chemical Physics, 2017)
The nature of the initial structural events during the base-induced unfolding of the native (N) state of proteins is poorly understood. Combining site-specific fluorescence resonance energy transfer, size exclusion chromatography, dynamic fluorescence quenching, red-edge excitation shift and circular dichroism spectroscopy, we show here that an early intermediate during the base-induced unfolding of a multidomain protein, i.e., the B form, has features of a dry molten globule. We show that the N (sic) B transition involves protein expansion and loosening of packing of inter-domain helices near domains I and II without the disruption of intra-domain packing or any change in hydration of the inter-domain region which resembles a molten hydrocarbon. Surprisingly, the disruption of inter-domain packing accounts for 40-45% of the total change in free energy of complete unfolding. Our results show that the disruption of van der Waals packing can be decoupled in different regions of a protein and could occur prior to hydrophobic solvation during base-induced unfolding, challenging the existing notion.

Dynamic metabolic reprogramming of steroidal glycol-alkaloid and phenylpropanoid biosynthesis may impart early blight resistance in wild tomato (Solanum arcanum Peralta) - Shinde, Balkrishna A.; Dholakia, Bhushan B.; Hussain, Khalid; Panda, Sayantan; Meir, Sagit; Rogachev, Ilana; Aharoni, Asaph; Giri, Ashok P.; Kamble, Avinash C. (Plant Molecular Biology, 2017)
Alternaria solani severely affects tomato (Solanum lycopersicum L.) yield causing early blight (EB) disease in tropical environment. Wild relative, Solanum arcanum Peralta could be a potential source of EB resistance; however, its underlying molecular mechanism largely remains unexplored. Hence, non-targeted metabolomics was applied on resistant and susceptible S. arcanum accessions upon A. solani inoculation to unravel metabolic dynamics during different stages of disease progression. Total 2047 potential metabolite peaks (mass signals) were detected of which 681 and 684 metabolites revealed significant modulation and clear differentiation in resistant and susceptible accessions, respectively. Majority of the EB-triggered metabolic changes were active from steroidal glycol-alkaloid (SGA), lignin and flavonoid biosynthetic pathways. Further, biochemical and gene expression analyses of key enzymes from these pathways positively correlated with phenotypic variation in the S. arcanum accessions indicating their potential role in EB. Additionally, transcription factors regulating lignin biosynthesis were also up-regulated in resistant plants and electrophoretic mobility shift assay revealed sequence-specific binding of rSaWRKY1 with MYB20 promoter. Moreover, transcript accumulation of key genes from phenylpropanoid and SGA pathways along with WRKY and MYB in WRKY1 transgenic tomato lines supported above findings. Overall, this study highlights vital roles of SGAs as phytoalexins and phenylpropanoids along with lignin accumulation unrevealing possible mechanistic basis of EB resistance in wild tomato.

Effect of Ru precursors and reduction conditions on catalyst performance in glycerol hydrogenolysis - Mane, R.B.; Patil, S.T.; Gurav, H.; Rayalu, S.S.; Rode, C.V. (ChemistrySelect, 2017)
Catalyst precursors, their reduction protocols and reaction conditions integrally influenced the activity and selectivity pattern in glycerol hydrogenolysis. Ru prepared from chloride precursor (Ru(Cl)/C−B) showed the maximum selectivity to C−C cleavage products EG (56 %) and methanol (17 %) with 23 % selectivity to 1,2-PDO. While, that prepared from nitrosyl precursor (Ru(n)/C−B) showed higher selectivity to 1,2-PDO (44 %) and lower to EG (42 %). The catalysts prepared either with chloride or nitrosyl precursors but reduced by H2 showed lower glycerol conversion (10-11 %) than NaBH4 reduced catalysts. For these catalysts, 1,2-PDO selectivity increased to 40–43 % along with the major formation of 2-propanol (48-49 %) and very less selectivities to C−C cleavage products. The lower activity of the H2 reduced catalysts can be related to their lower acidity and the bigger Ru metal particle size (3-5 nm). For Ru(Cl)/C−B catalyst, glycerol conversion increased from 28–97 % with a rise in temperature from 180 to 250 oC also favoring 1,2-PDO selectivity; indicating that C−O bond cleavage was favoured in comparison to C−C scission, at higher temperature.

Effective degradation of organic water pollutants by atmospheric non-thermal plasma torch and analysis of degradation process - Bansode, Avinash H.; More, Supriya Eknath; Siddiqui, Ejaz Ahmad; Satpute, Shruti; Ahmad, Absar; Bhoraskar, Sudha V.; Mathe, Vikas L. (Chemosphere, 2017)
The paper reports the use of atmospheric non-thermal plasma torch as a catalyst for degradation of various organic pollutants dissolved in water. A flow of He mixed with air was used to produce the dielectric barrier discharge (DBD), at the tip of the torch, using pulsed electric excitation at 12 kV. The torch, operated at a power of 750 mW/mm², was seen to completely degrade the aqueous solutions of the pollutants namely methylene blue (MB), methyl orange (MO) and rhodamine-B (RB), at around 10⁻⁴ M concentrations, the concentration of polluants is one order higher than of routinely used heterogeneous photocatalytic reactions, within 10 min of irradiation time at room temperature. UV Visible spectra of the organic dye molecules, monitored after different intervals of plasma-irradiation, ranging between 1 and 10 min, have been used as tools to quantify their sequential degradation. Further, instead of using He, only air was used to form plasma plume and used for degradation of organic dye which follow similar trend as that of He plasma. Further, Liquid Chromatography Mass Spectroscopy (LCMS) technique has been used to understand degradation pathway of methylene blue (MB) as a representative case. Total organic carbon (TOC) measurements indicates significant decrease in its content as a function of duration of plasma exposure onto methylene blue as a representative case. Toxicity studies were carried out onto Gram negative Escherichia coli. This indicated that methylene blue, without plasma treatment, shows growth inhibition, whereas with plasma treatment no inhibition was observed.

Efficient and durable oxygen reduction electrocatalyst based on CoMn alloy oxide nanoparticles supported over N-doped porous graphene - Singh, Santosh K.; Kashyap, Varchaswal; Manna, Narugopal; Bhange, Siddheshwar N.; Soni, Roby; Boukherroub, Rabah; Szunerits, Sabine; Kurungot, Sreekurnar (ACS Catalysis, 2017)
Transition metal oxide derived materials are very important for various applications, such as electronics, magnetism, catalysis, electrochemical energy conversion, and storage. Development of efficient and durable catalysts for the oxygen reduction reaction (ORR), an important reaction in fuel cells and metal air batteries, is highly desirable. Moreover, the futuristic catalysts for these applications need to be costeffective in order to ensure a competitive edge for these devices in the energy market. This article describes the synthesis of a cost-effective and efficient electrocatalyst for ORR It is based on supporting CoMn alloy oxide nano particles on N-doped porous graphene through a simple and scalable microwave irradiation method. Microwave irradiation was found to be very crucial for the fast creation of pores in the graphene framework with a concomitant formation of the CoMn alloy oxide nanoparticles. A series of catalysts have been synthesized by varying the Co:Mn ratio, among which, the one with the Co:Mn ratio of 2:1 [designated as CoMn/pNGr(2:1)] displayed remarkably higher ORR activity in 0.1 M KOH solution. It showed a similar to 60 mV potential shift with a low Tafel slope of 74 mV/decade, which is comparable to that derived from the commercial Pt/C catalyst. This high activity of CoMn/pNGr(2:1) has been credited to the cooperative effect arising from the metal entities and the defects present in the N-doped porous graphene. Finally, real system-level validations of the use of CoMn/pNGr(2:1) as cathode catalyst could be performed by fabricating and testing single-cells of an anion-exchange membrane fuel cell (AEMFC) and a primary Zn-air battery, which successfully demonstrated the efficiency of the catalyst to facilitate ORR in real integrated systems of the single-cell assemblies.
Keywords: anion-exchange membrane fuel cell; cooperativity effect; microwave synthesis; oxygen reduction reaction; porous N-doped graphene; Zn-air battery

Efficient organic photovoltaics with improved charge extraction and high short-circuit current - Mohan, Minu; Nandal, Vikas; Paramadam, Sanish; Reddy, Kasala Prabhakar; Ramkumar, Sekar; Agarwal, Sumanshu; Gopinath, Chinnakonda S.; Nair, Pradeep R.; Namboothiry, Manoj A. G. (Journal of Physical Chemistry C, 2017)
Exciton generation, dissociation, free carrier transport, and charge extraction play an important role in the short-circuit current (J(sc)) and power conversion efficiency of an organic bulk heterojunction (BHJ) solar cell (SC). Here we study the impact of band offset at the interfacial layer and the morphology of active layer on the extraction of free carriers. The effects are evaluated on an inverted BHJ SC using zinc oxide (ZnO) as a buffer layer, prepared via two different methods: ZnO nanoparticle dispersed in mixed solvents (ZnO A) and sol-gel method (ZnO B). The device with ZnO A buffer layer improves the charge extraction and J(sc),. The improvement is due to the better band offset and morphology of the blend near the ZnO A/active layer interface. Further, the numerical analysis of current-voltage characteristics illustrates that the morphology at the ZnO A/active layer interface has a more dominant role in improving the performance of the organic photovoltaic than the band offset.

Efficient synthesis of the opioid analgesic (R)-phenampromide via an aziridinium ion - Mujahid, Mohammad; Mujumdar, Prashant; Sasikumar, Murugesan; Deshmukh, Shirish P.; Muthukrishnan, Murugan (Tetrahedron-Asymmetry, 2017)
A simple and efficient synthesis of the opioid analgesic agent (R)-phenampromide with high enantiopurity (> 99% ee) via the formation of an aziridinium ion as a key step using commercially available starting material is described. (C) 2017 Elsevier Ltd. All rights reserved.

Electrodeposited nickel cobalt manganese based mixed sulfide nanosheets for high performance supercapacitor application - Sahoo, S.; Mondal, R.; Late, D. J.; Rout, C. S. (Microporous and Mesoporous Materials, 2017)
Porous multi component Nickel Cobalt Manganese Sulfide (NCMS) nanosheets have been grown on Ni foam by cathodic electrodeposition method. The as-prepared NCMS nanosheets sample is used as an electrode material for supercapacitor application due to its large electrochemically active surface and high porosity structure. Moreover, NCMS nanosheets have good electrical and mechanical connections to the conductive Ni foam to achieve enhanced reaction kinetics with improved electrode integrity. The NCMS nanosheets exhibit an ultrahigh specific capacitance of 2717 Fig at a current density of 1 Aug with excellent cyclic stability and energy density of 94.07 Wh/kg. The electrodeposited NCMS nanosheets with extraordinary electrochemical performance enable the novel electrodes to hold great potential for high efficient energy storage systems.

Enantioselective synthesis of functionalized β-lactones by NHC-catalyzed aldol lactonization of ketoacids - Mondal, Santigopal; Mukherjee, Subrata; Das, Tamal Kanti; Gonnade, Rajesh G.; Biju, Akkattu T. (Journal of Organic Chemistry, 2017)
N-Heterocyclic carbene (NHC)-catalyzed intramolecular aldol lactonization of readily available ketoacids leading to the enantioselective synthesis of cyclopentane-fused β-lactones is presented. The reaction proceeds via the generation of NHC-bound enolate intermediates formed from the ketoacids in the presence of the peptide coupling reagent HATU and NHC generated from the chiral triazolium salt. The functionalized β-lactones are formed under mild conditions in high yields and enantioselectivities.

Enantioselective synthesis of spiro γ-butyrolactones by N-heterocyclic carbene (NHC)-catalyzed formal [3+2] annulation of enals with 3-hydroxy oxindoles - Mukherjee, Subrata; Joseph, Sumi; Bhunia, Anup; Gonnade, Rajesh Ghanshyam; Reddy, Santhi Vardhan; Biju, Akkattu T. (Organic & Biomolecular Chemistry, 2017)
The N-heterocyclic carbene (NHC)-catalyzed enantioselective formal [3 + 2] annulation of α,β-unsaturated aldehydes with 3-hydroxy oxindoles is presented. Under oxidative conditions using the bisquinone oxidant, the reaction resulted in the synthesis of spiro γ-butyrolactones in moderate to good yields, enantioselectivity and diastereoselectivity. The reaction likely proceeds via the generation of the NHC-bound α,β-unsaturated acylazolium intermediate from enals, which was intercepted by the dioxindoles in a formal [3 + 2] pathway to form the spirocyclic compounds. However, a deeper mechanistic investigation revealed that the reaction can also proceed via the homoenolate intermediate. In this case, the dioxindole was oxidized to the corresponding isatin derivative using traces of air under basic conditions, and was intercepted with the NHC-bound homoenolate intermediate in a formal [3 + 2] pathway to afford the spiro compound.

Enhanced field emission characteristics of a 3D hierarchical Hfo2-Zno heteroarchitecture - Shisode, Raju T.; Suryawanshi, Sachin R.; Mistari, Chetan D.; Late, Dattatray J.; More, Mahendra A. (ChemistrySelect, 2017)
Three dimensional (3D) HfO2-ZnO heteroarchitecture comprised of thin coating of HfO2 on self assembled 3D ZnO urchins with pointed apex has been synthesized using hydrothermal route followed by Pulsed Laser Deposition (PLD). The as-synthesized HfO2-ZnO heteroarchitecture was characterized using XRD, SEM, EDS, and (HR) TEM, in order to reveal its structural, morphological, and chemical properties. The HfO2-ZnO heteroarchitecture emitter exhibits superior field emission (FE) behaviour in contrast to the pristine ZnO urchins, demonstrated by delivery of high emission current density of similar to 885 mA/cm2 at an applied field of similar to 3.35 V/mm, against similar to 383 mA/cm(2) at an applied field of similar to 4.32 V/mu m for the pristine ZnO urchins emitter. Interestingly, the HfO2-ZnO heteroarchitecture emitter exhibits excellent emission current stability characterized with fewer fluctuations, owing to very good ion-bombardment resistance offered by the HfO2 coating. Furthermore, the heteroarchitecture thus obtained facilitates tailoring of the morphology with high aspect ratio and modulation of electronic properties as well, thereby enhancing the FE behaviour. Despite HfO2 being wide band gap and high-k material, the HfO2-ZnO heteroarchitecture exhibits potential as promising candidate for fabrication of high current density cold cathode
Keywords: 3D heteroarchitecture; Field Emission (FE); hydrothermal; PLD; TEM

Enhanced field emission performance of MoO3 nanorods and MoO3-rGO nanocomposite - Bankar, Prashant K.; Khandare, Lina N.; Late, Dattatray J.; More, Mahendra A. (ChemistrySelect, 2017)
The graphene and semiconducting hybrid based nanostructures have emerged as a new class of multifunctional materials with improved performance in comparison to the pristine semiconductors. Here, as-synthesized MoO3-reduced graphene oxide (rGO) nanocomposite emitter exhibits enhanced field emission (FE) behavior as compared to the pristine 1D MoO3 nanorods. The hydrothermally synthesized 1D MoO3 nanorods (1D) are grafted on the rGO sheet (2D) using a simple room temperature sonochemical method. The morphological and structural analysis confirms the attachment of MoO3 nanorods with rGO and the improved conductivity of the sample indicates a strong electronic interaction between them. Furthermore, the FE studies of as-synthesized MoO3 nanorods and MoO3-rGO nanocomposite emitters, carried out at a base pressure -1 x 10(-8) mbar, reveals the values of turn on field (required to draw an emission current density of 1 mu A/cm(2)) as 1.6 and 1.4 V/mu m, respectively. Interestingly, the maximum emission current density of 2810 mA/cm(2) is achieved at a lower applied field of 2.7 V/mu m from the MoO3-rGO nanocomposite emitter. The enhancement in FE performance of MoO3-rGO nanocomposite is attributed to the improved electrical conductivity, mechanical properties and higher concentration of protruding edges (emission sites). This observation can be extended to other graphene-based 1D inorganic hybrid semiconductor nanocomposites, which can provide a valuable opportunity to explore novel hybrid materials for vacuum nano-electronic devices.

Enhanced field emission performance of NiMoO4 nanosheets by tuning the phase - Bankar, Prashant K.; Ratha, Satyajit; More, Mahendra A.; Late, Dattatray J.; Rout, Chandra Sekhar (Applied Surface Science, 2017)
In this paper we report, large scale synthesis of a and beta-NiMoO4 by a facile hydrothermal method and we observed that urea plays important role on the growth of beta-NiMoO4 nanosheets. We have also carried out field emission (FE) investigations of alpha and beta-NiMoO4 at a base pressure of similar to 1 x 10(-8) mbar. The obtained turn-on field at emission current density of 1 mu A/cm(2) for beta-NiMoO4 nanosheets and alpha-NiMoO4 is 1.3V/mu m and 2.2V/mu m respectively were observed. The maximum field emission current density of 1.006 mA/cm(2) at an applied electric field of 2.7V/mu m was achieved for beta-NiMoO4 nanosheets. Furthermore, we found that the beta-NiMoO4 nanosheets possess good field emission performance compared to alpha-NiMoO4. The results indicate that NiMoO4 can be used as a promising material in FE applications with possibility of tuning field emission performance by controlling the phase. (C) 2017 Elsevier B.V. All rights reserved.

Enhanced field emission performance of NiMoO4 nanosheets by tuning the phase - Bankar, P. K. (Applied Surface Science, 2017)
In this paper we report, large scale synthesis of α and β-NiMoO4 by a facile hydrothermal method and we observed that urea plays important role on the growth of β-NiMoO4 nanosheets. We have also carried out field emission (FE) investigations of α and β-NiMoO4 at a base pressure of ∼1 × 10−8 mbar. The obtained turn-on field at emission current density of 1 μA/cm2 for β-NiMoO4 nanosheets and α −NiMoO4 is 1.3 V/μm and 2.2 V/μm respectively were observed. The maximum field emission current density of 1.006 mA/cm2at an applied electric field of 2.7 V/μm was achieved for β-NiMoO4 nanosheets. Furthermore, we found that the β-NiMoO4 nanosheets possess good field emission performance compared to α-NiMoO4. The results indicate that NiMoO4can be used as a promising material in FE applications with possibility of tuning field emission performance by controlling the phase.
Keywords: Current stability; field emission; nanosheets; NiMoO4

Examination into the taxonomic position of Bacillus thermotolerans Yang et al., 2013, proposal for its reclassification into a new genus and species Quasibacillus thermotolerans gen. nov., comb. nov. and reclassification of B. encimensis Dastager et al., - Verma, Ashish; Pal, Yash; Khatri, Indu; Ojha, Anup Kumar; Gruber-Vodicka, Harald; Schumann, Peter; Dastager, Syed Gulam; Subramanian, Srikrishna; Mayilraj, Shanmugam; Krishnamurthi, Srinivasan (Systematic and Applied Microbiology, 2017)
Two novel Gram-staining positive, rod-shaped, moderately halotolerant, endospore forming bacterial strains 5.5LF 38TD and 5.5LF 48TD were isolated and taxonomically characterized from a landfill in Chandigarh, India. The analysis of 16S rRNA gene sequences of the strains confirmed their closest identity to Bacillus thermotolerans SgZ-8T with 99.9% sequence similarity. A comparative phylogenetic analysis of strains 5.5LF 38TD, 5.5LF 48TD and B. thermotolerans SgZ-8(T) confirmed their separation into a novel genus with B. badius and genus Domibacillus as the closest phylogenetic relatives. The major fatty acids of the strains are iso-C15:0 and iso-C16:0 and MK-7 is the only quinone. The major polar lipids are diphosphatidylglycerol, phosphatidylglycerol and phosphatidylethanolamine. The digital DNA-DNA hybridization (DDH) and ortho average nucleotide identity (ANI) values calculated through whole genome sequences indicated that the three strains showed low relatedness with their phylogenetic neighbours. Based on evidences from phylogenomic analyses and polyphasic taxonomic characterization we propose reclassification of the species B. thermotolerans into a novel genus named Quasibacillus thermotolerans gen. nov., comb. nov with the type strain SgZ-8(T) (=CCTCC AB2012108(T)=KACC 16706(T)). Further our analyses also revealed that B. encimensis SGD-V-25(T) is a later heterotypic synonym of Bacillus badius DSM 23(T).

Exploring the effect of hydroxylic and non-hydroxylic solvents on the reaction of [(VO)-O-IV(beta-diketonate)2] with 2-aminobenzoyl-hydrazide in aerobic and anaerobic conditions - Biswas, Nirmalendu; Patra, Debashis; Mondal, Bipul; Bera, Sachinath; Acharyya, Swarnali; Biswas, Anup Kumar; Mukhopadhyay, Titas Kumar; Pal, Amrita; Drew, Michael G. B.; Ghosh, Tapas (Dalton Transactions, 2017)
Refluxing [(VO)-O-IV(beta-diketonate)(2)], namely [(VO)-O-IV(acetylacetonate)(2)] and [(VO)-O-IV(benzoylacetonate)(2)], separately with an equivalent or excess amount of 2-aminobenzoylhydrazide (ah) in laboratory grade (LG) CH3OH in aerobic conditions afforded non-oxidovanadium(IV) and oxidovanadium(V) complexes of the type [V-IV(L-1)(2)] (1), [(VO)-O-V(L-1)(OCH3)](2) (3) and [V-IV(L-2)(2)] (2), and [(VO)-O-V(L-2)(OCH3)] (4), respectively. (L-1)(2-) and (L-2)(2-) represent the dianionic forms of 2-aminobenzoylhydrazone of acetylacetone (H2L1) and benzoylacetone (H2L2), respectively, (general abbreviation, H2L), which was formed by the in situ condensation of ah with the respective coordinated [beta-diketonate] in medium-to-good yield. The yield of different resulting products was dependent upon the ratio of ah to [(VO)-O-IV(beta-diketonate)(2)]. For example, the yield of 1 and 2 complexes increased significantly associated with a decrease in the amount of 3 and 4 with an increase in the molar ratio of ah. Upon replacing CH3OH by a non-hydroxylic solvent, LG CHCl3, the above reaction yielded only oxidovanadium(V) complexes of the type [(VO)-O-V(L-1)(OH)](2) (5), [(VO)-O-V(L-2)(OH)] (6) and [(V2O3)-O-V(L)(2)] (7, 8) whereas, upon replacing CHCl3 by another non-hydroxylic solvent, namely LG CH3CN, only the respective [(V2O3)-O-V(L)(2)] (7, 8) complex was isolated in 72-78% yield. However, upon performing the above reactions in the absence of air using dry CH3OH or dry CHCl3, only the respective [V-IV(L)(2)] complex was obtained, suggesting that aerial oxygen was the oxidising agent and the type of pentavalent product formed was dependent upon the nature of solvent used. Complexes 3 and 4 were converted, respectively, to 7 and 8 on refluxing in LG CHCl3 via the respective unstable complex 5 and 6. The DFT calculated change in internal energy (Delta E) for the reactions 2[(VO)-O-V(L-2)(OCH3)] + 2H(2)O -> 2[(VO)-O-V(L-2)(OH)] + 2CH(3)OH and 2[(VO)-O-V (L-2)(OH)] -> [(V2O3)-O-V(L-2)(2)] + H2O was, respectively, +3.61 and -7.42 kcal mol(-1), suggesting that the [(VO)-O-V(L-2) (OH)] species was unstable and readily transformed to the stable [(V2O3)-O-V(L-2)(2)] complex. Upon one-electron reduction at an appropriate potential, each of 7 and 8 generated mixed-valence [(L) (VO)-O-V-(mu-O)-OVIV(L)]species, which showed valence-delocalisation at room temperature and localisation at 77 K. Some of the complexes showed a wide range of toxicity in a dose-dependent manner against lung cancer cells comparable with that observed with cis-platin.
Keywords: Effective Core Potentials; Lung-cancer cells; Molecular-Orbital Methods; Non-oxido vanadium(iv); Non-Oxo; Oxovanadium(iv) Complexes; Tridentate ono ligand; Ray crystal-structure; Trigonal-prismatic Co-ordination; V-IV complex

Exploring the gem-dimethyl effect in the formation of imine-based macrocycles and cages - Madhu, Suresh; Rashmi, E. V.; Gonnade, Rajesh Ghanshyam; Sanjayan, Gangadhar J. (New Journal of Chemistry, 2017)
Using the gem-dimethyl effect as a platform, a variety of organic [2+2] macrocycles and [2+3] cofacial cages was obtained in high yields. Imine-based macrocyclization could be performed even at high concentrations (0.5 to 1.0 M), via instant mixing of aldehydes and amines.

Extraction of the very high tunneling current and extremely stable emission current from GdB6/W-tip source synthesized using arc plasma - Suryawanshi, Sachin R.; Kanhe, Nilesh; Mathe, Vikas L.; Phase, Deodatta M.; Late, Dattatray J.; More, Mahendra A. (ChemistrySelect, 2017)
Herein, we report the one step arc plasma synthesis of the GdB6 (Gadolinium hexaboride) nanoparticles and its field emission (FE) characteristics on tungsten point substrate (GdB6/ W). The SEM /TEM analysis revealed the GdB6 nanoparticles on W point substrate exhibit irregular shaped, grainy, dense, course morphology, i.e. uniformly covering the entire tip substrate surface. For GdB6/W point source, the values of the turn-on and threshold fields, defined as field required to draw an emission current density similar to 1 mA/cm(2) and similar to 100 mA/cm(2), respectively are found to be similar to 2.2 and similar to 2.7 V/mm, for anodecathode separation of similar to 1 mm. Interestingly, a very high emission current density of similar to 3.5 A/cm(2) has been drawn from the GdB6/W point emitter at relatively lower applied field of similar to 6.4 V/mm. The field enhancement factor found to be similar to 10,250. The GdB6/W point electron source exhibits a good emission current stability at similar to 10 mA for a period of 6 hr. The emission current stability is enumerated in terms of standard deviation and its magnitude has been measured to be only 1.72% with respect to the average value. The superlative field emission characteristics signify the GdB6/W point electron source as potential candidates for vacuum micro/nanoelectronics device applications.
Keywords: Arc Plasma; field emission; Thin films

Facile one-pot multi-component synthesis of spirooxindoles and 3, 3 `-disubstituted oxindoles via sp(3) C-H activation/functionalization of azaarenes - Pathan, Mohsinkhan Y.; Chavan, Santosh S.; Shaikh, Taufeekaslam M. Y.; Thorat, Shridhar H.; Gonnade, Rajesh G.; Mulla, Shafeek A. R. (Chemistryselect, 2017)
A novel one-pot multicomponent reaction (MCR) protocol has been demonstrated for the first time for sustainable and facile synthesis of spirooxindoles and 3, 3 `-disubstituted oxindoles in an excellent yield via sp(3) C-H activation/functionalization of 2-methyl azaarenes and (2-azaaryl)methanes with isatin, active methylene compounds using eco-friendly heterogeneous, reusable silica-supported dodecatungstophosphoric acid (DTP/SiO2) catalyst.
Keywords: 3; 3'-disubstituted oxindoles; azaarenes; silica-supported dodecatungstophosphoric acid (DTP/SiO2) catalyst; sp(3) C-H activation/functionalization; spirooxindoles

Facile synthesis and electrochemical evaluation of PANI/CNT/MoS2 ternary composite as an electrode material for high performance supercapacitor - Thakur, A.K.; Deshmukh, A. B.; Choudhary, R. B.; Karbhal, I.; Majumder, M.; Shelke, M.V. (Materials Science and Engineering B: Solid-State Materials for Advanced Technology, 2017)
Synthesis of a novel ternary composite consisting of polyaniline (PANI), functionalized multi-walled carbon nanotubes (CNTs) and molybdenum disulfide (MoS2), via an in-situ polymerization method is reported. Detailed structural and electrochemical characterization shows that incorporation of a small amount of MoS2 in PANI/CNT composite tends to eliminate agglomeration problem of CNT. The PANI/CNT/MoS2 ternary composite reaches a specific capacitance of 350 F/g at the current density 1 A/g corresponding to a 5% MoS2 content. This ternary composite shows good cycling stability even at a higher energy density of 10 A/g. Further, PANI/CNT/MoS2 composite electrode shows higher energy density (7.77 Wh/kg) and power density (2140 W/kg) as compared to PANI/CNT composite without MoS2.
Keywords: MoS2; polyaniline; supercapacitor; Ternary Composite

Facile synthesis and self-cleaning application of bimetallic (CuSn, CuNi) dendrites - Biswas, Anupam; Kulkarni, Mayuresh A.; Bakthavatsalam, Rangarajan; Mondal, Sourik K.; Dwivedi, Pravin K.; Shelke, Manjusha V.; Devi, Radhamonyamma N.; Banpurkar, Arun G.; Kundu, Janardan (Chemistryselect, 2017)
Bimetallic dendrites (Au, Ag, Pt, Pd) have received intense research interest due to their applications in catalysis and sensing. However, reports on rational synthesis of non-noble bimetallic dendrites that finds self-cleaning applications are scanty. Here, we demonstrate one step co-reduction based galvanic replacement reaction (GRR) for synthesis of alloyed bimetallic dendrites (CuSn, CuNi) with controlled surface roughness and chemical composition. Probing their growth process reveals that i) for CuSn dendrites, co-reduction of Cu2+ and Sn2+ is observed throughout GRR; ii) for CuNi dendrites, Cu nanoparticle, that deposits initially, augments the reduction of Ni2+ which leads to CuNi alloy phase formation during later stages of GRR. These dendrites, naturally having dual degree of surface roughness (micro/nano), have been exploited here for fabricating superhydrophobic surfaces (SHS) with excellent self-cleaning abilities. They show enabling properties such as high contact angle, minimal contact angle hysteresis, and excellent Cassie state stability with no impalement. They maintain superhydrophobicity when exposed to different environmental conditions (low temperature, high temperature, exposure to corroding solutions and UV radiation). The present facile methodology for fabrication of bimetallic dendrites is beneficial for low-cost production of functional nano/micro-materials.

Facile synthesis of ZnO-Ag nanocomposite and its photocatalytic activity - Sardar, Debasmita; Maity, Jayeta; Ghosalya, Manoj Kumar; Gopinath, Chinnakonda S.; Bala, Tanushree (Materials Research Express, 2017)
The evolution of photoactive hybrid materials (e.g. noble metal-semiconductor) has resulted in heterogeneous photocatalysis. We report a facile route for the synthesis of ZnO-Ag nanocomposites with varying percentage of loading of the noble metal, expecting a great boost in the photocatalytic behavior of ZnO. The as prepared material was thoroughly characterized by UV-Vis, FTIR, TEM, FESEM, XRD, XPS analyses. The photocatalytic activities of the nanocomposites have been assessed from the ability to degrade methylene blue dye in aqueous solution. The results suggest that incorporation of Ag nanoparticles on the surface of ZnO particles can enhance catalytic activity in comparison to pure ZnO particles under visible light by minimizing the recombination of photogenerated electron-hole pairs.

Facile synthesis of β-functionalized “push-pull” Zn(II) porphyrins for DSSC applications - Prakash, K. (Dyes and Pigments, 2017)
Three new β-substituted “push-pull” Zn(II) porphyrin dyes with various electron donors at meso-positions and cyanoacetic acid as acceptor at β-position have been designed and synthesized. These porphyrins have been characterized by UV-Vis, Fluorescence, 1H NMR and 13C NMR spectroscopic techniques and cyclic voltammetric studies. The Soret and Q band of Zn(II) porphyrin dyes were found to be red-shifted (30–35 nm) as compared to ZnTPP. The fluorescence quenching and the decrement in quantum yield and lifetime suggest intramolecular charge transfer from donor to acceptor. Zn porphyrins exhibited anodic shift in their first redox potentials (0.03–0.11 V) as compared to ZnTPP. The HOMO-LUMO energy levels of Zn porphyrin dyes were compared with the conduction band of TiO2 and the electrolyte I−/I3 −. The HOMO levels of all the dyes are sufficiently higher than the energy level of electrolyte I−/I3 − and LUMO levels significantly lower than the conduction band of TiO2 which reflect the feasibility of facile electron-transfer. ZnT(Mes)P(CN-COOH) has been co-sensitized with N719 dye to further improve the PCE efficiency. These dyes displayed power conversion efficiency (PCE) of η = 1.72–3.13% where co-sensitized ZnT(Mes)P(CN-COOH) (N719) dye demonstrated maximum PCE efficiency up to 5.35%, with a Jsc of 11.8 mA cm−2, a Voc of 630 mV and a fill factor (FF) of 72% due to better light harvesting capacity.
Keywords: charge transfer; Conduction Bands; Cyanoacetic Acid; Electrolytes; Floorescence; Redox Reaction; zinc compounds

ffects of cations, anions and H+ concentration of acidic ionic liquids on the valorization of polysaccharides into furfural - Matsagar, Babasaheb M.; Dhepe, Paresh L. (New Journal of Chemistry, 2017)
The valorization of hemicellulose into valuable chemicals, such as C5 sugars and furfural, in a one-pot fashion is crucial. In this work, acidic ionic liquids in the presence of water showed high yields of C5 sugars (>80%) with >99% conversion of hemicelluloses at 160 degrees C. With a water + toluene biphasic solvent system, within 4 h, an 85% furfural yield was obtained directly from hemicellulose in a one-pot fashion using a catalytic amount of 1-methyl-3-(3-sulfopropyl)-imidazolium hydrogen sulfate. It was seen that Bronsted acidic ionic liquids (BAILs) perform better than solid acid [Faujasite and Mordenite zeolites; ion exchange resin, Amberlyst-15] and mineral catalysts [HCl and H2SO4]. The higher activity of BAILs compared to solid acids and mineral acids was correlated to the Hammett acidity function (Ho) and ion-dipole type of interactions. The catalysts were characterized using NMR (H-1 and C-13), elemental analysis and TGA to confirm that they were stable under reaction conditions and were thus recyclable.

Fluoride-mediated dephosphonylation of alpha-diazo-beta-carbonyl phosphonates - Phatake, Ravindra S.; Mullapudi, Venkannababu; Wakchaure, Vivek C.; Ramana, Chepuri V. (Organic Letters, 2017)
The possibility of fluoride-mediated selective dephosphonylation of alpha-diazo-beta-carbonyl phosphonates such as the Ohira-Bestmann reagent has been proposed and executed. The resulting alpha-diazocarbonyl intermediates undergo a (3 + 2)pcycloaddition at room temperature with conjugated olefins and benzynes. Interestingly, under the current conditions, the resulting cycloaddition products underwent either N-acylation (with excess alpha-diazo-beta-carbonyl phosphonates) or Michael addition (with conjugated olefins).

Formal synthesis of bioactive indole alkaloids eburnamonine, eburnaminol, and vindeburnol - Mondal, Pravat; Argade, Narshinha P. (Synthesis-Stuttgart, 2017)
Starting from (+/-)-3-acetoxyglutarimide, diastereoselective formal synthesis of indole alkaloids (+/-)-eburnamonine, (+/-)-eburnaminol, and (+/-)-vindeburnol have been demonstrated via a common intermediate (+/-)-1-hydroxy-12-tosyl-2,3,6,7,12,12b-hexahydroindolo[2,3a] quinolizin-4(1H)-one in very good overall yields. The acetoxy group from (+/-)-3-acetoxyglutarimide was first used to induce the diastereoselectivity and also as a latent source of ketone carbonyl group. The stereoselective eliminations, reductions, and intramolecular cyclizations were the involved key steps.
Keywords: cyclizations; eburnaminol; eburnamonine; elimination; hexahydroindoloquinolizinone; reduction; vindeburnol

Fruit peel waste: characterization and its potential uses - Pathak, Pranav D.; Mandavgane, Sachin A.; Kulkarni, Bhaskar D. (Current Science, 2017)
Globally, India is the leading producer of fruits. Fruits after consumption leave a peel which is a nuisance to the environment as a solid waste. In this article, commonly available large volume-fruit peels (FP) (viz. banana, orange, citrus, lemon and jackfruit) were investigated for surface, physical and chemical characteristics with a view to propose their valorization in detail. Each FP was characterized by proximate and ultimate analysis, porosity, particle density, bulk density, point of zero charge (pH(pzc)), surface pH, surface charges, water absorption capacity, BET surface area, scanning electron microscopy, Fourier transform infrared spectroscopy and TGA/derivative of thermogravimetric. The BET surface area of FP is very less, between 0.60 and 1.2 m(2)/g. The pH(pzc) and surface pH values of orange peel (OP), citrus peel (CP), lemon peel (LP) and jackfruit peels (JFP) are in the range of 3-4. The pH(pzc) value and surface pH of banana peel (BP) is closer to 7. The order of surface acidity is OP > LP > CP > JFP > BP. From TG curves it is clear that FPs are stable below 150 degrees C. The results will be useful for rational design, when FP is used as a substrate for bioactive compounds, phenolic antioxidants, organic acids, enzymes, biofertilizer, production of energy and as adsorbents.

Functional stability and structural transitions of kallikrein: spectroscopic and molecular dynamics studies - Dalal, Sayli; Mhashal, Anil; Kadoo, Narendra; Gaikwad, Sushama M. (Journal of Biomolecular Structure & Dynamics, 2017)
Kallikrein, a physiologically vital serine protease, was investigated for its functional and conformational transitions during chemical (organic solvents, Gdn-HCl), thermal, and pH induced denaturation using biochemical and biophysical techniques and molecular dynamics (MD) simulations approach. The enzyme was exceptionally stable in isopropanol and ethanol showing 110% and 75% activity, respectively, after 96h, showed moderate tolerance in acetonitrile (45% activity after 72h) and much lower stability in methanol (40% activity after 24h) (all the solvents [90% v/v]). Far UV CD and fluorescence spectra indicated apparent reduction in compactness of KLKp structure in isopropanol system. MD simulation studies of the enzyme in isopropanol revealed (1) minimal deviation of the structure from native state (2) marginal increase in radius of gyration and solvent accessible surface area (SASA) of the protein and the active site, and (3) loss of density barrier at the active site possibly leading to increased accessibility of substrate to catalytic triad as compared to methanol and acetonitrile. Although kallikrein was structurally stable up to 90 degrees C as indicated by secondary structure monitoring, it was functionally stable only up to 45 degrees C, implicating thermolabile active site geometry. In GdnHCl [1.0M], 75% of the activity of KLKp was retained after incubation for 4h, indicating its denaturant tolerance. A molten globule-like structure of KLKp formed at pH 1.0 was more thermostable and exhibited interesting structural transitions in organic solvents. The above results provide deeper understanding of functional and structural stability of the serine proteases at molecular level.
Keywords: isopropanol tolerance; Kallikrein; MD Simulation; Molten globule; Serine protease; Thermostability

Genetic programming based drag model with improved prediction accuracy for fluidization systems - Sonolikar, R. R.; Patil, M. P.; Mankar, R. B.; Tambe, S. S.; Kulkarni, B. D. (International journal of Chemical Reactor Engineering, 2017)

Genomic and functional characterization of coleopteran insect-specific alpha-amylase inhibitor gene from amaranthus species - Bhide, Amey J.; Channale, Sonal M.; Yadav, Yashpal; Bhattacharjee, Kabita; Pawar, Pankaj K.; Maheshwari, V. L.; Gupta, Vidya S.; Ramasamy, Sureshkumar; Giri, Ashok P. (Plant Molecular Biology, 2017)
The smallest 32 amino acid alpha-amylase inhibitor from Amaranthus hypochondriacus (AAI) is reported. The complete gene of pre-protein (AhAI) encoding a 26 amino acid (aa) signal peptide followed by the 43 aa region and the previously identified 32 aa peptide was cloned successfully. Three cysteine residues and one disulfide bond conserved within known alpha-amylase inhibitors were present in AhAI. Identical genomic and open reading frame was found to be present in close relatives of A. hypochondriacus namely Amaranthus paniculatus, Achyranthes aspera and Celosia argentea. Interestingly, the 3'UTR of AhAI varied in these species. The highest expression of AhAI was observed in A. hypochondriacus inflorescence; however, it was not detected in the seed. We hypothesized that the inhibitor expressed in leaves and inflorescence might be transported to the seeds. Sub-cellular localization studies clearly indicated the involvement of AhAI signal peptide in extracellular secretion. Full length rAhAI showed differential inhibition against alpha-amylases from human, insects, fungi and bacteria. Particularly, alpha-amylases from Helicoverpa armigera (Lepidoptera) were not inhibited by AhAI while Tribolium castaneum and Callosobruchus chinensis (Coleoptera) alpha-amylases were completely inhibited. Molecular docking of AhAI revealed tighter interactions with active site residues of T. castaneum alpha-amylase compared to C. chinensis alpha-amylase, which could be the rationale behind the disparity in their IC50. Normal growth, development and adult emergence of C. chinensis were hampered after feeding on rAhAI. Altogether, the ability of AhAI to affect the growth of C. chinensis demonstrated its potential as an efficient bio-control agent, especially against stored grain pests.

Glycoprotein alpha-amylase inhibitor from Withania somnifera differentially inhibits various alpha-amylases and affects the growth and development of Tribolium castaneum - Kasar, Sainath S.; Marathe, Kiran R.; Bhide, Amey J.; Herwade, Abhijeet P.; Giri, Ashok P.; Maheshwari, Vijay L.; Pawar, Pankaj K. (PEST Management Science, 2017)
BACKGROUND: Identification and characterisation of plant defensive molecules enrich our resources to design crop protection strategies. In particular, plant-derived proteinaceous inhibitor(s) of insect digestive enzymes appear to be a safe, sustainable and attractive option. RESULTS: A glycoprotein having non-competitive alpha-amylase inhibitory activity with a molecular weight of 8.3 kDa was isolated and purified from seeds of Withania somnifera alpha-amylase inhibitor (WSAI). Its mass spectrometry analysis revealed 59% sequence coverage with Wrightide II-type alpha-amylase inhibitor from Wrightia religiosa. A dose-dependent inhibition of alpha-amylases from Aspergillus oryzae, Bacillus subtilis, Helicoverpa armigera and Tribolium castaneumwas recorded. Interestingly, WSAI did not inhibit human salivary alpha-amylase significantly. When adults of T. castaneum were fed with WSAI (1.6mg g(-1)), decrease inconsumption, growthandefficiency of conversion of ingested foodwas evident, along withover fourfold increases in feedingdeterrence index. Adecline inlarval residual alpha-amylase activity after feedingofWSAI resulted ina reduction in longevity of T. castaneum. CONCLUSION: The study reflects the significance of WSAI in affecting the overall growth and development of T. castaneum. Pre-and post-harvest pest resistive capability makes WSAI a potential candidate for insect pest management. Further, the effectiveness of this inhibitor could be explored either in formulations or through a transgenic approach. (C) 2016 Society of Chemical Industry

Growth of flower-like patterns of TiO2 nanorods over FTO substrate - Issar, Sheetal; Poddar, Pankaj; Mehra, N. C.; Mahapatro, Ajit K. (International Conference on Technologically Advanced Materials (ICTAM), 2017)
Nanostructures such as nanoparticles, nanowires, nanorods, nanotubes have attracted great interest with the understanding of shape and size dependence in the electronic and sensing properties. This work demonstrates growth and characterization of one-dimensional nanorods of titanium-dioxide (TiO2) on the fluorine doped tin oxide (FTO) substrate by using hydrothermal method. Field effect scanning electron microscopy shows flower-like morphology, and energy-dispersive X-ray spectroscopy confirms the presence of Ti and O. The X-ray diffraction peaks agree well with the JCPDS data. Initially, the 1D nanorods are formed and high concentration of precursor assists evolution of the short branches to form flower-like structures.

H-Bonding assisted self-assembly of anionic and neutral ligand on metal: a comprehensive strategy to mimic ditopic ligands in olefin polymerization - Mote, Nilesh R.; Patel, Ketan; Shinde, Dinesh R.; Gaikwad, Shahaji R.; Koshti, Vijay S.; Gonnade, Rajesh G.; Chikkali, Samir H. (Inorganic Chemistry, 2017)
Self-assembly of two neutral ligands on a metal to mimic bidentate ligand coordination has been frequently encountered in the recent past, but self-assembly of an anionic ligand on a metal template alongside a neutral ligand remains an elusive target. Such a self-assembly is hampered by additional complexity, wherein a highly negatively charged anion can form intermolecular hydrogen bonding with the supramolecular motif, leaving no scope for self-assembly with neutral ligand. Presented here is the self-association of anionic ligand 3-ureidobenzoic acid (2a) and neutral ligand 1-(3-(diphenylphosphanyl)phenyl)urea (1a) on a metal template to yield metal complex [{COOC6H4-NH(CO)NH2}{Ph2PC6H4NH(CO)NH2}PdMeDMSO] (4a). The identity of 4a was established by NMR and mass spectroscopy. Along the same lines, 3-(3-phenylureido)benzoic acid (2b) and 1-(3-(diphenylphosphanyl)phenyl)-3-phenylurea (1b) self-assemble on a metal template to produce palladium complex [{COOC6H4NH(CO)NHPh}{Ph2PC6H4NH(CO)NHPh}PdMePy] (5c). The existence of 5c was confirmed by Job plot, 1-2D NMR spectroscopy, deuterium labeling, IR spectroscopy, UV-vis spectroscopy, model complex synthesis, and DFT calculations. These solution and gas phase investigations authenticated the presence of intramolecular hydrogen bonding between hydrogen's of 1b and carbonyl oxygen of 2b. The generality of the supramolecular approach has been validated by preparing six complexes from four monodentate ligands, and their synthetic utility was demonstrated in ethylene polymerization. Complex 4a was found to be the most active, leading to the production of highly branched polyethylene with a molecular weight of 55700 g/mol and melting temperature of 112 degrees C.

Hydrogen production from reforming of biogas: review of technological advances and an Indian perspective - Nahar, G.; Mote, D.; V. Dupont (Renewable and Sustainable Energy Reviews, 2017)
This paper examines the benefits and potential of biogas generation and uses in India, with focus on advances made in hydrogen production by catalytic reforming technologies with steam, O2, and CO2 as the oxidants. Utilization of biomass by means of generating biogas is one of the easiest and cost effective methods of harnessing renewable energy. As India is an agricultural country, a tremendous amount of biomass and livestock waste is generated every year. Likewise the large population of India generates much food and municipal solid waste that is not being utilized for biogas generation. Fuel cells are one of the effective means of utilizing biogas, although the synthesis gas or hydrogen generated from biogas can also be used in internal combustion engines. Higher efficiency of fuel cells (45%) compared to internal combustion engines (30%) and even higher with co-generation systems (70%) make them highly desirable for biogas utilization for power generation. Investigations of hydrogen productionfor fuel cell use are in their infancy stage in India. Apart from a few scattered investigations not much work has been undertaken in the area of research. Large scale hydrogen production is achieved by steam reforming of hydrocarbons, in particular natural gas. Although the process is a proven technology it has come under considerable scrutiny due to its environmental impact and the energy intensive nature of the process. Several technical and scientific challenges have to be overcome for assimilation of the technology for hydrogen production from biogas and wide scale application in India. These challenges include development of less energy intensive features, highly active and poisons-resistant catalyst, and fuel cell development for utilization of biogas generated hydrogen. Hydrogen production from reforming of biogas: Review of technological advances and an Indian perspective. Available from: https://www.researchgate.net/publication/315896154_Hydrogen_production_from_reforming_of_biogas_Review_of_technological_advances_and_an_Indian_perspective [accessed Oct 16 2017].

Hydrogenolysis of sorbitol over Ni, Pt and Ru supported on SBA-15 - Banu, M.; Sankaranarayanan, T. M.; Venuvanalingam, P.; Magesh, G.; Sivasanker, S. (Indian Journal of Chemistry. Section A: Inorganic, Physical, Theoretical & Analytical Chemistry, 2017)
Hydrogenolysis of sorbitol (15% aqueous solution) has been carried out in a batch reactor over Ni (6 wt%), Pt (1 wt%) and Ru (1 wt%) supported on SBA-15 and carbon coated SBA-15 (SBA-15(C)). For comparison, the three metals have also been supported on activated carbon (AC). The catalysts are characterized by XRD, N-2 and H-2 adsorption measurements. Addition of Ca(OH)(2) to the reaction mixture increases conversion and selectivity for the dihydroxy compounds, 1,2-propanediol (PD) and ethylene glycol (EG). Based on yield of dihydric alcohols (PD+EG), the performance of the catalysts at 220 degrees C and 60 bar in the presence of Ca(OH)(2) is in the order: Ru-AC similar to Ru-SBA-15(C) > Ru-SBA-15 similar to Ni-SBA-15, the yields being 40, 39, 31 and 29 wt%, respectively.

Identification and functionality prediction of pathogenesis-related protein 1 from legume family - Tellis, Meenakshi; Mathur, Monika; Gurjar, Gayatri; Kadoo, Narendra; Gupta, Vidya (Proteins-Structure Function and Bioinformatics, 2017)
The production and accumulation of pathogenesis-related (PR) proteins in plants is one of the important responses to biotic and abiotic stress. Large number of identified PR proteins has been categorized into 17 functional families based on their structure, phylogenetics, and biological activities. However, they are not widely studied in legume crops. Using 29 PR1 proteins from Arabidopsis thaliana, as query, here we have predicted 92 candidate PR1 proteins through the PSI-BLAST and HMMER programs. These candidate proteins were comprehensively analyzed with, multiple sequence alignment, domain architecture studies, signal peptide, and motif extraction followed by phylogenetic analysis. Further, response of two candidate PR1 proteins from chickpea against Fusarium oxysporum f.sp.ciceri attack was validated using qRT-PCR followed by their 3D structure prediction. To decipher mode of action for PR1s, docking of pathogen extracellular matrix components along with fungal elicitors was performed with two chickpea PR1 proteins. Based on these findings, we propose carbohydrate to be the unique pathogen-recognition feature for PR1 proteins and beta-glucanase activity via beta-glucan binding or modification.

Identification of biomolecules involved in the biosynthesis of gold nanoparticles from living peanut seedlings - Raju, D.; Siddiqui, Ejaz Ahmad; Prasanth, S.; Khan, Bashir M.; Mehta, Urmil J.; Ahmad, Absar (Journal of Nanoscience and Nanotechnology, 2017)
In present work, we have fabricated gold nanoparticles by treating an aqueous solution of 10(-4) M HAuCl4 with the proteins extracted from roots of in vitro raised peanut seedlings and purified them by FPLC at room temperature. These proteins which tested positive for the reduction of 10(-4) M HAuCl4 were identified as Mannose glucose binding lectin and Ara h 8 allergen isoforms by ESI MS/MS. It is a well known fact that aromatic amino acids possess delocalized pi electrons in their ring structures, rendering them as the best electron donors which can transfer electrons and reduce the acceptor. These results suggest that the aromatic amino acids present in the proteins from the peanut seedlings are the primary biomolecules involved in the reduction of Au (III) to Au (0). We isolated different protein of molecular weight 16.4, 28.3 and 30 kDa involved in the formation of nanoparticles. The protein with molecular weight 16.4 kDa (allergens) yielded NPs of 25-60 nm whereas, the proteins with molecular weight 28.3 kDa and 30 kDa (lectins) yielded highly monodispersed NPs of 5-20 nm in size. The results clearly indicate that the size of nanoparticles can be controlled by different proteins.

Impact of rare-earth metal oxide (Eu 2 O 3 ) on the electrochemical properties of a polypyrrole/CuO polymeric composite for supercapacitor applications - Majumder, Mandira; Choudhary, Ram Bilash; Thakur, Anukul. K.; Karbhal, Indrapal (RSC Advances, 2017)
A ternary composite of polypyrrole/copper oxide/europium oxide (PPY/CuO/Eu2O3), synthesized via a facile in situ chemical oxidative polymerization method, exhibits the maximum specific capacitance of 320 F g⁻¹ at the current density of 1 A g⁻¹. Incorporation of the rare-earth metal oxide Eu2O3 in the PPY/CuO matrix can promote charge transportation in the resulting ternary nanocomposite by enhancing the porosity. The interconnected mesoporous networks reduce the internal resistance and the charge transfer resistance (Rct) of the composite electrode material. Moreover, the incorporation of Eu2O3 in the PPY/CuO provides support to the fragile polymer backbone resulting in an excellent cycle stability and a markedly enhanced thermal stability. These together with the exhibition of an excellent coulombic efficiency demonstrates that incorporation of rare earth metal oxide can play a significant role in improving the performance of a polymeric composite opted as an electrode material for high-performance supercapacitor.

Impact of science, technology and innovation on the economic and political power - Mashelkar, Raghunath Anant (AI & Society, 2017)

In situ grown nickel nanoparticles in a calixarene nanoreactor on a graphene-MoS2 support for efficient water electrolysis - Waghmode, Babasaheb J.; Bhange, Siddheshwar N.; Unni, SreeKuttan M.; Patil, Kashinath R.; Malkhede, Dipalee D. (Sustainable Energy & Fuels, 2017)
Electrochemical production of hydrogen, facilitated in electrolysers, holds great promise for energy storage and solar fuel production. Catalysis of the oxygen evolution reaction (OER) is a bottleneck of this process. However, the sluggish OER kinetics and the utilization of precious metal catalysts are key obstacles in the broad deployment of this energy technology. We report the preparation and use of an inexpensive GrMoS(2)SC(8)Ni nanocomposite material as a highly effective OER catalyst in an alkaline electrolyte. Experimental investigations have shown that improvements can be realized in the catalytic performance of Ni metal if it is a component of the composite material. We propose an explanation for these enhancements based on a hydrogen acceptor concept. This concept comprises the stabilization of an *-OOH intermediate, which effectively lowers the potential needed for breaking bonds on the surface. Herein, an inexpensive immobilized SC8 layer was used as the nanoreactor to synthesize metallic Ni nanoparticles (NPs) through an in situ redox process. The process was applied to form immobilized NPs on flat and curved 2D surfaces. The outstanding OER performance of Ni NPs could be attributed to their large surface area, efficient mass and charge transport, and high structural stability arising from the unique SC8 cage structure, built on the GrMoS(2) substrate. The GrMoS(2)SC(8)Ni nanocomposite shows the highest activity, exhibiting a 214 mV overpotential at 10 mA cm(-2) (equivalent to 10% efficiency of solarto-fuel conversion) and a Tafel slope of 31 mV dec(-1) in 1 M KOH solution. It further demonstrates high stability as there is no apparent OER activity loss (based on a chronoamperometry test) or particle aggregation (based on SEM image observation) after a 10 h anodization test. The facile preparation method and high efficiency and durability enable this electrocatalyst to be a promising candidate for future large-scale applications in water splitting. Thus, this work opens a new avenue toward the development of highly efficient, inexpensive OER catalysts.

Influence of carbon based supports on selectivity behavior of diols and propanol in Ru catalyzed glycerol hydrogenolysis - Mane, Rasika B.; Patil, S.; Shirai, Masayuki; Rayalu, Sadhana S.; Rode, Chandrashekhar V. (Applied Catalysis B: Environmental, 2017)
Activated carbon (AC) and three graphite materials were studied as supports for Ru catalyzed glycerol hydrogenolysis to propanediols and 1-propanol. Structural characteristics of AC and graphite materials were found to greatly affect the reducibility and particle size of supported Ru and hence, the activity and product distribution in glycerol hydrogenolysis. XRD of graphite materials showed distinctly (002) plane having highly organized layered structure and the peak intensity decreased in the order of Ru/KS150 > Ru/HSAG100 > Ru/KS6 due to decrease in the graphite sheet thickness. In Raman, the intense D band in HSAG100 compared to that in KS6 and KS150 samples indicated its highly amorphous nature or mixed carbon hybridization. Glycerol conversion for Ru on AC was higher than that on graphite and among different graphites, it showed a descending activity order of Ru/KS6 > Ru/HSAG100 > Ru/KS150. The product distribution for AC and HSAG100 supported Ru was similar, giving 1-propanol (45%) alongwith 1,2-propanediol (1,2-PDO) (37%) and 1,3-propanediol (1,3-PDO) (9–11%). For graphite supports, availability of Ru although bigger in size (4–5 nm), would be higher on the surface than in case of AC which formed deep hydrogenolysis products like 1-, 2- propanol, ethanol etc.
Keywords: activated carbon; Amorphous carbon; catalysis; Glycerol; Glycerol conversions; Glycerol hydrogenolysis; graphite composites; Graphite supports; Hydrogenolysis; Hydrolysis; layered structures; Particle size; Product distributions; Propanediols; Propanol; Selectivity behavior; Structural characteristics; Structural effect; Structural effects

Influence of hyperglycemic conditions on self-association of the alzheimer's amyloid beta (a beta(1-42)) peptide - Menon, Sneha; Sengupta, Neelanjana (ACS Omega, 2017)
<div id="absImg" style="position: relative; margin: 0px; padding: 5px; border: 1px solid rgb(204, 204, 204); border-radius: 5px; background-image: initial; background-position: initial; background-size: initial; background-repeat: initial; background-attachment: initial; background-origin: initial; background-clip: initial; text-align: center; color: rgb(0, 0, 0); font-family: Helvetica, Arial, sans-serif; font-size: 14px;"><img alt="Abstract Image" src="http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/acsodf/2017/acsodf.2017.2.issue-5/acsomega.7b00018/20170517/images/medium/ao-2017-00018p_0003.gif" style="border: 0px; max-width: 100%;"> <p class="articleBody_abstractText" style="margin: 0px 0px 1.5em; line-height: 1.6em; padding: 0pt; width: 610px; word-wrap: break-word; color: rgb(0, 0, 0); font-family: Helvetica, Arial, sans-serif; font-size: 14px;">Clinical studies have identified a correlation between type-2 diabetes mellitus and cognitive decrements en route to the onset of Alzheimer’s disease (AD). Recent studies have established that post-translational modifications of the amyloid β (Aβ) peptide occur under hyperglycemic conditions; particularly, the process of glycation exacerbates its neurotoxicity and accelerates AD progression. In view of the assertion that macromolecular crowding has an altering effect on protein self-assembly, it is crucial to characterize the effects of hyperglycemic conditions via crowding on Aβ self-assembly. Toward this purpose, fully atomistic molecular dynamics simulations were performed to study the effects of glucose crowding on Aβ dimerization, which is the smallest known neurotoxic species. The dimers formed in the glucose-crowded environment were found to have weaker associations as compared to that of those formed in water. Binding free energy calculations show that the reduced binding strength of the dimers can be mainly attributed to the overall weakening of the dispersion interactions correlated with substantial loss of interpeptide contacts in the hydrophobic patches of the Aβ units. Analysis to discern the differential solvation pattern in the glucose-crowded and pure water systems revealed that glucose molecules cluster around the protein, at a distance of 5–7 Å, which traps the water molecules in close association with the protein surface. This preferential exclusion of glucose molecules and resulting hydration of the Aβ peptides has a screening effect on the hydrophobic interactions, which in turn diminishes the binding strength of the resulting dimers. Our results imply that physical effects attributed to crowded hyperglycemic environments are incapable of solely promoting Aβ self-assembly, indicating that further mechanistic studies are required to provide insights into the self-assembly of post-translationally modified Aβ peptides, known to possess aggravated toxicity, under these conditions.
Keywords: Conformation; Drug discovery and Drug delivery systems; Free energy; Glycoproteins; Molecular association; Molecular dynamics simulation

Influence of thermocleavable functionality on organic field-effect transistor performance of small molecules - Mahale, Rajashree Y.; Dharmapurikar, Satej S.; Chini, Mrinmoy Kumar; Venugopalan, Vijay (Chemical Physics Letters, 2017)
Diketopyrrolopyrrole based donor-acceptor-donor conjugated small molecules using ethylene dioxythiophene as a donor was synthesized. Electron deficient diketopyrrolopyrrole unit was substituted with thermocleavable (tert-butyl acetate) side chains. The thermal treatment of the molecules at 160 degrees C eliminated the tert-butyl ester group results in the formation of corresponding acid. Optical and theoretical studies revealed that the molecules adopted a change in molecular arrangement after thermolysis. The conjugated small molecules possessed p-channel charge transport characteristics in organic field effect transistors. The charge carrier mobility was increased after thermolysis of tert-butyl ester group to 5.07 x 10(-5) cm(2)/Vs. (C) 2017 Elsevier B.V. All rights reserved.

Influences of functionalized nanoclays on morphology and mechanical properties of polyvinyl alcohol based composites by twin-screw extruder - Rajeswari, B.; Malarvizhi, N.; Elumalai, Deenadayalan; Jaisankar, Sellamuthu N. (Polymer-Plastics Technology and Engineering, 2017)
Polyvinyl alcohol (PVA) based nanocomposites filled with different weight percentage of functionalized nanoclays were prepared by melt processing with a twin-screw extruder. The effective incorporation of amine modified bentonite nanoclays (AMB) in the PVA matrix leads to increase in thermal stability, stress-strain properties. The effect of addition of functionalized nanoclays in PVA matrix exhibits intercalated nanocomposite structure. The thermal decomposition (Td) temperature of the composites increases up to 30 °C, than pristine PVA. The morphology influences were studied by TEM. These clay nanocomposite films could be useful for wound dressing material and for enhancing the moisture absorbance properties.

Investigation into the taxonomy of “ B. aminovorans” and its reclassification to the genus Domibacillus as Domibacillus aminovorans sp. nov. - Verma, Ashish; Ojha, Anup Kumar; Pal, Yash; Kumari, Parveen; Schumann, Peter; Gruber-Vodicka, Harald; Dastager, Syed Gulam; Natarajan, Ramesh Kumar; Mayilraj, Shanmugam; Krishnamurthi, Srinivasan (Systematic and Applied Microbiology, 2017)
The species "Bacillus aminovorans" was categorized as species Incertae Sedis meaning taxa with uncertain taxonomic position because of insufficient description of phenotypic properties and lack of understanding of its phylogenetic relationship (Claus and Berkeley [5]). In this study two strains "B. aminovorans" DSM 1314T and DSM 4337 were phenotypically and phylogenomically analyzed. The strains are Gram-staining-positive, spore forming rods and unable to utilize/ferment most of the sugars tested except glucose. The major fatty acids are anteiso-C15:0 and iso-C15:0. The major polar lipids are diphosphatidylglycerol, phosphatidylglycerol and an aminophosphoglycolipid. The cell wall peptidoglycan is of A1γ type with meso-Dpm as the diamino acid. The menaquinone type present is MK-6. The G+C content of the genomic DNA of the type strain is 40.8mol%. These characteristics were found to be in line with description of the genus Domibacillus. Moreover phylogenetic analysis based on 16S rRNA gene sequence retrieved "B. aminovorans" within the genus Domibacillus with D. antri XD 80T as the closest relative. Additionally genome sequencing of the strains and their comparison with whole genome sequences of other Domibacillus spp. confirmed their distinctiveness and separate species status within the genus based on parameters of genome to genome distance calculator (GGDC) and average nucleotide identity (ANI) values. Therefore a novel species Domibacillus aminovorans sp. nov. (DSM 1314T =LMG 16796T) is proposed.
Keywords: 16S rRNA; Domibacillus aminovorans; MALDI-TOF; ``Bacillus aminovorans''

Investigation of the biocompatibility and cytotoxicity associated with ROP initiator and its role in bulk polymerization of L-lactide - Parwe, Sharad P.; Warkad, Shrikant D.; Mane, Manoj V.; Shedage, Pranita S.; Garnaik, Baijayantimala (Polymer, 2017)
Poly (L-lactide) (PLLA) is one of the most attractive polymers for use in biomedical applications. In such applications it is necessary to reduce the use of toxic chemicals and catalysts used in PLLA synthesis, to minimize any adverse effects. In view of this, we have performed ring opening polymerization (ROP) of Llactide (LA) using biocompatible initiator, namely, Zinc L-Proline (ZnP) in bulk. High molecular weight PLLA (Mw up to 1.45 x 10(5) Da) was obtained using the ZnP complex. The ZnP complex is safe, easy to prepare, store and handle. H-1 and C-13 NMR spectra of PLLA were used to determine the extent of monomer conversion and stereo sequence respectively. Differential Scanning Calorimetry (DSC) and Size Exclusion Chromatography (SEC) were used to determine thermal properties, Mn, Mw and polydispersity index respectively. The mechanism of ROP of LA in the presence of ZnP was studied using Density Functional Theory (DFf) which was in good agreement with results from H-1 NMR and Matrix-Assisted Laser Desorption/Ionization Spectrometry (MALDI-TOF). Biocompatibility/non toxicity of PLLA prepared using ZnP was studied in-vitro using MTT assay by examining the proliferation rate of mouse myoblast C2C12 cell line. Escherichia coli and Staphylococcus aureus were used for the study of antibacterial activity of PLLA. (C) 2017 Elsevier Ltd. All rights reserved.

Isobaric vapor-liquid equilibrium data for the binary systems of dimethyl carbonate with xylene isomers at 93.13 kPa - Yadav, S.S. (Journal of Chemical and Engineering Data, 2017)
Isobaric binary vapor-liquid equilibrium (VLE) data for dimethyl carbonate with xylene isomers (p-xylene, m-xylene, o-xylene, and ethylbenzene) were measured at the local atmospheric pressure of 93.13 kPa by using a dynamic recirculation still. The experimental VLE data were tested and found to be thermodynamically consistent by Herington and Van Ness consistency test. The experimental VLE data were correlated using the Wilson, NRTL, and UNIQUAC activity coefficient models and binary interactions parameters were estimated using a suitable objective function. The absolute mean deviation between the experimental and the model predicted values of vapor phase composition and total pressure was well within acceptable limits. No azeotrope was observed in any of the binary pairs and appeared to be easy for separation using conventional distillation method.
Keywords: Atmospheric Pressure; binary mixture; Distillation; Xylene

Less frustration, more Activity—theoretical insights into frustrated lewis pairs for hydrogenation catalysis - Mane, M.V. (ChemCatChem, 2017)
The field of frustrated Lewis pair (FLP) chemistry has seen rapid development in only a few years. FLPs have performed most spectacularly in hydrogenation catalysis: a wide variety of FLP-based systems can catalyze the hydrogenation of a range of different substrates, including imines, enamines, ketones, alkynes, and alkenes. However, FLP-based hydrogenation catalysts are yet to match the efficiency of their transition-metal counterparts. The current investigation reveals an important aspect of FLPs that can be exploited to improve their efficiency, that is, the more sterically hindered the FLP catalyst is, the lower is its turnover frequency. Full quantum chemical calculations with DFT for a family of different, experimentally known hydrogenation FLP catalysts shows that superior FLP catalysts can be designed by reducing the frustration (by reducing the steric demand and acid/base strength) in the FLP. However, as lowering the steric demand without reduction in the frustration can result in unwanted side reactions, the design of the most efficient FLP catalysts depends on tuning the system so that both the steric demand and the frustration are reduced appropriately.
Keywords: Boranes; Hydrogenation; reaction mechanism; Steric Hindrance

Linking catalyst-coated isotropic colloids into ``active'' flexible chains enhances their diffusivity - Biswas, Bipul; Manna, Raj Kumar; Laskar, Abhrajit; Kumar, P. B. Sunil; Adhikari, Ronojoy; Kumaraswamy, Guruswamy (ACS Nano, 2017)
Active colloids are not constrained by equilibrium: ballistic propulsion, superdiffusive behavior, or enhanced diffusivities have been reported for active Janus particles. At high concentrations, interactions between active colloids give rise to complex emergent behavior. Their collective dynamics result in the formation of several hundred particle-strong flocks or swarms. Here, we demonstrate significant diffusivity enhancement for colloidal objects that neither have a Janus architecture nor are at high concentrations. We employ uniformly catalyst-coated, viz. chemo-mechanically, isotropic colloids and link them into a chain to enforce proximity. Activity arises from hydrodynamic interactions between enchained colloidal beads due to reaction-induced phoretic flows catalyzed by platinum nanoparticles on the colloid surface. This results in diffusivity enhancements of up to 60% for individual chains in dilute solution. Chains with increasing flexibility exhibit higher diffusivities. Simulations accounting for hydrodynamic interactions between enchained colloids due to active phoretic flows accurately capture the experimental diffusivity. These simulations reveal that the enhancement in diffusivity can be attributed to the interplay between chain conformational fluctuations and activity. Our results show that activity can be used to systematically modulate the mobility of soft slender bodies.
Keywords: active matter; Brownian motion; colloidal assembly; diffusivity; ice templating

Ln(8) (Ln = Gd, Ho, Er, Yb) Butterfly core-exhibiting magnetocaloric effect and field-induced SMM behavior for Er analouge - Bala, Sukhen; Adhikary, Amit; Bhattacharya, Sudeshna; Sen Bishwas, Mousumi; Poddar, Pankaj; Mondal, Raju (ChemistrySelect, 2017)
In this article, we report four pyridyl-pyrazolyl based poly-nuclear cluster complexes with Ln(8) {Ln = [Gd-8(III)(mu(3)-OH)(4)(L-1)(4)(DEA)(4)Cl-4](DMF)(2)(MeOH)(1), [Ho-8(III)(mu(3)-OH)(4)(L-1)(4)(DEA)(4)Cl-4](2), [Er-8(III)(mu(3)-OH)(4)(L-1)(4)(DEA)(4)Cl-4](DMF)(MeOH)(H2O)(3), [Yb-8(III)(mu(3)-OH)(4)(L-1)(4)(DEA)(4)Cl-4](DMF)(MeOH)(4) [DEA = Diethanolamine] cores. The impetus for this study was to explore the magnetic behaviour of lanthanide ions which are often ignored or overlooked. X-ray crystal analysis show that these complexes are isostructural and exhibit an interesting butterfly like topology. The semi-rigidity and asymmetric nature of the ligand led to different coordination environment around the metal centres. The lanthanide ions adopt two types of geometry, a bicapped trigonal prism and a distorted square antiprismatic geometry around the metal center. Such dissimilar coordination environments around the lanthanide centre can have profound effects on their magnetic behaviour. Indeed, the magnetic measurements revealed significant magnetocaloric effect for octanuclear gadolinium complex 1 with magnetic entropy change (-Delta S-m ) of 31.4 J kg(-1) K-1 for Delta H = 9 T at T = 3 K whereas Er analogue complex 3 displayed SMM behavior.

Low-dimensional hybrid perovskites as high performance anodes for alkali-ion batteries - Tathavadekar, Mukta; Krishnamurthy, Shrreya; Banerjee, Aparna; Nagane, Satyawan; Gawli, Yogesh; Suryawanshi, Anil; Bhat, Suresh; Puthusseri, Dhanya; Mohite, Aditya D.; Ogale, Satishchandra (Journal of Materials Chemistry A, 2017)
State-of-the-art Li (or Na) ion batteries work by insertion/extraction of the alkali metal ions into a porous electrode material, where the overall capacity is strongly dependent on the accessibility of the host material interior to the ions. On the other hand, the performance stability depends on various factors governed by the specific constitution of the electrode. Here we show that molecularly engineered low-dimensional hybrid perovskites can work as excellent anode materials for alkali-ion batteries. We measure a high reversible capacity of 646 mA h g(-1) at 100 mA g(-1) with good stability tested up to 250 cycles for the benzidine mediated lead iodide based 1D system. An ex situ analysis of the electrodes reveals that the storage primarily occurs via the Li-x(or Na-x)Pb alloying/de-alloying process. We anticipate that these results open a new direction for the use of low-dimensional hybrid perovskites for energy storage applications.
Keywords: Generation; Inorganic-Organic Hybrid; Lead Iodide; lithiation-intramolecular electrophilic reaction; Na-Air Battery; Negative Electrodes; Organometal Halide perovskites; PB; Sequential Deposition; Solar-cells

Magnetic reduced graphene oxide loaded hydrogels: highly versatile and efficient adsorbents for dyes and selective Cr(VI) ions removal - Halouane, Fatima; Oz, Yavuz; Meziane, Dalila; Barras, Alexandre; Juraszek, Jean; Singh, Santosh K.; Kurungot, Sreekumar; Shaw, Pankaj K.; Sanyal, Rana; Boukherroub, Rabah; Sanyal, Amitav; Szunerits, Sabine (Journal of Colloid and Interface Science, 2017)
The formation of composites of reduced graphene oxide (rGO) and magnetic nanoparticles (MP) has flourished in recent years as they combine the advantages of both nanomaterials. Most of these composite materials are prepared by in situ formation of MP onto rGO or by the post-adsorption onto rGO. We report here on a simple and highly controlled method for the fabrication of different magnetic 3D rGO-loaded hydrogels. Cellulose bound magnetic nanoparticles (MP@cellulose) were synthesized by chemical co-precipitation and loaded together with rGO into poly(ethylene glycol) dimethacrylate based hydrogels during their fabrication using photo-polymerization. The magnetic rGO-loaded hydrogels proved to be highly adaptable to different applications. The as-formed composites allowed for efficient dye removal with an adsorption capacity of 111.9 +/- 4 mg g(-1) in the case of methylene blue (MB). Integration of poly(ethyleneimine) (PEI) allowed for the selective capturing of Cr6+ ions with an adsorption capacity of 313 12 mg g-1. Most importantly, independent of the application, the magnetic rGO-loaded hydrogel can be regenerated without loss of its adsorption capacity. (C) 2017 Elsevier Inc. All rights reserved.

Mapping architectural and transcriptional alterations in non-lesional and lesional epidermis in vitiligo - Singh, Archana; Gotherwal, Vishvabandhu; Junni, Paivi; Vijayan, Vinaya; Tiwari, Manisha; Ganju, Parul; Kumar, Avinash; Sharma, Pankaj; Fatima, Tanveer; Gupta, Aayush; Holla, Ananthaprasad; Kar, Hemanta K.; et al. (Scientific Reports, 2017)
In vitiligo, chronic loss of melanocytes and consequent absence of melanin from the epidermis presents a challenge for long-term tissue maintenance. The stable vitiligo patches are known to attain an irreversible depigmented state. However, the molecular and cellular processes resulting in this remodeled tissue homeostasis is unclear. To investigate the complex interplay of inductive signals and cell intrinsic factors that support the new acquired state, we compared the matched lesional and non-lesional epidermis obtained from stable non-segmental vitiligo subjects. Hierarchical clustering of genome-wide expression of transcripts surprisingly segregated lesional and non-lesional samples in two distinct clades, despite the apparent heterogeneity in the lesions of different vitiligo subjects. Pathway enrichment showed the expected downregulation of melanogenic pathway and a significant downregulation of cornification and keratinocyte differentiation processes. These perturbations could indeed be recapitulated in the lesional epidermal tissue, including blunting of rete-ridges, thickening of stratum corneum and increase in the size of corneocytes. In addition, we identify marked increase in the putrescine levels due to the elevated expression of spermine/spermidine acetyl transferase. Our study provides insights into the intrinsic self-renewing ability of damaged lesional tissue to restore epidermal functionality in vitiligo.

Mapping of optimum operating condition for LiBr-water refrigeration cycles - Mali, Nilesh A.; Bhagwat, Sunil S. (Sadhana: Academy Proceedings in Engineering Sciences, 2017)
In this work, optimum operating condition maps are generated covering wide ranges of refrigeration and sink temperatures for single-and double-effect LiBr-water vapour absorption refrigeration cycle. These optimum condition maps will be useful to choose optimum operating conditions while designing LiBr-water cycle for desired applications. Methodology for generating such maps is discussed in detail, which can also be used for other absorption refrigeration cycles with various working fluids. Three configurations of LiBr-water absorption refrigeration cycles, single effect, double-effect series flow and double-effect parallel flow, are analysed with the most accurate thermodynamic property correlation available in the literature. Sensitivity of cycle performance to various operating variables such as generator, absorber and condenser temperatures is determined. Second law analysis shows that when a higher temperature heat source is available, double-effect cycles are more effective over single effect as they have higher coefficient of performance.

Mass spectrometry based identification of galectin-3 interacting proteins potentially involved in lung melanoma metastasis - Dange, Manohar C.; Bhonsle, Hemangi S.; Godbole, Rashmi K.; More, Shyam K.; Bane, Sanjay M.; Kulkarni, Mahesh J.; Kalraiya, Rajiv D. (Molecular Biosystems, 2017)
Adhesive interactions between molecules on tumor cells and those on target organs play a key role in organ specific metastasis. Poly-N-acetyl-lactosamine (polyLacNAc) substituted N-oligosaccharides on melanoma cell surface glycoproteins promote lung specific metastasis via galectin-3 by facilitating their arrest and extravasation. This study reports the identification and characterization of galectin-3 interacting proteins using a combination of galectin-3 sepharose affinity and leucoagglutinating phytohemagglutinin (L-PHA) columns. A total of 83 proteins were identified as galectin-3 interacting glycoproteins, of which 35 were constituents of the L-PHA bound fraction, suggesting that these proteins carry polyLacNAc substituted beta 1,6 branched N-glycans. The identities of some of these proteins, like LAMP-1, LAMP-3, basigin, embigin, and alpha 5 and beta 1 Integrin, have been confirmed by western blotting, and functional relevance with respect to metastatic properties has been established.

Mechanism of unfolding of human prion protein - Singh, R. K.; Chamachi, N. G.; Chakrabarty, S.; Mukherjee, A. (Journal of Physical Chemistry B, 2017)
Misfolding and aggregation of prion proteins are associated with several neurodegenerative diseases. Therefore, understanding the mechanism of the misfolding process is of enormous interest in the scientific community. It has been speculated and widely discussed that the native cellular prion protein (PrPC) form needs to undergo substantial unfolding to a more stable PrPC* state, which may further oligomerize into the toxic scrapie (PrPSc) form. Here, we have studied the mechanism of the unfolding of the human prion protein (huPrP) using a set of extensive well-tempered metadynamics simulations. Through multiple microsecond-long metadynamics simulations, we find several possible unfolding pathways. We show that each pathway leads to an unfolded state of lower free energy than the native state. Thus, our study may point to the signature of a PrPC*. form that corresponds to a global minimum on the conformational free-energy landscape. Moreover, we find that these global minima states do not involve an increased beta-sheet content, as was assumed to be a signature of PrPSc formation in previous simulation studies. We have further analyzed the origin of metastability of the PrPC form through free energy surfaces of the chopped helical segments to show that the helices, particularly H2 and H3 of the prion protein, have the tendency to form either a random coil or a beta-structure. Therefore, the secondary structural elements of the prion protein are only weakly stabilized by tertiary contacts and solvation forces so that relatively weak perturbations induced by temperature, pressure, pH, and so forth can lead to substantial unfolding with characteristics of intrinsically disordered proteins.

Mechanochemical synthesis of N-salicylideneaniline: thermosalient effect of polymorphic crystals - Mittapalli, Sudhir; Perumalla, D. Sravanakumar; Nangia, Ashwini (IUCRJ, 2017)
Polymorphs of the dichloro derivative of N-salicylideneaniline exhibit mechanical responses such as jumping (Forms I and III) and exploding (Form II) in its three polymorphs. The molecules are connected via the amide N-H center dot center dot center dot O dimer synthon and C-Cl center dot center dot center dot O halogen bond in the three crystal structures. A fourth high-temperature Form IV was confirmed by variable-temperature single-crystal X-ray diffraction at 180 degrees C. The behaviour of jumping exhibited by the polymorphic crystals of Forms I and III is due to the layered sheet morphology and the transmission of thermal stress in a single direction, compared with the corrugated sheet structure of Form II such that heat dissipation is more isotropic causing blasting. The role of weak C-Cl center dot center dot center dot O interactions in the thermal response of molecular crystals is discussed.
Keywords: crystal design; crystal engineering; Halogen bonding; hydrogen bonding; intermolecular interactions; materials science; mechanochemistry; polymorphism

Metal-free radical trifluoromethylation of beta-nitroalkenes through visible-light photoredox catalysis - Midya, Siba P.; Rana, Jagannath; Abraham, Thomas; Aswin, Bhaskaran; Balaraman, Ekambaram (Chemical Communications, 2017)
A catalytic method for functional group interconversion is immensely important in modern sciences. Here, we report an efficient catalytic conversion of nitroalkenes to highly stereoselective 1-trifluoromethylalkenes at room temperature. This unprecedented metal-free photocatalytic strategy is simple and operates under visible-light irradiation using the commercially available CF3 source.

Microvirga indica sp. Nov., an arsenite-oxidizing alphaproteobacterium, isolated from metal industry waste soil - Tapase, S. R. (International Journal of Systematic and Evolutionary Microbiology, 2017)
A novel Gram-stain-negative bacterium, strain S-MI1bT, belonging to the genus Microvirga was isolated from a metal industry waste soil sample in Pirangut village, Pune District, Maharashtra, India. Cells were non-spore-forming, small rod-shapes, motile and strictly aerobic with light-pink colonies. The strain grew in 0-7.0 % (w/v) NaCl and at 25-45 °C, with optimal growth at 40 °C. The predominant fatty acids detected were summed feature 8 (C18 : 1 ω7c and/or C18 : 1 ω6c) and C19 : 0 cyclo ω8c. The predominant isoprenoid quinone was Q-10. The G+C content was 67.2 mol% and DNA-DNA relatedness values between strain S-MI1bTand Microvirga subterranea DSM 14364T and Microvirgaaerophila 5420S-12T were 53.9 and 54.8 %, respectively. Phylogenetic analysis, based on 16S rRNA gene sequences, indicated that strain S-MI1bT is a member of the genus Microvirga, with greatest sequence similarities of 97.7 and 97.4 % with M. subterranea DSM 14364T and M.aerophila 5420S-12T, respectively. Phylogenetic analysis showed that strain S-MI1bT forms a clade with the type strain of M. subterranea DSM 14364T, and was readily distinguishable from it due to various phenotypic characteristics. The combination of genotypic and phenotypic data suggests that the isolate represents a novel species of the genus Microvirga, for which the name Microvirga indica sp. nov. is proposed. The type strain is S-MI1bT (=NCIM-5595T=KACC 18792T=BCRC 80972T)

Microwave-assisted synthesis of 5-substituted 1H-tetrazoles via [3+2] cycloaddition over a heterogeneous Cu-based catalyst: application to the preparation of N-13-labelled tetrazoles - Joshi, Sameer M.; Mane, Rasika B.; Pulagam, Krishna R.; Gomez-Vallejo, Vanessa; Llop, Jordi; Rode, Chandrashekhar (New Journal of Chemistry, 2017)
The [3+2] cycloaddition between various nitriles and sodium azide proceeds smoothly in the presence of a new Cu-II catalyst in N-methyl-2-pyrrolidone (NMP) to give the corresponding 5-substituted 1H-tetrazoles. The desired tetrazoles were obtained in high yields within 3-30 min by employing controlled microwave heating. The reaction most probably proceeds through the activation of the nitrile groups by the Cu-II species, followed by a successive [3+2] cycloaddition with the sodium azide. The good performance of the catalyst enabled the preparation of selected tetrazoles labelled with the positron emitter nitrogen-13 even under conventional heating. The short reaction time, simple work-up procedure, and recyclability of the catalyst are advantages of the method reported here.

Mixed-stack charge transfer crystals of pillar[5]quinone and tetrathiafulvalene exhibiting ferroelectric features - Shivakumar, Kilingaru I.; Swathi, Kadaba; Goudappagouda; Das, Tamal C.; Kumar, Ashwani; Makde, Ravindra D.; Vanka, Kumar; Narayan, Kavassery S.; Babu, Sukumaran Santhosh; Sanjayan, Gangadhar J. (Chemistry- A European Journal, 2017)
Ferroelectric materials find extensive applications in the fabrication of compact memory devices and ultra-sensitive multifunctional detectors. Face-to-face alternate stacking of electron donors and acceptors effectuate long-range unidirectional ordering of charge-transfer (CT) dipoles, promising tunable ferroelectricity. Herein we report a new TTF-quinone system-an emerald green CT complex consisting pillar[5]quinone (P5Q) and tetrathiafulvalene (TTF). The CT crystals, as determined by single crystal synchrotron X-ray diffraction, adopt a 1:1 mixed-stack arrangement of donor and acceptor with alternating dimers of TTF and 1,4-dioxane encapsulated P5Q. The TTF-P5Q.dioxane crystal possesses a macroscopic polarization axis giving rise to ferroelectricity at room temperature. The CT complex manifests ferroelectric features such as optical polarization rotation, temperature-dependent phase transition and piezoelectric response in single crystals. Ferroelectric behavior observed in P5Q-based CT complex widens the scope for further work on this structurally intriguing and readily accessible cyclic pentaquinone.
Keywords: Acceptor; Charge-transfer complexes; Chemistry; Conductors; DDQ; Donor; ferroelectric; Macrocycles; Organic Metals; Pi-interaction; Pillar[5]quinone; salts; Transfer Complexes; Transport

Multilocus sequence typing of Ochrobactrum spp. isolated from gastric niche - Kulkarni, Girish (Journal of Infection and Public Health, 2017)
The human stomach is colonized by diverse bacterial species. The presence of non-Helicobacter pylori bacteria in urease-positive biopsies of individuals has been reported. Bacteria belonging to the Ochrobactrum genus have been documented in the human gastric niche. The co-occurrence of Ochrobactrum spp. with H. pylori was previously reported in an antral biopsy of a non-ulcer dyspeptic (NUD) subject from Northern India. There is no information on the genetic diversity of Ochrobactrum spp. isolated from the gastric niche in the stomach. We aimed to study the species distribution and diversity of Ochrobactrum spp. with and without H. pylori in urease-positive biopsies across three different geographical regions in India. Sixty-two Ochrobactrum isolates recovered from patients with an upper gastric disorder (n=218) were subjected to molecular identification and multilocus sequence typing. H. pylori DNA was found in the majority of biopsies, which had a variable degree of Ochrobactrum spp present. Interestingly, some of the urease-positive biopsies only had Ochrobactrum without any H. pylori DNA. Based on phylogenetic analysis, the Ochrobactrum isolates were distributed into the O. intermedium, O. anthropi and O. oryzae groups. This indicates there are multiple species in the gastric niche irrespective of the presence or absence of H. pylori. Antibiotyping based on colistin and polymyxin B could differentiate between O. intermedium and O. anthropi without revealing the resistance-driven diversity. Considering the prevalence of multiple Ochrobactrum spp. in the human gastric niche, it is important to evaluate the commensal and/or pathogenic nature of non-H. pylori bacteria with respect to their geographical distribution, lifestyle and nutrition needs.
Keywords: Helicobater Pyroli; MLST; Non-Ulcer Dyspepsia; Ochrobactrum

Multi-mode hydrogen storage in nanocontainers - Shervani, Suboohi; Mukherjee, Puspal; Gupta, Anshul; Mishra, Gargi; Illath, Kavya; Ajithkumar, Thallaseril G.; Sivakumar, Sri; Sen, Pratik; Balani, Kantesh; Subramaniam, Anandh (International Journal of Hydrogen Energy, 2017)
Hydrogen can be stored in containers or in materials (in molecular or atomic forms). The atomic form can further exist as multiple phases. Molecular hydrogen can be adsorbed on the surface or can be present inside the material. By invoking multiple modes of hydrogen storage, we establish a paradigm shift in the philosophy of hydrogen storage. Using a novel strategy of storage of molecular hydrogen in metal (Pd) nanocontainers, we observe that 18% hydrogen is in molecular form. Interestingly, this is achieved at 25 °C and 1 atm pressure; which is in contrast to storage in MOFs and carbonaceous materials like nanotubes. Enhancement in storage capacity as compared to Pd nanocrystals of the same mass is observed (36% increase at 1 atm & 25 °C), along with fast kinetics (0.5 wt% hydrogen absorption in 5 s). A new mechanism for hydrogen storage involving the dual catalytic role of Pd is established.

Multipronged quantitative proteomics reveals serum proteome alterations in breast cancer intrinsic subtypes - Gajbhiye, Akshada; Dabhi, Raju; Taunk, Khushman; Jagadeeshaprasad, Mashanipalya G.; RoyChoudhury, Sourav; Mane, Anupama; Bayatigeri, Santhakumari; Chaudhury, Koel; Santra, Manas K.; Rapole, Srikanth (Journal of Proteomics, 2017)
Being molecularly heterogeneous, breast cancer tends to be a complicated oncological disease with high incidence rates throughout the world. The primary aim of this study was to identify the set of serum proteins with discriminatory capabilities towards the four major subtypes of breast cancer. We employed multipronged quantitative proteomic approaches like 2D-DIGE, iTRAQ and SWATH-MS and identified 307 differentially regulated proteins. Luminal A subtype consisted of 24, Luminal B subtype 38, HER2 Enriched subtype 17 and Triple negative breast cancer subtype 10 differentially regulated subtype specific proteins. These specific proteins were further subjected to bioinformatic tools which revealed the involvement in platelet degranulation, fibrinolysis, lipid metabolism, immune response, complement activation, blood coagulation, glycolysis and cancer signaling pathways in the subtypes of the breast cancer. The significant discrimination efficiency of the models generated through multivariate statistical analysis was decent to distinguish each of the four subtypes from controls. Further, some of the statistically significant differentially regulated proteins were verified and validated by immunoblotting and mass spectrometry based selected reaction monitoring (SRM) approach. Our Multipronged proteomics approaches revealed panel of serum proteins specifically altered for individual subtypes of breast cancer. The mass spectrometry data are available via ProteomeXchange with identifier PXD006441. Biological significance: Worldwide, breast cancer continues to be one of the leading causes of cancer related deaths in women and it encompasses four major molecular subtypes. As breast cancer treatment majorly depends on identification of specific subtype, it is important to diagnosis the disease at subtype level. Our results using multipronged quantitative proteomics identified 307 differentially regulated proteins in which 24 were specific for Luminal A, 38 for Luminal B, 17 for HER2 enriched and 10 proteins were specific for TN subtype. Bioinformatic analysis of these proteins revealed certain biological processes and pathways altered at subtype level and validation experiments of some of these proteins using immunoblotting and SRM assays are consistent with discovery data. This is the first comprehensive proteomic study on serum proteome alterations at subtype level which will not only help to distinguish subtype of breast cancer but also contribute to a better understanding of the molecular characteristic of breast cancer at individual subtype level. (C) 2017 Elsevier B.V. All rights reserved.

N - heterocyclic - carbene - catalyzed umpolung of imines - Patra, Atanu; Mukherjee, Subrata; Das, Tamal Kanti; Jain, Shailja; Gonnade, Rajesh Ghanshyam; Biju, Akkattu T. (Angewandte Chemie International Edition, 2017)
N-Heterocyclic carbene (NHC) catalysis has been widely used for the umpolung of aldehydes, and recently for the umpolung of Michael acceptors. Described herein is the umpolung of aldimines catalyzed by NHCs, and the reaction likely proceeds via aza-Breslow intermediates. The NHC-catalyzed intramolecular cyclization of aldimines bearing a Michael acceptor resulted in the formation of biologically important 2-(hetero)aryl indole 3-acetic-acid derivatives in moderate to good yields. The carbene generated from the bicyclic triazolium salt was found to be efficient for this transformation.

Nano-heteroarchitectures of two-dimensional MoS 2 @ one-dimensional brookite TiO 2 nanorods: prominent electron emitters for displays - Devan, Rupesh S.; Thakare, Vishal P.; Antad, Vivek V.; Chikate, Parameshwar R.; Khare, Ruchita T.; More, Mahendra; Dhayal, Rajendra S.; Patil, Shankar I.; Ma, Yuan-Ron; Schmidt-Mende, Lukas (ACS Omega, 2017)
We report comparative field electron emission (FE) studies on a large-area array of two-dimensional MoS2-coated @ one-dimensional (1D) brookite (β) TiO2 nanorods synthesized on Si substrate utilizing hot-filament metal vapor deposition technique and pulsed laser deposition method, independently. The 10 nm wide and 760 nm long 1D β-TiO2 nanorods were coated with MoS2 layers of thickness ∼4 (±2), 20 (±3), and 40 (±3) nm. The turn-on field (Eon) of 2.5 V/μm required to a draw current density of 10 μA/cm² observed for MoS2-coated 1D β-TiO2 nanorods emitters is significantly lower than that of doped/undoped 1D TiO2 nanostructures, pristine MoS2 sheets, MoS2@SnO2, and TiO2@MoS2 heterostructure-based field emitters. The orthodoxy test confirms the viability of the field emission measurements, specifically field enhancement factor (βFE) of the MoS2@TiO2/Si emitters. The enhanced FE behavior of the MoS2@TiO2/Si emitter can be attributed to the modulation of the electronic properties due to heterostructure and interface effects, in addition to the high aspect ratio of the vertically aligned TiO2 nanorods. Furthermore, these MoS2@TiO2/Si emitters exhibit better emission stability. The results obtained herein suggest that the heteroarchitecture of MoS2@β-TiO2 nanorods holds the potential for their applications in FE-based nanoelectronic devices such as displays and electron sources. Moreover, the strategy employed here to enhance the FE behavior via rational design of heteroarchitecture structure can be further extended to improve other functionalities of various nanomaterials.

Nanoparticle assembly: a perspective and some unanswered questions - Kumar, Sanat K.; Kumaraswamy, Guruswamy; Prasad, Bhagavatula L. V.; Bandyopadhyaya, Rajdip; Granick, Steve; Gang, Oleg; Manoharan, Vinothan N.; Frenkel, Daan; Kotov, Nicholas A. (Current Science, 2017)
In early 2016, the Royal Society of Chemistry arranged a meeting on the topic 'Nanoparticle Assemblies: from Fundamentals to Applications' which was hosted at IIT-Bombay, Mumbai. The meeting brought several leading nanoscience and nanotechnology researchers to India and is only the second Faraday Discussions meeting to have been held in the country. The papers presented at the meeting and the resulting active discussions have been summarized in a Faraday Discussion issue(1). The broad range of topics discussed at the meeting led to an understanding on where we stand in the field of nanoparticle assembly, and also enunciated some of the outstanding fundamental and practical issues that remain to be resolved before these ideas can be applied to practical situations. Driven by these ideas, here we focus on four topics/questions: (i) Can we achieve function-driven design of nanoparticle assemblies? (ii) What is the minimal information needed to build a desired assembly? (iii) How complex a structure can one build? How can one make it responsive? What are the relative roles of equilibrium versus dynamics in the assembly process, and are we at a point where we can now pursue active assembly as a viable mode for creating complex assemblies? (iv) What are the applications that are being targeted and what are the barriers to implementation? In this perspective, we do not present an exhaustive survey of the vast literature in this area, but indicate overarching themes/questions that require immediate attention, largely based on the discussions at the Mumbai meeting.

Nanotubular hard carbon derived from renewable natural seed gel for high performance sodium-ion battery anode - Sharma, Neha; Gawli, Yogesh; Ahmad, Absar; Muhammed, Musthafa; Ogale, Satishchandra (Chemistryselect, 2017)
Electrical energy storage devices such as batteries and supercapacitors are perhaps the most researched topic today in view of its critical implications for the successful implementations of various renewable energy harvesting initiatives. Amongst the various battery systems being currently examined, the Li-battery continues to be a main player, but the Na-ion battery has been attracting significant attention lately due to the concerns about the limited reserves and high cost of Li. Hard carbon is recognized to be a good anode material for Na-battery. In this work we present a novel approach to synthesize such hard carbon from a natural gel derived from the commonly used Basil seeds (Osimum Basilicum) which swell 30 times their weight by absorbing water. The hard carbon obtained by pyrolysis of the freeze-dried mucilage possesses sheet-like and tubular morphology with decorated surface defects attributed to the presence of oxygen functionalities. This hard carbon shows a good reversible capacity of 195 mAh g(-1) at 0.1A g(-1) with an impressive approximate to 91% retention of initial capacity after 300 cycles and sustains high current densities with not much change in capacity value.

Nature of selenium hydrogen bonding: gas phase spectroscopy and quantum chemistry calculations - Mishra, Kamal K.; Singh, Santosh K.; Ghosh, Paulami; Ghosh, Debashree; Das, Aloke (Physical chemistry Chemical physics, 2017)
<div class="block-record-info" style="margin: 0px 22px 22px; list-style: none; padding: 0px; line-height: 20px; font-size: 13px; color: rgb(51, 51, 51); font-family: arial, helvetica, sans-serif; background-color: rgb(248, 248, 248);"> Subsequent to the recent re-definition of hydrogen bonding by the IUPAC committee, there has been a growing search for finding the presence of this ever interesting non-covalent interaction between a hydrogen atom in an X-H group and any other atom in the periodic table. In recent gas phase experiments, it has been observed that hydrogen bonding interactions involving S and Se are of similar strength to those with an O atom. However, there is no clear explanation for the unusual strength of this interaction in the case of hydrogen bond acceptors which are not conventional electronegative atoms. In this work, we have explored the nature of Se hydrogen bonding by studying indole...dimethyl selenide (indmse) and phenol...dimethyl selenide (phdmse) complexes using gas phase IR spectroscopy and quantum chemistry calculations. We have found through various energy decomposition analysis (EDA) methods and natural bond orbital (NBO) calculations that, along with electrostatics and polarization, charge transfer interactions are important to understand Se/S hydrogen bonding and there is a delicate balance between the various interactions that plays the crucial role rather than a single component of the interaction energy. An in-depth understanding of this type of non-covalent interaction has immense significance in biology as amino acids containing S and Se are widely present in proteins and hence hydrogen bonding interactions involving S and Se atoms contribute to the folding of proteins.
Keywords: Center-Dot-O; Clusters; Co-Ordination; Complexes; intermolecular interactions; Proteins; Replacement; spectra; Strength; Sulfur

New and efficient enantioselective synthesis of both enantiomers of the calcium channel blocker bepridil - Mujahid, Mohammad; Subramanian, Jambu; Nalla, Viswanadh; Sasikumar, Murugesan; Kunte, Sunita Sharad; Muthukrishnan, Murugan (New Journal of Chemistry, 2017)
A concise and efficient enantioselective synthesis of both enantiomers of bepridil, a calcium channel blocker, is reported. Jacobsen's hydrolytic kinetic resolution method was utilized to resolve racemic 2-(isobutoxymethyl) oxirane. The incorporation of the succinimide moiety by the Mitsunobu reaction, which was investigated in detail, occurred without any loss of enantioselectivity. Using this strategy, both enantiomers of the target molecule were obtained in good yield and with high enantiopurity (ee > 99%).

New bithiazolyl hydrazones: novel synthesis, characterization and antitubercular evaluation - Bhalerao, Mahendra B.; Dhumal, Sambhaji T.; Deshmukh, Amarsinh R.; Nawale, Laxman U.; Khedkar, Vijay M.; Sarkar, Dhiman; Mane, Ramrao A. (Bioorganic & Medicinal Chemistry Letters, 2017)
New bithiazolyl hydrazones (6a–l) have been first time synthesized by carrying novel one pot cyclocondensation of 5-acyl thiazoles (1a–b), thiosemicarbazide (2) and substituted phenacyl chlorides (4a–f) in freshly prepared ionic liquid, diisopropyl ethyl ammonium acetate (DIPEAc) at room temperature. The newly synthesized compounds have been evaluated for their antitubercular activity and the compounds 3b, 6a, 6b, 6d, 6e, 6f, 6g, and 6l have displayed noticeable antitubercular activity compared to Rifampicin with tolerable cytotoxicity. All these compounds were also screened for their antibacterial activity and found that, compounds 6j and 6k have exhibited a very good antibacterial activity. Molecular docking study has shown better harmony with the evaluation trend shown by these compounds under in vitro antitubercular screening.

New pyrene cored small organic molecule with a flexible alkyl spacer: a potential solution processable blue emitter with bright photoluminescence - Valsange, Nitin G.; Wong, F. L.; Shinde, Durgaprasad; Lee, C. S.; Roy, V. A. L.; Manzhos, Sergei; Feron, K.; Chang, Samuel; Katoh, Ryuzi; Sonar, Prashant; Wadgaonkar, Prakash P. (New Journal of Chemistry, 2017)
A new pyrene cored small organic molecule viz. 1,3,6,8-tetrakis(4-((5-(9H-carbazol-9-yl) pentyl)oxy) phenyl)pyrene (PY-II) was designed and synthesized. The carbazole moiety with an alkyl spacer was introduced at 1, 3, 6 and 8 positions of the pyrene core to improve the charge transport properties and solution processability. PY-II exhibited excellent solubility in common organic solvents and high thermal stability up to 345 degrees C. The photoluminescence quantum yield (PLQY) of PY-II in solution was found to be 0.9 with bright blue emission near 450 nm which is just appropriate for the human eye. The solution processed non-doped OLED device fabricated using PY-II as an emissive layer afforded a pure blue emission with CIE coordinates of 0.16 and 0.16, a power efficiency of 0.17 lm W-1, a maximum current efficiency of 0.41 cd A(-1) and a maximum brightness of 202 cd m(-2).

N-Heterocyclic carbene-catalyzed aldol-lactonization of ketoacids via dynamic kinetic resolution - Mondal, Santigopal; Mukherjee, Subrata; Das, Tamal Kanti; Gonnade, Rajesh; Biju, Akkattu T. (ACS Catalysis, 2017)
N-Heteroryclic carbene (NHC)-catalyzed enantioselective aldol lactonization of acyclic ketoacids, proceeding via dynamic kinetic resolution, is presented. The carbene generated from the chiral anninoinclanol-derived triazolium salt in the presence of LiCl was the key for the success of this transformation. The reaction allowed the diastereoselective and enantioselective synthesis of cyclopentane-fused beta-lactones having three contiguous stereocenters. The reaction products are shown to undergo substrate-controlled beta-lactone opening in the presence of amines to afford succinimide derivatives with four contiguous stereocenters.
Keywords: aldol lactonization; beta-lactones; DKR strategies; ketoacids; N-heterocyclic carbenes; organocatalysis

Nonlinear Fowler-Nordheim behavior of a single SnO2 nanowire - Joshi, Padmashree D.; Joag, Dilip S.; Late, Dattatray J.; Mulla, Imtiaz S. (Journal of Vacuum Science & Technology B, 2017)
The present work deals with the field emission study on multiple SnO2 nanowires synthesized by a simple thermal evaporation method. The randomly oriented multiple nanowires grown by the vapor-liquid-solid mechanism exhibit low turn on field (0.8V/mu m defined for the current density of 1 mu A/cm(2)) and linear Fowler-Nordheim nature (FN). However, for the understanding of the nature of the FN plot, field emission behavior of a single SnO2 nanowire is investigated. The FN plot is observed to be nonlinear in nature. A simple model explaining the field emission mechanism from the semiconducting single SnO2 nanowire is proposed. (C) 2017 American Vacuum Society.

Novel interaction study of Th(IV) and Zr(IV) with 4-sulfonatocalix[6]arene: experimental and theoretical investigation - Rathod, N.V. (Polyhedron, 2017)
Calixarenes based ligands are well known in the extraction of heavy metal ions. The modifications at lower as well as upper rim increase the new possibilities of metal extraction in terms of quantum and selectivity of metal. In comparison to calix[4]arene, complexing nature of calix[6]arene is less studied due to its large size and flexible nature. In the present study, 4-sulfonatocalix[6]arene (SCX6) is synthesized and an attempt has been made to understand its complexation behavior with Th(IV) and Zr(IV) metal ions. The effect of different solvents has been examined along with calculation of binding constants for better complexation possibilities. Though in general, its complexation proves to be at 1:1 stoichiometry with respect to ligand and metal, the specific metals show its characteristic modes of interaction with the ligand. This has been understood through IR spectroscopic analysis and density functional theory based first principle studies. 1H NMR spectra of SCX6 and its complexes with Th(IV) and Zr(IV) metal ions was established. IR, UV–Vis, fluorescence spectroscopic studies provided a systematic understanding about the binding behavior of these two metals including interference possibilities from other metals.
Keywords: 4-Sulfonatocalix[6]arene; DFT; metal complexation; Th(IV) Zr(IV)

Novel silaproline (Sip)-incorporated close structural mimics of potent antidepressant peptide drug rapastinel (GLYX-13) - Madica, Krishnaprasad; Nadimpally, Krishna Chaitanya; Sanjayan, Gangadhar J. (Tetrahedron Letters, 2017)
Rapastinel (GLYX-13) is a C-amidated tetrapeptide drug under clinical development for adjunctive treatment of major depressive disorder (MDD). Rapastinel features two consecutive proline residues centered at the peptide sequence (Thr-Pro-Pro-Thr-NH2), which are detrimental to its biological activity. In this communication, we report the synthesis of very close structural analogues of rapastinel comprising silaproline (Sip) as proline surrogate. By virtue of its enhanced lipophilicity and metabolic stability, Sip introduction in the native rapastinel sequence is expected to improve its pharmacokinetic profiles.

Optimization for the production of mycelial biomass from Benjaminiella poitrasii to isolate highly deacetylated chitosan - Mane, S. R.; Pathan, Ejaj K.; Kale, D.; Ghormade, Vandana; Gadre, Ramchandra V.; Rajamohanan, Pattuparambil Ramanpillai; Badiger, Manohar V.; Deshpande, Mukund V. (Journal of Polymer Materials, 2017)
Benjaminiella poitrasii, a dimorphic zygomycetous fungus contains more chitosan in the mycelial cell wall than the cell wall of its yeast form. The optimized medium containing yeast extract, peptone, MgSO4, KH2PO4, trace metals (Fe2+, Mn2+ Zn2+ and Co2+ ) solution and 1% starch produced 10-12 g/L(dry wt.) of mycelial biomass in 48 h in a 2L fermenter. Using 1N NaOH treatment from 1 g of dried biomass 51.00 ± 0.52 mg of chitosan of 42.82 KDa molecular weight and 94.24 % degree of deacetylation was extracted. With Metarhizium anisopliae chitin deacetylase (CDA), chitosan yield was 59.00 ± 0.84 mg while treatment with CDA of B. poitrasii it was 78.05 ± 0.58 mg/g of dry wt. of biomass. The chitosan dissolved in 2% acetic acid showed higher antifungal activity against Candida albicans (MIC90 0.025 mg/mL) and Candida glabrata (MIC90 0.2 mg/mL) than chitosan extracted from marine source (MIC90 >1.6 mg/mL) suggesting use of fungal chitosan in healthcare.

Optimizing culture conditions for establishment of hairy root culture of semecarpus anacardium L. - Panda, Bhuban Mohan; Mehta, Urmil J.; Hazra, Sulekha (3 Biotech, 2017)
Semecarpus anacardium L. is a tree species which produces secondary metabolites of medicinal importance. Roots of the plant have been traditionally used in folk medicines. Different strains of Agrobacterium rhizogenes (A4, ATCC15834 and LBA 9402) were used for induction of hairy roots in in vitro grown tissues of the plant. Hairy root initiation was observed after 25-30 days of infection. Optimum transformation frequency of 61% was achieved on leaf explants with ATCC15834 strain. Infection time of 30 min resulted in greater transformation frequency compared to 10 and 20 min, respectively. The hairy roots cultured in growth regulator-free semi-solid woody plant medium differentiated into callus. Whole shoots infected with ATCC 15834 were found to produce more transformants upon co-cultivation for 4 (65%) and 5 (67%) days. Induction of hairy roots in stem explants infected with ATCC 15834 was lower (52%) compared to leaves (62%) after 4 days of co-cultivation. In A4 and LBA9402 strains transformation efficiency was 49 +/- 2.8% and 36 +/- 5.7% in shoots after 4 days of co-cultivation. Transformation frequency was higher in ATCC15834 strain, irrespective of explants. The hairy roots of S. anacardium elongated slowly upon transfer to half-strength liquid medium. After 3-4 passages in liquid medium slender hairy roots started differentiating which were separated from the original explants. Visible growth of the roots was observed in hormone-free liquid medium after 2-3 months of culturing. Polymerase chain reaction with gene-specific primers from rol A, B and C genes confirms the positive transformation events.
Keywords: Hairy root culture; In vitro culture; rol genes; Semecarpus anacardium; Transformation

Organocatalytic enantioselective vinylogous michael-aidoi cascade for the synthesis of spirocyclic compounds - Mondal, Santigopal; Mukherjee, Subrata; Yetra, Santhivardhana Reddy; Gonnade, Rajesh G.; Biju, Akkattu T. (Organic Letters, 2017)
Enantioselective synthesis of pyrazolone-fused spirocyclohexenols by the secondary amine-catalyzed cascade reaction of alpha,beta-unsaturated aldehydes with alpha-arylidene pyrazolinones is reported. This formal [3 + 3] organocascade reaction proceeds through a vinylogous Michael-aldol sequence to furnish the spiroheterocycles with three stereocenters including an all-carbon quaternary center in good yields and selectivities. The catalytic generation of alpha,beta-unsaturated iminium ions from enals and tandem dienolate/enolate formation from pyrazolinones are the key for the success of this spiroannulation reaction.

Organocatalyzed efficient one-pot synthesis, biological evaluation, and molecular docking studies of 4,4-(Arylmethylene)bis-(3-methyl-1-phenyl-1H-pyrazol-5-ols) - Mahajan, Pravin S.; Nikam, Mukesh D.; Khedkar, Vijay; Jha, Prakash; Badadhe, Pravin V.; Gill, Charansingh H. (Journal of Heterocyclic Chemistry, 2017)
The synthesis of 4,4-(arylmethylene)bis-(3-methyl-1-phenyl-1H-pyrazol-5-ol) derivatives catalyzed by ?-proline is a simple, versatile, and efficient method. In vitro antioxidant, anti-inflammatory, and antimicrobial activities of compounds 4a, 4b, 4c, 4d, 4e, 4f, 4g, 4h, 4i, 4j were studied. Furthermore, to rationalize the observed anti-inflammatory activity data, molecular docking study has been performed against COX-2 enzyme which revealed a good binding affinity for these molecules and could provide an insight into the various bonded and non-bonded interactions guiding their binding affinity.

Overcoming the lack of oral availability of cyclic hexapeptides: design of a selective and orally available ligand for the integrin alpha v beta 3 - Weinmueller, Michael; Rechenmacher, Florian; Marelli, Udaya Kiran; Reichart, Florian; Kapp, Tobias G.; Raeder, Andreas F. B.; Di Leva, Francesco Saverio; Marinelli, Luciana; Novellino, Ettore; Munoz-Felix, Jose M.; Hodivala-Dilke, Kairbaan; Schumacher, Adi; et al. (Angewandte Chemie-International Edition, 2017)
Ahighly systematic approach for the development of both orally bioavailable and bioactive cyclic N-methylated hexapeptides as high affinity ligands for the integrin alpha v beta 3 is based on two concepts: a) screening of systematically designed libraries with spatial diversity and b) masking of the peptide charge with a lipophilic protecting group. The key steps of the method are 1) initial design of a combinatorial library of Nmethylated analogues of the stem peptide cyclo(d-Ala-Ala(5)); 2) selection of cyclic peptides with the highest intestinal permeability; 3) design of sublibraries with the bioactive RGD sequence in all possible positions; 4) selection of the best ligands for RGD-recognizing integrin subtypes; 5) finetuning of the affinity and selectivity by additional Ala to Xaa substitutions; 6) protection of the charged functional groups according to the prodrug concept to regain intestinal and oral permeability; 7) proof of biological effects in mice after oral administration.

Palladium supported ionic liquid phase catalyst (Pd@SILP-PS) for room temperature Suzuki-Miyaura cross-coupling reaction - More, S.; Jadhav, S; Salunkhe, R.; Kumbhar, A. (Molecular Catalysis, 2017)
A new Pd-SILP based on amino functionalized imidazolium ionic liquid immobilized on Merrifield resin (Pd@SILP-PS) has been synthesized. The catalyst was characterized by different techniques like FT-IR, SEM-EDS, TEM, TGA-DTA and XPS. The catalyst has shown to be highly active in Suzuki-Miyaura cross-coupling reaction of various aryl halides and aryl boronic acids in ethanol at room temperature. The activity of catalyst and the nature of product were highly dependent on the type of the solvent used, as well as the substituents present on the aryl halides. The protic polar solvent ethanol gave desired cross-coupling product in good to excellent yields at room temperature. However the aprotic polar solvent THF gave homocoupling product. The catalyst showed at least five times recyclability without a decrease in product yield.
Keywords: Immobilization; Ionic liquid; Palladium; SILP; Suzuki-Miyaura reaction

Panchromatic sensitizer for dye-sensitized solar cells: un-symmetrical squaraine dyes incorporating benzodithiophene π-spacer with alkyl chains to extend conjugation, control the dye assembly on TiO2 and retard charge recombination - Bisht, Rajesh; Munavvar, Fairoos Mk; Singh, Ambarish Kumar; Nithyanandhan, Jayaraj (Journal of Organic Chemistry, 2017)
Metal-free near-infrared (NIR) active unsymmetrical squaraine dyes, RSQ1 and RSQ2, with benzodithiophene (BDT) π-spacer and cyanoacrylic acid acceptor were synthesized by utilizing palladium catalyzed direct (hetero)arylation reaction. Methyl and 2-ethylhexyl groups were strategically placed at the BDT unit for RSQ1 and RSQ2 respectively, to investigate the effect of alkylated π-spacer on dye aggregation on the TiO2 surface and recombination reactions at TiO2/dye/electrolyte interface. These dyes have strong absorption ( ε>10(5) M(-1)cm(-1)) in near-infra red (NIR) region and exhibit similar optical and electrochemical properties as they have same conjugated framework. RSQ2 performed better than RSQ1 owing to its higher open-circuit voltage (Voc) and fill factor (ff) in spite of having comparable short-circuit current density (Jsc). The panchromatic incident photon-to-current conversion efficiency (IPCE) response was also observed for both the dyes. RSQ2 showed power conversion efficiency (PCE) of 6.72% with short-circuit current density (Jsc) of 18.53 mA/cm(2), open circuit voltage (Voc) of 0.538 V, and fill factor (ff) of 67.4%, without any co-adsorbent. Attenuation of the charge recombination for RSQ2 was revealed by electrochemical impedance analysis (EIS) and open-circuit potential decay transients (OCVD), which attributes to its higher Voc and ff in comparison to RSQ1.

PbS nanostar-like structures as field emitters - Pawar, Mahendra S.; Bankar, Prashant K.; More, Mahendra A.; Late, Dattatray J. (Chemistryselect, 2017)
The crystalline PbS nanostars were synthesized by thermal decomposition of thioacetamide (TAA) in aqueous solutions of lead acetate and acetic acid at 80 8 degrees C. The structure and morphology of the PbS nanostars have been characterized using X-Ray Diffraction (XRD), Raman Spectroscopy, Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The optical properties of the PbS nanostars have been studied using UV-Visible absorption Spectroscopy (UVVis). The field emission investigations have been carried out on the as synthesized PbS nanostars at the base pressure of similar to 13 10(-8) mbar. The turn on field required to draw an emission current density of 1 mu A/cm(2) is found to be 1.8 V/mm. The emission current-time plots show good emission current stability of the PbS nanostar emitter over a period of 4 hrs. The results in terms of low turn-on field and long term emission current stability of the PbS nanostars emitter reveals that it can be used in field emission based vacuum microelectronics / nanoelectronic devices.

Pd-catalyzed regioselective mono-arylation: quinazolinone as the inherent directing group for C(sp(2))-H activation - Garad, Dnyaneshwar N.; Viveki, Amol B.; Mhaske, Santosh B. (Journal of Organic Chemistry, 2017)
The Pd-catalyzed quinazolinone-directed regioselective monoarylation of aromatic rings by C-H bond activation is developed. A broad substrate scope is demonstrated for both quinazolinone as well as diary-liodonium triflates. The use of a base was found to be crucial for this transformation, unlike for the known nitrogen-directed arylations. All of the novel quinazolinones of biological interest were synthesized by using the operationally simple Pd(II)-catalyzed arylation reaction.
Keywords: Aromatic rings; catalysis; Chemical activation; Chemical reactions; Palladium compounds; Regioselectivity

Phenol oxidative dearomatization of modified nucleoside templates: a simple access to the c7-spiroannulated octosyl acid framework - Mullapudi, Venkannababu; Bhogade, Ravindra B.; Deshpande, Mukund V.; Ramana, Chepuri V. (Synthesis-Stuttgart, 2017)
Phenol oxidative dearomatization and cyclization has been executed successfully on nucleoside templates to synthesize C7-spiroannulated perhydrofuropyran nucleosides and C6-spiroannulated perhydrofurofuran nucleosides as novel analogues of octosyl acid and related peptidyl nucleosides.
Keywords: Analogs; antibiotics; Biosynthesis; Chitin synthase; Derivatives; Ezomycins; Glucose Diacetonide Natural-products; Griseofulvin; Malayamycin; Modified nucleosides; Moiety; Peptidyl Glycosides; Phenol Oxidative Dearomatization; Vorbruggen Glycosylation

Photo-induced cytotoxicity and anti-metastatic activity of ruthenium(II)-polypyridyl complexes functionalized with tyrosine or tryptophan - Ramu, Vadde; Aute, Sunil; Taye, Nandaraj; Guha, Rweetuparna; Walker, Michael G.; Mogare, Devaraj; Parulekar, Apoorva; Thomas, Jim A.; Chattopadhyay, Samit; Das, Amitava (Dalton Transactions, 2017)
The synergistic effect of oxygen, light, and photosensitizer (PS) has found applications in medicine for the treatment of cancer through photodynamic therapy (PDT). Induction of apoptosis to cancerous cells will prevent tumor metastasis that spreads cancer cells to the neighboring organs/tissues. Herein, we report the two apoptotic Ru(II)-polypyridyl complexes that are functionalized with pendant amino acid moieties tyrosine (1) and tryptophan (2), respectively. These two water soluble complexes were found to interact strongly (K-a(1) = (1.18 +/- 0.28) x 10(5) M-1 and K-a(2) = (1.57 +/- 0.77) x 10(5) M-1) with CT-DNA. Isothermal titration calorimetry (ITC) studies revealed that these complexes bind to CT-DNA through an entropically driven process. Both the complexes showed photo-induced cytotoxicity and exhibit apoptotic activity under photo-irradiation conditions. The comet assay indicated that these complexes can damage cellular DNA, which is attributed to the significant build-up of O-1(2) level even on irradiation with low intensity light (10 J cm(-2), lambda(Range) 450-480 nm). This photoinduced DNA damage and apoptosis in A549 cells was induced by reactive oxygen species (ROS) and occurred through up-regulation of apoptotic marker caspase-3. Control experiments under dark conditions revealed an insignificant cytotoxicity towards these cells for two photosensitive molecules.

pi-Conjugated chromophore incorporated polystyrene nanobeads as single optical agent for three-channel fluorescent probe in bioimaging application - Makkad, Sarabjot Kaur; Asha, S. K. (ACS Biomaterials Science & Engineering, 2017)
Fluorescent polystyrene (PS) nanobeads in the size range similar to 70-120 nm incorporating perylene bisimide (PBI-PS) and/or oligo(p-phenylenevinylene) (OPV-PS) was developed by miniemulsion polymerization technique. A dye loading content (DLC) of <3% was sufficient to impart high fluorescence emission capability to the PS beads. OPV-PS exhibited emission in the range 400-550 nm with peak emission at 450 nm (lambda(ex) = 350 nm; phi(FL) = 26%); PBI-PS showed emission from 520-650 nm with peak emission at 545 nm (lambda(ex) = 490 nm; phi(FL) = 9.7%) in 1x PBS buffer, whereas OPV(PBI)-PS nanobeads incorporating both the fluorophores exhibited multicolor emission capabilities (lambda(ex) from 350 to 490 nm). The nanoparticles were characterized by field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and dynamic light scattering (DLS) for size and zeta potential for surface charge. For bioimaging applications, the PS nanoparticles were incubated with HeLa cells. Cell viability analysis involving HeLa cells showed more than 90% cell viability confirming the biocompatibility of the PS The cellular uptake of the nanoparticles was confirmed by flow cytometry analysis and confocal laser scanning microscopy (CLSM) images. The subcellular localization of the nanoparticles in the cytoplasm could be precisely established by their simultaneous multicolor emission. The PS-based single optical agent presented here that can function as three-channel fluorescent probe to meet the requirements for multicolor bioimaging is advantageous.
Keywords: Biocompatibility; bioimaging

Placental proteomics provides insights into pathophysiology of pre-eclampsia and predicts possible markers in plasma - Mary, Sheon; Kulkarni, Mahesh J.; Malakar, Dipankar; Joshi, Sadhana Ramchandra; Mehendale, Savita S.; Giri, Ashok P. (Journal of Proteome Research, 2017)
Pre-eclampsia is a hypertensive disorder characterized by the new onset of hypertension >140/90 mmHg and proteinuria after the 20th week of gestation. The disorder is multi-factorial and originates with abnormal placentation. Comparison of the placental proteome of normotensive (n=25) and pre-eclamptic (n=25) patients by gel-free proteomic techniques, identified a total of 2145 proteins in the placenta of which 180 were differentially expressed (>1.3 fold, p<0.05). Gene ontology enrichment analysis of biological process suggested that the differentially expressed proteins belonged to various physiological processes such as angiogenesis, apoptosis, oxidative stress, hypoxia, placental development, which are implicated in the pathophysiology of pre-eclampsia. Some of the differentially expressed proteins were monitored in the plasma by multiple reaction monitoring (MRM) analysis, which showed an increase in Apolipoprotein AI and AII in gestational week 26-30th (2-fold, p<0.01) while haptoglobin and hemopexin decreased in gestational week 26-30th and 40th week/at delivery (1.8 fold, p<0.01) in pre-eclamptic patients. This study provides a proteomic insight into the pathophysiology of pre-eclampsia. Identified candidate proteins can be evaluated further for the development of potential biomarkers associated with pre-eclampsia pathogenesis.

Plant cholesterol biosynthetic pathway overlaps with phytosterol metabolism - Sonawane, P. D.; Pollier, J.; Panda, S.; Szymanski, J.; Massalha, H.; Yona, M.; Unger, T.; Malitsky, S.; Arendt, P.; Pauwels, L.; Almekias-Siegl, E.; Rogachev, I.; et al. (Nature Plants, 2017)
The amount of cholesterol made by many plants is not negligible. Whereas cholesterogenesis in animals was elucidated decades ago, the plant pathway has remained enigmatic. Among other roles, cholesterol is a key precursor for thousands of bioactive plant metabolites, including the well-known Solanum steroidal glycoalkaloids. Integrating tomato transcript and protein co-expression data revealed candidate genes putatively associated with cholesterol biosynthesis. A combination of functional assays including gene silencing, examination of recombinant enzyme activity and yeast mutant complementation suggests the cholesterol pathway comprises 12 enzymes acting in 10 steps. It appears that half of the cholesterogenesis-specific enzymes evolved through gene duplication and divergence from phytosterol biosynthetic enzymes, whereas others act reciprocally in both cholesterol and phytosterol metabolism. Our findings provide a unique example of nature's capacity to exploit existing protein folds and catalytic machineries from primary metabolism to assemble a new, multi-step metabolic pathway. Finally, the engineering of a 'high-cholesterol' model plant underscores the future value of our gene toolbox to produce high-value steroidal compounds via synthetic biology.

Polylactic acid (PLA) biocomposites filled with waste leather buff (WLB) - Ambone, Tushar; Joseph, Seena; Deenadayalan, E.; Mishra, Satyendra; Jaisankar, S.; Saravanan, P. (Journal of Polymers and the Environment, 2017)
A large amount of leather waste is generated from tanning industries and most of which are disposed of landfill or discharged into the natural water bodies without any treatment, causing environmental problems. The aim of this study is to develop eco-biocomposites using waste leather buff (WLB) as filler in Polylactic acid (PLA) matrix to reduce the environmental issues and provide sustainable solution. WLB/PLA composites were prepared by twins-screw micro extruder varying the WLB content from 2% to 30 wt%. These composite were extensively characterise by several techniques. Tensile properties of the composites showed addition of WLB resulted in improvement of tensile property of composite and reduction in percentage crystallinity of PLA matrix observed with increase in WLB content. The effect of WLB on properties of interfacial adhesion and dispersion in WLB/PLA composites were studied by SEM. Wettability of composites was tested by contact angle and water absorption studies. WLB/PLA composite showed increase in water absorption with WLB loading. These WLB/PLA composite could be used to develop low cost eco-friendly product material.

Polymerization-incompetent uromodulin in the pregnant stroke-prone spontaneously hypertensive rat - Mary, Sheon; Small, Heather Yvonne; Siwy, Justyna; Mullen, William; Giri, Ashok; Delles, Christian (Hypertension, 2017)
The kidney is centrally involved in blood pressure regulation and undergoes extensive changes during pregnancy. Hypertension during pregnancy may result in an altered urinary peptidome that could be used to indicate new targets of therapeutic or diagnostic interest. The stroke-prone spontaneously hypertensive rat (SHRSP) is a model of maternal chronic hypertension. Capillary electrophoresis-mass spectrometry was conducted to interrogate the urinary peptidome in SHRSP and the control Wistar-Kyoto strain at three time points: prepregnancy and gestational days 12 and 18. The comparison within and between the Wistar-Kyoto and SHRSP peptidome at all time points detected 123 differentially expressed peptides (fold change >1.5; P<0.05). Sequencing of these peptides identified fragments of collagen a-chains, albumin, prothrombin, actin, serpin A3K, proepidermal growth factor, and uromodulin. Uromodulin peptides showed a pregnancy-specific alteration in SHRSP with a 7.8-fold (P<0.01) and 8.8-fold (P<0.05) increase at gestational days 12 and 18, respectively, relative to the Wistar-Kyoto. Further investigation revealed that these peptides belonged to the polymerization-inhibitory region of uromodulin. Two forms of uromodulin (polymerization competent and polymerization incompetent) were found in urine from both Wistar-Kyoto and SHRSP, where the polymerizationincompetent form was increased in a pregnancy-specific manner in SHRSP. Nifedipine-treated pregnant SHRSP showed only polymerization-competent uromodulin, indicating that calcium may be mechanistically involved in uromodulin polymerization. This study highlights, for the first time, a potential role of uromodulin and its polymerization in hypertensive pregnancy.
Keywords: Hypertension; Kidney; Nifedipine; pregnancy; uromodulin

Porous porphyrin organic polymer (PPOP) for visible light triggered hydrogen production - Mukherjee, Gargi; Thote, Jayshri; Aiyappa, Harshitha Barike; Kandambeth, Sharath; Banerjee, Subhrashis; Vanka, Kumar; Banerjee, Rahul (Chemical Communications, 2017)
A visible light active porphyrin-based porous organic polymer having high chemical stability and surface area has been synthesized and its ability to influence the photocatalytic activity of large band gap-TiO2 nanoparticles has been tested. The resultant composite shows improved photocatalytic activity as compared to the parent precursors. This study provides insights into the photosensitizing ability of the polymer in addition to its ability to firmly harbor nanoparticles onto its surface.

Porous reduced graphene oxide modified electrodes for the analysis of protein aggregation. part 1: lysozyme aggregation at pH 2 and 7.4 - Vasilescu, Alina; Boulahneche, Samia; Chekin, Fereshteh; Gaspar, Szilveszter; Medjram, Mohamed Salah; Diagne, Abdou Aziz; Singh, Santosh K.; Kurungot, Sreekumar; Boukherroub, Rabah; Szunerits, Sabine (Electrochimica Acta, 2017)
Protein instability due to misfolding and aggregation is of big concern for protein based therapeutics because it impacts the bioavailability and immunogenicity of such drugs. The development of simple and cost-effective methods for the analysis of pharmaceutical formulations, indicating the presence or absence of protein aggregates, is consequently of high importance. This work proposes a novel electrochemical interface based on porous reduced graphene oxide coated glassy carbon electrode (GC/prGO) allowing for the early and sensitive identification of protein aggregation by following the change in the oxidative current of the proteins. The novelty of this work lies in the exploration of the ability of GC/prGO interfaces to capture different aggregation behaviors. Lysozyme is used as a model to follow by electrochemistry its aggregation at two pH values, pH 2 and pH 7.4, leading to the formation of amyloid and amorphous aggregates, respectively. Comparing the oxidation peak of lysozyme by differential pulse voltammetry (DPV) for different electrode architectures allowed validating the higher sensitivity of the GC/prGO interface versus bare glassy electrodes or electrodes coated with non-porous reduced graphene oxide. Parallel experiments were performed by fluorescence with thioflavin T, size exclusion chromatography and Atomic Force Microscopy (AFM) imaging. These tests further highlighted the usefulness of GC/prGO electrode to visualize in a fast and reliable manner the changes in the protein structure and the differences between the processes occurring at pH 2 and pH 7.4. In particular, the ability to emphasize changes related to the first steps in aggregation that could be indicative of the aggregation course, recommend the GC/prGO electrode in combination with DPV as a new analytical tool for aggregation studies of biopharmaceuticals. Part 2 of this work will demonstrate later the utility of this approach for the analysis of a fast acting injectable human insulin formulation, Humulin R, used for diabetes treatment as well as for calcitonin. (C) 2017 Elsevier Ltd. All rights reserved.

Predesigned metal-anchored building block for in situ generation of Pd nanoparticles in porous covalent organic framework: application in heterogeneous tandem catalysis - Bhadra, Mohitosh; Sasmal, Himadri Sekhar; Basu, Arghya; Midya, Siba P.; Kandambeth, Sharath; Pachfule, Pradip; Balaraman, Ekambaram; Banerjee, Rahul (ACS Applied Materials & Interfaces, 2017)
The development of nanoparticle-polymer-hybrid-based heterogeneous catalysts with high reactivity and good recyclability is highly desired for their applications in the chemical and pharmaceutical industries: Herein, we have developed a novel synthetic strategy by choosing a predesigned metal-anchored building block for in situ generation of metal (Pd) nanoparticles in the stable, porous, and crystalline covalent organic framework (COF), without using conventional reducing agents. In situ generation of Pd nanoparticles in the COF Skeleton is explicitly confirmed' from PXRD, XPS, TEM images, and N-15 NMR spectral analysis. This hybrid material is found to be an excellent reusable heterogeneous catalyst for the synthesis of biologically and pharmaceutically important 2-substituted benzofurans from 2-bromophencils and terminal alkynes via a tandem process with the turnover number up to 1101. The heterogeneity of the catalytic process is unambiguously verified by a mercury poisoning experiment and leaching test. This hybrid material shows superior catalytic performance compared to commercially available homogeneous as well as heterogeneous Pd catalysts.

Proton-coupled electron-transfer processes in ultrafast time domain: evidence for effects of hydrogen-bond stabilization on photoinduced electron transfer - Dey, Ananta; Dana, Jayanta; Aute, Sunil; Maity, Partha; Das, Amitava; Ghosh, Hirendra N. (Chemistry-A European Journal, 2017)
The proton-coupled electron-transfer (PCET) reaction is investigated for a newly synthesized imidazoleanthraquinone biomimetic model with a photoactive RuIIpolypyridyl moiety that is covalently coupled to the imidazole fragment. Intramolecular H-bonding interactions between imidazole and anthraquinone moieties favor the PCET process; this can be correlated to an appreciable positive shift in the one-electron reduction potential of the coordinated anthraquinone moiety functionalized with the imidazole fragment. This can also be attributed to the low luminescence quantum yield of the RuII-polypyridyl complex used. The dynamics of the intramolecular electron-transfer (ET) and PCET processes are studied by using femtosecond transient absorption spectroscopy. The steady- state spectroscopic studies and the results of the time- resolved absorption studies confirm that H- bonded water molecules play a major role in both ET and PCET dynamics as a proton relay in the excited state. The electron- transfer process is followed by a change in the H- bonding equilibrium between AQ and imidazole in acetonitrile solvent, and protonation of AQ(-) water leads to PCET in the presence of water. A slower forward and backward electron- transfer rate is observed in the presence of D2O compared with that in H2O. These results provide further experimental support for a detailed understanding of the PCET process.

Ratiometric sensor for DNA based on a dual emission Ru(dppz) light-switch complex - Walker, Michael G.; Ramu, Vadde; Meijer, Anthony J. H. M.; Das, Amitava; Thomas, Jim A. (Dalton Transactions, 2017)
Herein we describe the DNA binding properties of two new water-soluble ruthenium complexes; experimental and computational data reveal that both complexes display dual emission from MLCT and LLCT excited states. The interaction of the new complexes with DNA was also investigated. Although one of the complexes only binds DNA though groove binding, the second complex has separate ligands capable of groove binding and intercalation. Nevertheless, it was found that both complexes interact with duplex DNA with high affinity. DNA induced distinctive changes in the emission of the complexes; although the groove binding complex only displays a modest increase in emission on binding, the complex that contains the intercalating Ru-II(dppz) moiety displays a large increase in MLCT-based emission on DNA binding while emission from the LLCT excited state is unaffected. This means that the complex functions as the first ratiometric sensor for DNA.

Reaction engineering of urea alcoholysis: alkyl carbamates - Mote, Dhananjay R.; Ranade, Vivek V. (Indian Journal of Chemical Technology, 2017)
Urea alcoholysis is a reversible reaction generating alkyl carbamate and ammonia as products. The reaction can be performed non-catalytically or in presence of catalyst. The first step in Reaction engineering analysis is to finalize the reactor configuration. In this case it is important to determine the necessity of reactive separation (simultaneous reaction and separation). This has been addressed by first establishing the reversibility of the reaction through theoretical and experimental investigation. Based on this analysis, an experimental setup comprising tubular reactor and a separator has been built. Experiments have been performed for different alcohols at different flow rates and temperatures. The experimental data is used to establish kinetic parameters. Systematic reaction engineering analysis based on multi-stage ideal reactors with and without simultaneous mass transfer is then carried out in terms of three dimensionless numbers. The analysis presented in this work can be readily applied to a general class of reversible reactions with volatile products and the methodology can be used to develop and design reactors for them. The approach and results presented here will be useful to establish optimal reactor configuration and design for urea alcoholysis reactions.

Reactive distillation for the production of methoxy propyl acetate: experiments and simulation - Gadekar-Shinde, Shambala; Reddy, Bhoja; Khan, Mohammad; Chavan, Sanjay; Saini, Dauiat; Mahajani, Sanjay (Industrial & Engineering Chemistry Research, 2017)
Propylene glycol methyl ether acetate is an industrially important solvent. In this work, we study the applicability of reactive distillation (RD) for its synthesis in the presence of an ion-exchange resin, Amberlyst 15, as a catalyst. Simultaneous separation of water during the course of reaction shifts the reaction in the forward direction, which renders cost effectiveness and compactness to the process. The presence of an azeotrope between methoxy propanol and water complicates the separation, leading to a loss of reactants in the product streams, thereby hampering both conversion and purity. Toluene is thus used as an entrainer to further intensify the process. In this work, the intrinsic kinetic parameters are determined from batch reactor data, and used subsequently to simulate the column performance. An experimentally validated simulator is used to examine the effect of various operating and design parameters. Reactant and product losses are minimized to negligible levels and a significant increase in the conversion is realized.

Recovery of radio-cesium from actual high level liquid waste using solvents containing calix[4]arene-crown-6 ligands - Jagasia, P.; Dhami, P. S.; Mohapatra, P. K.; Ansari, S. A.; Jadhav, S. Y.; Kalyankar, G. K.; Gandhi, P. M.; Kharul, U. K. (Journal of Environmental Chemical Engineering, 2017)
This paper gives two methods, viz. a solvent extraction method and a hollow fiber contactor based liquid membrane method, for the separation of radio-cesium from actual high level liquid waste (HLLW) solutions using calix[4]arene-crown-6 based solvent systems. While the solvent extraction method involved calix[4]arene-bis-benzo-crwon-6 (CBC) in PTMS (phenyltrifluoromethyl sulphone), the hollow fiber supported liquid membrane method used a polysulphone fiber containing contactor and bis-octyl-benzo-calix[4]arene-mono-crown-6 (CMC) in 40% iso-decanol + 60% n-dodecane. Both methods reported selective radio-cesium separation with almost no contamination from the associated fission product radionuclides. The radiolytic stability of the hollow fiber contactor was checked by keeping the contactor module in contact with the diluted HLLW for 50 days. The second run carried out after 50 days resulted in excellent reproducibility suggesting efficacy of this method for radioactive waste remediation.
Keywords: 137Cs; Calix-crown-6; Cesium; fibers; Fission products; Hollow fiber contactor; Liquid membranes; liquids; PUREX-HLLW; Radioactive wastesSolvent extraction; solvent extraction; Solvents

Resistin mediates sex-dependent effects of perivascular adipose tissue on vascular function in the shrsp - McNeilly, Sarah; Small, Heather Y.; Mary, Sheon; Sheikh, Adam; Delles, Christian (20th Annual Meeting of the Scottish-Cardiovascular-Forum, 2017)

Resolution of the identity and cholesky representation of EOM-MP2 approximation: implementation, accuracy and efficiency - Kumar, Dinesh; Dutta, Achintya Kumar; Manohar, Prashant Uday (Journal of Chemical Sciences, 2017)
We present a Resolution of Identity and Cholesky Decomposition Based Implementation of EOM-MP2 approximation. The RI and CD based EOM-MP2 shows significant speed-up and less storage requirement than the conventional canonical version and can be applied to very large systems. The new algorithm used for this implementation eliminates the most storage requiring four-index quantities resulting in the decrease of storage requirement, reduction in I/O penalties and improved parallel performance, at the expense of more floating point operations. Therefore, the speed-up compared to conventional EOM-MP2 method is more prominent in case of EA, EE and SF case where the storage bottleneck is significant than the EOM-IP-MP2 method, where the storage requirement is significantly less. However, the RI/CD based EOM-IP-MP2 can be coupled with frozen natural orbitals to gain further speed-up.
Keywords: CC; CD; Cholesky decomposition; EA; EE; electron attachment; electron correlation; EOM; equation-of-motion; excited state; ionization; IP; MP2; Resolution-of-identity; RI; SF; spinflip

Rigid peptide scaffold-incorporated structural analogs of the potent antidepressant peptide drug rapastinel (GLYX-13) - Nadimpally, Krishna Chaitanya; Chakrapani, Aswathi; Prabhu, Priyanka J.; Madica, Krishnaprasad; Sanjayan, Gangadhar J. (Chemistryselect, 2017)
Rapastinel (GLYX-13) is a natural amidated tetrapeptide (Thr-Pro-Pro-Thr-NH2)endowed with strong antidepressant property. Rapastinel shows considerable promise for treating drug-resistant major depressive disorder (MDD), and is under clinical phase III development. Herein, we report the synthesis of a novel class of analogues of the potent antidepressant peptide drug rapastinel featuring rigid dipeptide scaffolds comprising proline (L/D) and amino thiophene carboxylates (Atc). Amino thiophene carboxylate is a conformationally constrained aromatic beta-amino acid, known to rigidify peptide backbones thereby limiting the conformational flexibility of peptides and improving proteolytic stability.

Salts and cocrystals of furosemide with pyridines: differences in π-Stacking and color polymorphism - Sangtani, Ekta; Mandal, Suman Kumar; Sreelakshmi, A. S.; Munshi, Parthapratim; Gonnade, Rajesh G. (Crystal Growth & Design, 2017)
Furosemide (FS), a loop diuretic drug that has a potential to exhibit polymorphism, produced color polymorphs of orange (form 1I) and yellow (form 1II) concomitantly with coformer 1, 2-bis(4-pyridyl)ethylene. However, cocrystallization of FS with other pyridines yielded colorless salts (2 and 4) and cocrystals (3 and 5). The significant color difference between the two polymorphs (forms 1I and 1II) could be attributed to the dissimilar π-stacking patterns between the two components and differences in their highest occupied molecular orbital−lowest unoccupied molecular orbital gap. The molecular packing of form 1I and 2 is very similar, but 2 is colorless due to lack of extended π-conjugation.

Secondary interactions arrest the hemiaminal intermediate to invert the modus operandi of schiff base reaction: a route to benzoxazinones - Patel, Ketan; Deshmukh, Satej S.; Bodkhe, Dnyaneshwar; Mane, Manoj; Vanka, Kumar; Shinde, Dinesh; Rajamohanan, Pattuparambil R.; Nandi, Shyamapada; Vaidhyanathan, Ramanathan; Chikkali, Samir H. (Journal of Organic Chemistry, 2017)
Discovered by Hugo Schiff, condensation between amine and aldehyde represents one of the most ubiquitous reactions in chemistry. This classical reaction is widely used to manufacture pharmaceuticals and fine chemicals. However, the rapid and reversible formation of Schiff base prohibits formation of alternative products, of which benzoxazinones are an important class. Therefore, manipulating the reactivity of two partners to invert the course of this reaction is an elusive target. Presented here is a synthetic strategy that regulates the sequence of Schiff base reaction via weak secondary interactions. Guided by the computational models, reaction between 2,3,4,5,6-pentafluoro-benzaldehyde with 2-amino-6methylbenzoic acid revealed quantitative (99%) formation of 5-methyl-2-(perfluoropheny01,2-dihydro-4H-benzo[d][1,3]oxazin-4-one (15). Electron donating and electron withdrawing ortho-substituents on 2-aminobenzoic acid resulted in the production of benzoxazinones 936. The mode of action was tracked using low temperature NMR, IN vis spectroscopy, and isotopic (O-18) labeling experiments. These spectroscopic mechanistic investigations revealed that the hemiaminal intermediate is arrested by the hydrogen-bonding motif to yield benzoxazinone. Thus, the mechanistic investigations and DFT calculations categorically rule out the possibility of in situ imine formation followed by ring-closing, but support instead hydrogen-bond assisted ring-closing to prodrugs. This unprecedented reaction represents an interesting and competitive alternative to metal catalyzed and classical methods of preparing benzoxazinone.

Selective isolation and eradication of E. coli associated with urinary tract infections using anti-fimbrial modified magnetic reduced graphene oxide nanoheaters - Halouane, Fatima; Jijie, Roxana; Meziane, Dalila; Li, Chengnan; Singh, Santosh K.; Bouckaert, Julie; Jurazek, Jean; Kurungot, Sreekumar; Barras, Alexandre; Li, Musen; Boukherroub, Rabah; Szunerits, Sabine (Journal of Materials Chemistry B, 2017)
The fast and efficient elimination of pathogenic bacteria from water, food or biological samples such as blood remains a challenging task. Magnetic isolation of bacteria from complex media holds particular promise for water disinfection and other biotechnological applications employing bacteria. When it comes to infectious diseases such as urinary tract infections, the selective removal of the pathogenic species in complex media such as human serum is also of importance. This issue can only be accomplished by adding pathogen specific targeting sites onto the magnetic nanostructures. In this work, we investigate the potential of 2-nitrodopamine modified magnetic particles anchored on reduced graphene oxide (rGO) nanocomposites for rapid capture and efficient elimination of E. coli associated with urinary tract infections (UTIs) from water and serum samples. An optimized magnetic nanocarrier achieves a 99.9% capture efficiency even at E. coli concentrations of 1 x 10(1) cfu mL(-1) in 30 min. In addition, functionalization of the nanostructures with poly(ethylene glycol) modified pyrene units and anti-fimbrial E. coli antibodies allowed specific elimination of E. coli UTI89 from serum samples. Irradiation of the E. coli loaded nanocomposite with a near-infrared laser results in the total ablation of the captured pathogens. This method can be flexibly modified for any other pathogenic bacteria, depending on the antibodies used, and might be an interesting alternative material for a magnetic-based body fluid purification approach.

Selective molecular separation by interfacially crystallized covalent organic framework thin films - Dey, K.; Das, A; Mukherjee, R.; Kharul, U. K.; Banerjee, R. (Journal of the American Chemical Society, 2017)
Exponential interest in the field of covalent organic frameworks (COFs) stems from the direct correlation between their modular design principle and various interesting properties. However, existing synthetic approaches to realize this goal mainly result in insoluble and unprocessable powders, which severely restrict their widespread applicability. Therefore, developing a methodology for easy fabrication of these materials remains an alluring goal and a much desired objective. Herein, we have demonstrated a bottom-up interfacial crystallization strategy to fabricate these microcrystalline powders as large-scale thin films under ambient conditions. This unique design principle exploits liquid-liquid interface as a platform, allowing simultaneous control over crystallization and morphology of the framework structure. The thin films are grown without any support in free-standing form and can be transferred onto any desirable substrate. The porous (with Tp-Bpy showing highest SBET of 1a151 m2 g-1) and crystalline thin films, having high chemical as well as thermal stability, also hold the merit to tune the thickness as low as sub-100 nm. These nanostructured thin COF films demonstrate remarkable solvent-permeance and solute-rejection performance. A prominent instance is the Tp-Bpy thin film, which displays an unprecedented acetonitrile permeance of 339 L m-2 h-1 bar-1.

Selective molecular sieving in self-Standing porous covalent-Organic-framework membranes - Kandambeth, S.; Biswal, B. P.; Chaudhari, H. D.; Rout, K. C.; Kunjattu, H. S.; Mitra, S.; Karak, S.; Das, A.; Mukherjee, R.; Kharul, U. K.; Banerjee, R. (Advanced Materials, 2017)
Self-standing, flexible, continuous, and crack-free covalent-organic-framework membranes (COMs) are fabricated via a simple, scalable, and highly cost-effective methodology. The COMs show long-term durability, recyclability, and retain their structural integrity in water, organic solvents, and mineral acids. COMs are successfully used in challenging separation applications and recovery of valuable active pharmaceutical ingredients from organic solvents.

Selective synthesis of WO3 and W18O49 nanostructures: ligand-free pH-dependent morphology-controlled self-assembly of hierarchical architectures from 1D nanostructure and sunlight-driven photocatalytic degradation - Shirke, Yogita Manikrao; Mukherjee, Shatabdi Porel (CrystEngComm, 2017)
In this study, simple inorganic routes for the synthesis of WO3 and W18O49 nanostructures with variable size and self-assembly are reported. The morphologies and formation of stoichiometric WO3 as well as substoichiometric W18O49 single-crystal phase could be controlled by changing the pH of the reactions medium. This synthesis strategy has the advantages that it is one step, aqueous medium-based, and requires no surfactant or stabilizing agent. Furthermore, it also enables the self-assembly of 1D nanorods of WO3 and W18O49 into hierarchical nanostructures as nanorods bundles, cocoons, urchins, fishbones, etc. This synthesis method may open up a new way to control and tune the stoichiometric and substoichiometric composition of metal oxide nanostructures. Efficient sunlight-driven photocatalytic performance to degrade Rhodamine B (100 mL; 40 mg L-1.) with these tungsten oxide nanostructures was also demonstrated.

Self-exfoliated guanidinium-based ionic covalent organic nanosheets (iCONs) - Mitra, Shouvik; Kandambeth, Sharath; Biswal, Bishnu P.; Khayum, Abdul M.; Choudhury, Chandan Kumar; Mehta, Mihir R.; Kaur, Gagandeep; Banerjee, Subhrashis; Prabhune, Asmita; Verma, Sandeep; Roy, Sudip; Kharul, Ulhas K.; et al. (Journal of the American Chemical Society, 2017)
Covalent organic nanosheets (CONs) have emerged as functional two-dimensional materials for versatile applications. Although pi-pi stacking between layers, hydrolytic instability, possible restacking prevents their exfoliation on to few thin layered CONs from crystalline porous polymers. We anticipated rational designing of a structure by intrinsic ionic linker could be the solution to produce self-exfoliated CONs without external stimuli. In an attempt to address this issue, we have synthesized three self-exfoliated guanidinium halide based ionic covalent organic nanosheets (iCONs) with antimicrobial property. Self-exfoliation phenomenon has been supported by molecular dynamics (MD) simulation as well. Intrinsic ionic guanidinium unit plays the pivotal role for both self-exfoliation and antibacterial property against both Gram-positive and Gram-negative bacteria. Using such iCONs, we have devised a Mixed matrix membrane which could be useful for antimicrobial coatings with plausible medical benefits.

Silk degumming and utilization of silk sericin by hydrolysis using alkaline protease from beauveria Sp. (MTCC 5184): a green approach - More, Snehal V.; Chavan, Sakalya; Prabhune, Asmita Ashutosh (Journal of Natural Fibers, 2017)
Conventionally, degumming is carried out at 90°C--110°C temperature by boiling the raw silk with Marseilles soap and sodium bicarbonate which eventually requires a lot of water and energy. In this study, degumming of Chinese bivoltine raw silk fibres with alkaline protease produced by Beauveria sp. (MTCC 5184) is studied. Complete degumming was obtained in 45 min with 75 units of enzyme per gram of silk. Degumming was found to be optimal at 50°C and pH 9.0. Scanning electron micrographs showed that the sericin deposits were removed and the obtained fibres were clean, separated, had smooth feel with shine as compared to untreated fibres. Sericin isolated from silk cocoon (by-product which goes waste) was hydrolyzed with the same alkaline protease obtained from Beauveria sp. to get small molecular weight peptides. These peptides can be utilized further for cosmetic, pharmaceutical, and various industrial applications.
Keywords: Alkaline Protease; bivoltine; degumming; Silk; weight loss

Simple cobalt(II) chloride catalyzed N-alkylation of amines with alcohols - Midya, Siba P.; Mondal, Akash; Begum, Ayesha; Balaraman, Ekambaram (Synthesis-Stuttgart, 2017)
A facile cobalt-catalyzed N-alkylation of amines with alcohols using inexpensive, commercially available CoCl2 center dot 6H(2)O is reported. Employing this readily available cobalt catalyst, a variety of amines with wide functional group tolerance were selectively alkylated under benign conditions.
Keywords: (Hetero)Aromatic Amines; Alcohols; Amination; amines; Anilines; Aromatic-amines; Cobalt Catalysis; Dehydrogenation Borrowing Hydrogen; Efficient Catalysts; Hydrogen Autotransfer; Iridium; N-alkylation; Pincer-complex; Secondary Alcohols; Selective Alkylation

Size reduction of bulk alumina for mass production of fluorescent nanoalumina by fungus humicola sp. - Moeez, Sana; Siddiqui, Ejaz Ahmad; Khan, Shadab; Ahmad, Absar (Journal of Cluster Science, 2017)
In recent years, nanomaterials have made their way into hundreds of biomedical, life-sciences and technological applications. One such nanomaterial of extreme importance is nanoalumina (Al2O3 nanoparticles). This nanomaterial is an epitome of diversity with applications exhibited in the fields of catalysis, cosmetics, theranostics, energy generation, biosensors, drug-delivery, tumor-regression, etc. However, problems persist in terms of biocompatibility, cost-effectiveness, reproducibility and mass-production of nanoalumina by the presently existent physical, chemical and biological methodologies. Herein, we for the first time are presenting a top-down biofabrication method by which size reduction of commercial bulk alumina/aluminum oxide (5 A mu m) into nanoalumina (5-25 nm) is carried out by a thermophilic fungus Humicola sp. within 96 h of reaction at just 50 A degrees C. The so-formed nanoalumina is highly stable, water dispersible, fluorescent and natural protein capped; characterization engaged standard techniques. These nanoparticles exhibit anti-bacterial properties against Gram-positive Bacillus subtilis strain and may serve as broad spectrum bactericidal agents. We believe that our novel top-down approach may be extensively used in the facile, inexpensive, eco-friendly and reliable fabrication of abundant quantities of nanomaterials of different chemical compositions, sizes and shapes with better control and predictability over the properties as derived from their substrates. The mechanistic aspect of said protocol is underway.

Sorption of metaldehyde using granular activated carbon - Salvestrini, S.; Vanore, P.; Bogush, A.; Mayadevi, S.; Campos, L. C. (Journal of Water Reuse and Desalination, 2017)
In this work, the ability of granular activated carbon (GAC) to sorb metaldehyde was evaluated. The kinetic data could be described by an intra-particle diffusion model, which indicated that the porosity of the sorbent strongly influenced the rate of sorption. The analysis of the equilibrium sorption data revealed that ionic strength and temperature did not play any significant role in the metaldehyde uptake. The sorption isotherms were successfully predicted by the Freundlich model. The GAC used in this paper exhibited a higher affinity and sorption capacity for metaldehyde with respect to other GACs studied in previous works, probably as a result of its higher specific surface area and high point of zero charge.
Keywords: Degradation; Diffusion-controlled Sorption; Environmental Pollution; Granular Activated Carbon; Metaldehyde; Sorption Adsorption

Step-growth polymers from cashew nut shell liquid (CNSL)-based aromatic difunctional monomers - Chatterjee, Deepshikha; Sadavarte, Nilakshi V.; Shingte, Rahul D.; More, Arvind S.; Tawade, Bhausaheb V.; Kulkarni, Arun D.; Ichake, Amol B.; Avadhani, C. V.; Wadgaonkar, Prakash P. (Cashew Nut Shell Liquid, 2017)
Cashew nut shell liquid (CNSL) is an attractive renewable resource material which is available in abundance (44,50,000 tonnes worldwide and 7,53,000 tonnes in India in 2013) at low cost (around 0.27 $/kg in 2015) and is mainly composed of anacardic acid, cardanol, cardol and 2-methyl cardol. Cardanol is obtained as a major product during hot oil extraction or roasting process of CNSL. Cardanol possesses interesting structural features. The aromatic ring of cardanol can undergo electrophilic substitution reactions; the unsaturated side chain can undergo epoxidation, hydrogenation, metathesis, etc., while the phenolic hydroxyl group can undergo various reactions such as esterification and alkylation. Such opportunities of chemical modifications offered by cardanol have been extensively explored to synthesise a range of interesting aromatic difunctional monomers that have subsequently been utilised to prepare a host of step-growth polymers. Summarised herein are research efforts that have contributed towards the synthesis of step-growth polymers based on aromatic difunctional monomers derived from cardanol. The properties of high-performance polymers, with a particular focus on processability and thermal characteristics, are highlighted.

Structural insights into the hydrogen-bonding and folding pattern in ant-ant-pro-gly tetrapeptides - Baravkar, Sachin B.; Kotmale, Amol S.; Mobin, Samir R.; Gonnade, Rajesh Ghanshyam; Sanjayan, Gangadhar J. (European Journal of Organic Chemistry, 2017)
In this paper, we provide structural insights into the hydrogen-bonding and folding pattern in Ant-Ant-Pro-Gly tetrapeptides (Ant: anthranilic acid; Pro: proline; and Gly: glycine). Comparison of the C-terminal esters and their amide analogs revealed strikingly different H-bonding networks. Whereas the ester analogs displayed an open structure without terminal H-bonding interactions, the amide analogs showed a completely folded structure. Structural details were revealed by using a combination of X-ray crystal structure studies and NOE-based molecular dynamics (MD) simulation studies.

Structural, magnetic, dielectric and magnetodielectric properties of Bi1-xCaxFe1-xMnxO3 in the morphotropic phase boundary region - Manjunath, B.; Thakuria, P.; Joy, P. A. (Materials Research Express, 2017)
Structural, magnetic, dielectric and magnetodielectric properties of Ca and Mn co-substituted bismuth ferrite, Bi1-xCaxFe1-xMnxO3 (0 <= x <= 0.4) are reported. Structural studies by Rietveld refinement of XRD patterns revealed rhombohedral R3c structure for x <= 0.11 and orthorhombic Pbnm structure for x >= 0.2. For compositions in the range 0.11 < x < 0.2, mixed phase behaviour is observed showing a morphotropic phase boundary (MPB) region. Magnetisation at room temperature increases with increasing Ca and Mn content, showing weak ferromagnetism. Coercivity and remanence initially increase and then decrease with increasing x, showing a maximum for x = 0.175 in the MPB region. Dielectric constant also shows a maximum value in the mixed phase region. Magnetodielectric (MD) studies revealed positive MD for the R3c phase and a negative MD for the Pbnm phase, showing a maximum MD (similar to 1%) for x approximate to 0.1 and crossover at x approximate to 0.175. The studies show strong interplay between the structure and properties, suggesting tuneable bismuth ferrite based compositions for magnetoelectric applications.

Structure and short time degradation studies of sodium zirconium phosphate ceramics loaded with simulated fast breeder (FBR) waste - Ananthanarayanan, A.; Ambashta, R. D.; Sudarsan, V.; Ajithkumar, T.; Sen, D.; Mazumder, S.; Wattal, P. K. (Journal of Nuclear Materials, 2017)
Sodium zirconium phosphate (NZP) ceramics have been prepared using conventional sintering and hot isostatic pressing (HIP) routes. The structure of NZP ceramics, prepared using the HIP route, has been compared with conventionally sintered NZP using a combination of X-ray diffraction (XRD) and (P-31 and Na-23) nuclear magnetic resonance (NMR) spectroscopy techniques. It is observed that NZP with no waste loading is aggressive toward the steel HIP -can during hot isostatic compaction and significant fraction of cations from the steel enter the ceramic material. Waste loaded NZP samples (10 wt% simulated FBR waste) show significantly low can -interaction and primary NZP phase is evident in this material. Upon exposure of can -interacted and waste loaded NZP to boiling water and steam, P-31 NMR does not detect any major modifications in the network structure. However, the Na-23 NMR spectra indicate migration of Na+ ions from the surface and possible re -crystallization. This is corroborated by Small -Angle Neutron Scattering (SANS) data and Scanning Electron Microscopy (SEM) measurements carried out on these samples.

Studies on use of sodium poly acrylate (SPA) for low salt animal skinpreservation - Sandhya, K. V.; Brindha, Velappan; Abinandan, Sudharsanam; Vedaraman, N.; John, Sundar V.; Suresha, P. R.; Badiger, Manohar; Chinnaraj, Velappan kandukalpatti; Muralidharan, C. (IULTCS CONGRESS 2017, 2017)
In this study, commercial sodium poly acrylate (SPA) is used along with sodium chloride for low salt skin preservation. SPA is a super-absorbent polymer which can absorb water many times of its own weight.

Study of nanofiber scaffolds of PAA, PAA/CS, and PAA/ALG for its potential use in biotechnological applications - Rodolfo, Velasco; Ricardo, Vera-Graziano; López-Maldonado, E.A.; Mercedes, Oropeza; Dastager, Syed; Adriana, Álvarez-Andrade; Ana, leticia Iglesias; Luis, Jesús Villarreal-Gómez (International Journal of Polymeric Materials, 2017)
In recent times, electrospun nanofibers have been widely studied from several biotechnological approaches; in this work, poly (acrylic acid) solutions mixed with chitosan and alginate were electrospun and characterized in order to determine the behavior of these fibers when used in combination with bacteria, different samples were incubated with the bacterial strains: Streptomyces spp., Micromonospora spp. and Escherichia coli and a OD600 test was performed. The formation of nanofibers via electrospinning and the physicochemical properties of the obtained fibers were evaluated. Results showed that the presence of Chitosan enhanced the thermal stability of poly (acrylic acid), since poly (acrylic acid)/alginate fibers lost 5% of their mass at 41°C while poly (acrylic acid)/chitosan lost this amount at around 125°C. The fibers demonstrated suitable characteristics to be used as a bacteria bioreactor.

Study of the effect of operating parameters on the extractive distillation of isopropyl alcohol–water mixture using dimethyl sulphoxide as an entrainer - Ghuge, Pravin D.; Mali, Nilesh A.; Sirsam, R. S. (Indian Chemical Engineer, 2017)
Abstract: In this paper, the simulation analysis of separation of isopropyl alcohol (IPA)–water via extractive distillation by using dimethyl sulphoxide as an entrainer is presented. The steady-state simulation for this process was done using Aspen Plus simulator. The aim of this work is to study the effect of various operating parameters such as number of stages, molar reflux ratio, binary feed stage number, entrainer feed stage number, temperature of entrainer feed and entrainer to feed molar ratio on the purity and energy consumption. The sensitivity of these parameters serves as a basis to choose the optimum operating conditions to maximize the IPA purity and minimize the energy requirement. In this analysis, among various operating parameters, those which directly affect the IPA purity and the parameters which affect the reboiler duty, for the given separation task, are identified. Simulation results with optimum operating conditions and their economic analysis are also presented.
Keywords: Aspen Plus Simulators; Azeotrope; Computer software; Distillation; Energy requirements; Energy utilization; Extractive distillation; Isopropyl alcohol/water; Isopropyl alcohols; Operating parameters; Optimum operating conditions; Sensitivity analysis; simulation; SimulationSteady-state simulations; Solvents

Study of thermally coupled distillation systems for energy-efficient distillation - Saxena, Neha; Mali, Nilesh; Satpute, Satchidanand (Sadhana-Academy Proceedings in Engineering Sciences, 2017)
Distillation is one of the most widely used separation unit operations in process industries, although it is quite energy intensive. In many cases, the enormous energy requirements for distillation make it economically infeasible to carry out the separation. Thermally coupled distillation system (TCDS) is an advanced distillation method that provides significant energy savings of about 30% as compared with conventional distillation column sequences. The most well-known TCDS sequence, the Petlyuk configuration, has some operational challenges due to bidirectional vapour flow, which makes its implementation difficult in two-column mode. To overcome these limitations, a number of unidirectional vapour flow configurations have been proposed in the literature. The work on simulation analysis for such configurations is limited. In this paper, simulation models for two such configurations are developed, analyzed and compared with the Petlyuk and conventional distillation column sequences for separation of equimolar mixture of benzene-toluene-ethylbenzene.
Keywords: Distillation; energy efficient; Petlyuk; simulation; thermally coupled

Study on doped heterojunctions in TiO2 nanotubes: an efficient photocatalyst for solar water splitting - Preethi, L. K.; Antony, Rajini P.; Mathews, Tom; Walczak, Lukasz; Gopinath, Chinnakonda S. (Scientific Reports, 2017)
The two important factors that affect sunlight assisted water splitting ability of TiO2 are its charge recombination and large band gap. We report the first demonstration of nitrogen doped triphase (anatase-rutile-brookite) TiO2 nanotubes as sun light active photocatalyst for water splitting with high quantum efficiency. Nitrogen doped triphase TiO2 nanotubes, corresponding to different nitrogen concentrations, are synthesized electrochemically. Increase in nitrogen concentration in triphase TiO2 nanotubes is found to induce brookite to anatase phase transformation. The variation in density of intra-band states (Ti3+ and N 2p states) with increase in nitrogen doping are found to be critical in tuning the photocatalytic activity of TiO2 nanotubes. The presence of bulk heterojunctions in single nanotube of different nitrogen doped TiO2 samples is confirmed from HRTEM analysis. The most active nitrogen doped triphase TiO2 nanotubes are found to be 12 times efficient compared to pristine triphase TiO2, for solar hydrogen generation. The band alignment and charge transfer pathways in nitrogen doped TiO2 with triphase heterojunctions are delineated. Bulk heterojunctions among the three phases present in the nanotubes with intra-band defect states is shown to enhance the photocatalytic activity tremendously. Our study also confirms the theory that three phase system is efficient in photocatalysis compared to two phase system.

Synthesis and antimycobacterial screening of new thiazolyl-oxazole derivatives - Abhale, Yogita K.; Sasane, Amit V.; Chavan, Abhijit P.; Shekh, Saddam Husen; Deshmukh, Keshav K.; Bhansali, Sujit; Nawale, Laxman; Sarkar, Dhiman; Mhaske, Pravin C. (European Journal of Medicinal Chemistry, 2017)
In the present study a series of 4-methyl-2-aryl-5-(2-aryl/benzyl thiazol-4-yl) oxazole (4a-v) have been synthesized and evaluated for their preliminary antitubercular, antimicrobial and cytotoxicity activity. Among all the synthesized compounds, 4v reported comparable activity against dormant M. tuberculosis H37Ra and M. bovis BCG strains with respect to standard drug rifampicin. The active compounds from the antitubercular study were further tested for anti-proliferative activity against HeLa, A549 and PANC-1 cell lines using MU assay and showed no significant cytotoxic activity at the maximum concentration evaluated. Further, the synthesized compounds were found to have potential antibacterial activities with MIC range of 2.1-26.8 mu g/mL. High potency, lower cytotoxicity and promising antimycobacterial activity suggested that these compounds could serve as good leads for further optimisation and development. (C) 2017 Elsevier Masson SAS. All rights reserved.

Synthesis and antitubercular activity of new thiazolidinones with pyrazinyl and thiazolyl scaffolds - Dhumal, Sambhaji T.; Deshmukh, Amarsinh R.; Khillare, Lalit D.; Arkile, Manisha A.; Sarkar, Dhiman; Mane, Ramrao A. (Journal of Heterocyclic Chemistry, 2017)
Emergence of multidrug resistant and extensively drug resistant tuberculosis has prompted to develop new molecular entities to treat the disease. A series of new 4-thiazolidinones with pyrazinyl and thiazolyl scaffolds has been synthesized, and their antitubercular activity is reported. The title 4-thiazolidinones, N-(pyrazinyl substituted thiazoloylamino)-2-aryl-4-thiazolidinones () have been first time prepared using pyrazinamide as a starting material via five successive steps. The purity and the structures of the intermediates (carboethoxythiazole, acid hydrazide, and azomethines) and title thiazolidinones () have been confirmed by TLC and spectral analyses, respectively. An antitubercular screening of the new 4-thiazolidinones has been performed on bacterial strains, Mycobacterium tuberculosis H37Ra and Mycobacterium BCG using the solutions of different concentrations of the compounds () and the screening results are presented. Compound has displayed notable antitubercular activity.

Synthesis and biological evaluation of new fluconazole β-lactam conjugates linked via 1,2,3-triazole - Divse, Jaisingh M.; Mhaske, Santosh B.; Charolkar, Chaitanya R.; Sant, Duhita G.; Tupe, Santosh G.; Deshpande, Mukund V.; Khedkar, Vijay M.; Nawale, Laxman U.; Sarkar, Dhiman; Pore, Vandana S. (New Journal of Chemistry, 2017)
Novel 1,2,3-triazole-linked β-lactam–fluconazole conjugates 12(a–l) were designed and synthesized. The compounds showed potent antifungal activity against two pathogenic Candida strains; Candida albicans ATCC 24433 and Candida albicans ATCC 10231 with MIC values in the range of 0.0625–2 μg mL−1. Compounds 12h, 12j and 12k showed promising antifungal activity against all the tested fungal pathogens except C. neoformans ATCC 34554 compared to fluconazole. Compound 12j in which the β-lactam ring was formed using para-anisidine and benzaldehyde was found to be more potent than fluconazole against all the fungal strains with an IC50 value of <0.015 μg mL−1 for Candida albicans (ATCC 24433). Mechanistic studies for active compounds revealed that the antifungal action was due to ergosterol inhibition. Compounds 12h and 12j at a concentration of 0.125 μg mL−1 caused 91.5 and 96.8% ergosterol depletion, respectively, compared to fluconazole which at the same concentration caused 49% ergosterol depletion. The molecular docking study revealed that all the fluconazole β-lactam conjugates 12(a–l) could snugly fit into the active site of lanosterol 14α-demethylase (CYP51) with varying degrees of affinities. As anticipated, the binding energy for compound 12j (−58.961 kcal mol−1) was much smaller than that for fluconazole (−52.92 kcal mol−1). The synthesized compounds have therapeutic potential for the control of candidemia.

Synthesis, antimycobacterial screening and molecular docking studies of 4-aryl-4′-methyl-2′-aryl-2,5′-bisthiazole derivatives - Abhale, Yogita K.; Shinde, Abhijit D.; Deshmukh, Keshav K.; Nawale, Laxman U.; Sarkar, Dhiman; Choudhari, Prafulla B.; Kumbhar, Santosh S.; Mhaske, Pravin C. (Medicinal Chemistry Research, 2017)
A series of 4-aryl-4′-methyl-2′-aryl-2,5′-bisthia- zole derivatives (5a–o) were synthesized and screened for inhibitory activity against Mycobacterium tuberculosis H37Ra (ATCC 25177) and Mycobacterium bovis BCG (ATCC 35743) strains. Five lead compounds (5e, 5f, 5g, 5h, and 5o) were further confirmed from their dose dependent effect against MTB and Bovine–Calmette–Guerin. The most promising compounds 5f (MIC90: 11.32 μg/mL), 5h (MIC90: 11.59 μg/mL), and 5o (MIC90: 23.64 μg/mL) showed strong antitubercular activity against dormant MTB and BCG as well as almost insignificant cytotoxicity up to 100μg/mL against HeLa, A549, and PANC-1 human cancer cell lines. Further, the synthesized compounds were found to have potential antibacterial activity against Gram-negative bac- teria, Escherichia coli, Pseudomonas flurescence and Gram- positive bacteria, Staphylococcus aureus, Bacillus subtilis. Most of the synthesized compounds showed moderateactivity against fungal strain Candida albicans. Molecular docking studies of these compounds showed significant interactions with crystal structure of the cytochrome P45014α-sterol demethylase (CYP51) PDB ID: 1E9X. Hydrogen bond interactions with SER261 and VAL395 are important interactions for selective inhibition of designed inhibitors. Compounds 5f, 5h, and 5o showed significant interactions with 1E9X. All the experimental results promote us to consider this series as a starting point for the devel- opment of novel, selective and more potent antitubercular agents in the future.

Synthesis, antitubercular and antimicrobial potential of some new thiazole substituted thiosemicarbazide derivatives - Abhale, Y. K.; Shinde, A.; Deshmukh, K. K.; Nawale, L.; Sarkar, D.; Mhaske, P. C. (Medicinal Chemistry Research, 2017)
The increase in antibiotic resistance due to multiple factors has warranted the need for the search of new compounds which are active against multidrug resistant pathogens. In this context a small focused library of thiosemicarbazide derivatives of 2-arylthiazole-4-carbaldehyde, 4-methyl-2-arylthiazole-5-carbaldehyde and 1-(4-methyl-2-arylthiazol-5-yl) ethanone, (5a–l) has been synthesized. The title compounds were screened for inhibitory activity against Mycobacterium tuberculosis H37Ra (ATCC 25177) and Mycobacterium bovis Bacille Calmette Guerin (ATCC 35743) strains. The synthesized compounds, 5a–l were further assayed for their cytotoxic activity against the two human cancer cell lines, HeLa and human colon carcinoma 116 cell lines and showed no significant cytotoxic activity against these two cell lines at the maximum concentration evaluated. Further, the synthesized compounds were found to have potential antibacterial activity against Gram-negative bacteria, Escherichia coli, Pseudomonas flurescence and Gram-positive bacteria, Staphylococcus aureus, Bacillus subtilis. Most of the synthesized compounds showed moderate activity against fungal strain Candida albicans. This study provides valuable directions to our ongoing endeavor of rationally designing more potent antimycobacterial agent. © 2017, Springer Science+Business Media, LLC.
Keywords: Antimicrobial activity; Antitubercular activit; Cytotoxicity; Thiazole; Thiosemicarbazide

Synthesis of amphiphilic isoindigo co-polymers for organic field effect transistors: A comparative study - Dharmapurikar, Satej S.; Arulkashmir, Arulraj; Mahale, Rajashree Y.; Chini, Mrinmoy Kumar (Journal of the apllied polymer science, 2017)
In this work, the amphiphilic isoindigo (am-iInd) based conjugated polymers namely poly(am-iInd-DT) and poly(am-iInd-TT) and their regular counterpart poly(reg-iInd-DT) and poly(reg-iInd-TT) were synthesized to compare their opto-electronic and charge transport properties. They were used to fabricate organic field effect transistors. Charge transport properties in conjugated polymers depend upon intermolecular interaction which is strongly affected by the nature of side chains. The amphiphilic nature of the conjugated polymers has little impact on the charge transport properties. The charge carrier mobility of amphiphilic conjugated polymers was comparable with the regular polymers except poly(reg-iInd-DT) which can be correlated by X-ray diffraction and thin film morphology. (c) 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45461.
Keywords: Alkyl; Applications; Conducting polymers; Copolymers; Optical and Photovoltaic applications; conjugated polymers; High-performance; mobility; Packaging; Semicondoctors; Side-chains; Solar-cells; Thin-film Transformer

Synthesis of extended conjugated indolyl chalcones as potent anti-breast cancer, anti-inflammatory and antioxidant agents - Bhale, Pravin S.; Chavan, Hemant V.; Dongare, Sakharam B.; Shringare, Sadanand N.; Mule, Yoginath B.; Nagane, Samadhan S.; Bandgar, Babasaheb P. (Bioorganic & Medicinal Chemistry Letters, 2017)
In the present investigation, synthesis of a series of extended conjugated delta-chloro-alpha-cyano substituted indolyl chalcones (5a-p) was accomplished by reacting 3-cyanoacetylindole 2 with 3-chloro-3-phenylpropenal 4 in the presence of piperidine. The structural interpretations of newly synthesized compounds were based on chemical and spectroscopic evidences. Anti-tumor evaluation of the synthesized compounds in vitro against MCF-7 (breast carcinoma) cell line revealed that they possess high anti-tumor activities. Among them, compound 5e and 5a demonstrated excellent activity against breast carcinoma (GI(50) <0.1 and mu M respectively) as good as adriamycin (GI(50) <0.1 mu M). The compounds were also screened against the normal Vero monkey cell line, which showed moderate selectivity against inhibition of cancer cells. The effect of extended conjugation on activity authenticated by comparing activity profile of compound 5a, 5i and 5m with their simple analogues. Among the synthesized compounds, 5i and 51 were found to be active anti-inflammatory agents in addition to having noteworthy antioxidant potential. These results suggest the possible use of these compounds for the design and development of novel anti breast cancer agents. (C) 2017 Elsevier Ltd. All rights reserved.

Synthesis of isohexide-di(ether-ene)s and ADMET polymerization - Rajput, Bhausaheb S.; Lekshmy, Kalpakasseril Girija; Menon, Shamal K.; Chikkali, Samir H. (Green Materials, 2017)
As the fossil fuel reserves deplete and the greenhouse gases increase, the scientific community is challenged to provide sustainable solutions. Sugar-based isohexides can be modified to prepare a library of isohexide-diene monomers for polymerization. Such isohexide diene monomers can be subjected to Acyclic Diene Metathesis Polymerization to obtain green materials. Here we report a single step synthetic protocol to access a small family of isohexide-di(ether-ene)s and the corresponding polymers. The isohexide di(ether-ene)s 2a-2c could be isolated in good to excellent yields under optimized conditions. The resultant isohexide-di(ether-ene)s 2a-2c are potential versatile building blocks for pharmaceuticals and material science. The synthetic utility of 2a-2c was demonstrated by subjecting them to ADMET polymerization using Grubbs 1st and 2nd generation catalysts. The resultant viscous material was evaluated using 1H NMR and MALDI-ToF-MS, which suggests the formation of anticipated ADMET polymers

Synthesis of meta-substituted monodentate phosphinite ligands and implication in hydroformylation - Deshmukh, Satej S.; Gaikwad, Shahaji R.; Pandey, Swechchha; Mali, Pramod S.; Chikkali, Samir H. (Journal of Chemical Sciences, 2017)
Synthesis of meta-substituted phosphinite ligands 3,3'-(methoxyphosphanediyl) bis(N, N-diethylaniline) (4a) and methoxybis(3-methoxyphenyl) phosphane (4b), in high yields, has been demonstrated. Typical phosphorus chemical shift between 110-120 ppm, appearance of methoxy protons and corresponding carbon, as well as ESI-MS spectra unambiguously confirmed the existence of phosphinite ligands 4a and 4b. To demonstrate the synthetic usefulness of 4a and 4b, these ligands were tested in the rhodium catalyzed hydroformylation of 1-octene. The diethylamine substituted ligand 4a was found to be highly active, whereas 4bwas less reactive but revealed slightly better regioselectivity of 62% under optimized conditions. Additionally, 4a and 4b were found to catalyze the hydroformylation of styrene, 1-undecenol and 1,1-disubstituted functional olefin, methyl methacrylate. Both the ligands displayed excellent conversion of styrene, and 4b revealed an excellent branch selectivity of 75%. Although 1-undecenol proved to be amenable to hydroformylation (85-90% conversion to aldehyde), both the ligands failed to discriminate between the linear and branched products. Substrate methyl methacrylate proved to be highly challenging and reduced conversion (between 33-42%) was observed under optimized conditions. Ligand 4a was found to be highly selective towards linear aldehyde (81% linear selectivity).

Synthesis of methyl-protected (+/-)-chlorizidine A - Mahajan, Jyoti P.; Mhaske, Santosh B. (Organic Letters, 2017)
The first total synthesis of the methyl-protected (+/-)-chlorizidine A has been achieved in 10 steps. Pd-catalyzed decarboxylative coupling and late-stage oxidation were utilized to, construct the 5H-pyrrolo[2,1-a]isoindol-5-one scaffold. Samarium(II) iodide mediated Reformatsky reaction and intramolecular Mitsunobu reactions were efficiently applied for the synthesis of the 2,3-dihydropyrrolizine ring system. Chlorizidine A is highly prone to degradation; hence, methyl-protected (+/-)-chlorizidine A was prepared.

Synthesis of o-methyl trifluoromethyl sulfide substituted benzophenones via 1,2-difunctionalization of aryne by insertion into the C-C bond - Ahire, Milind M.; Khan, Ruhima; Mhaske, Santosh B. (Organic Letters, 2017)
An efficient process for the preparation of valuable o-methyl trifluoromethyi sulfide substituted benzopheriones has been developed. The transition-metal-free method features insertion of aryne into a C-C sigma-bond under mild reaction conditions for the first time to achieve ortho-difunctionalized arenes containing a pharmaceutically important trifluoromethylthio functional group. A wide substrate, scope has been demonstrated for the developed protocol.

Synthesis of orthorhombic-molybdenum trioxide (α-MoO3) thin films by hot wire-CVD and investigations of its humidity sensing properties - Jadkar, Vijaya; Pawbake, Amit S.; Waykar,Ravindra G.; Jadhavar, Ashok Arjun; Mayabadi, Azam; Date, Abhijit; Late, Dattatray J.; Pathan, Habib M.; Gosavi, Suresh W.; Jadkar, Sandesh R. (Journal of Materials Science Materials in Electronics, 2017)
In present work, we report synthesis of orthorhombic-molybdenum trioxide (α-MoO 3) thin films using home-build hot wire-CVD (HW-CVD) method simply by heating the Mo filament in a controlled O 2 atmosphere. The formation of α-MoO 3 was confirmed by low angle-XRD and Raman spectroscopy. Low angle-XRD analysis revealed that α-MoO 3 crystallites have orientations along (110), (101) and (111) directions while Raman spectroscopy analysis shows two prominent vibrational modes ~819 and ~994 cm −1 associated with Mo 2–O and Mo=O respectively. SEM and TEM analysis show the formation of nano-sheets like morphology of α-MoO 3 thin films. The SAED pattern shows highly crystalline nature of α-MoO 3. The humidity-sensing properties were investigated at room temperature by fabricating the two probe device. The humidity sensing results showed n-type behavior of α-MoO 3. The maximum humidity sensitivity of ~6957% along with response time of ~66 s and recovery time of ~5 s were observed for α-MoO 3 thin film humidity sensor device. Our results have opened up a new avenue to grow α-MoO 3 for humidity sensor applications.

Synthesis of succinimide derivatives by NHC-catalyzed stetter reaction of aromatic aldehydes with N-substituted itaconimides - Ahire, Milind M.; Mhaske, Santosh B. (ACS Omega, 2017)
An N-heterocyclic carbene-catalyzed intermolecular Stetter reaction of aromatic aldehydes with N-substituted itaconimides has been developed. A delicate balance between the Stetter reaction and the competing isomerization of the itaconimide double bond has been achieved in this operationally simple reaction to afford valuable new succinimide derivatives containing 1,4 and 1,5 dicarbonyl scaffolds in good to excellent yields. The reaction tolerates variable substituents on both aldehydes and N-substituted itaconimides.

Synthesis route to pyrrolones from -cyano ,-unsaturated ketones and -isocyano esters by oxidative dearomatization of 2-aminofuran intermediates - Mahida, Anil K.; Kale, Someshwar B.; Das, Utpal (European Journal of Organic Chemistry, 2017)
An efficient method for the catalyst/promoter-free synthesis of tetrasubstituted furan derivatives proceeding through the [4+1] cycloaddition of isocyanoacetates with electron-deficient olefins was developed. The products were obtained in good to excellent yields without any column chromatography. Oxidative dearomatization of these furans was achieved only in the presence of oxygen, which led to pyrrolones in high yields.

Tailoring the properties of mPEG-PLLA nanoparticles for better encapsulation and tuned release of the hydrophilic anticancer drug - Surwase, Sachin S.; Munot, Neha Manish; Idage, Bhaskar B.; Idage, Susheela B. (Drug Delivery and Translational Research, 2017)
Gemcitabine is used as a first-line drug for treating many solid tumours. However, it suffers from a major drawback of strong side effects and short plasma half-life because of degradation by enzyme when administered intravenously. Polyesters and copolyesters are the most widely used and preferred class of biodegradable polymer. In the present work, efforts have been made to prepare poly(ethylene glycol) monomethoxy ether-poly(l-lactide) (mPEG-PLLA), a biodegradable amphiphilic copolymer with a view to improve the entrapment and tuned release of hydrophilic drug gemcitabine. The different mPEG-PLLA copolymers were synthesized with the varying ratios of mPEG and characterized by different techniques namely FTIR and ¹H NMR spectroscopy, solution viscosity, differential scanning calorimetry (DSC) and gel permeation chromatography (GPC). Gemcitabine-loaded nanoparticles were prepared using mPEG-PLLA copolymers by two methods i.e. nanoprecipitation and double emulsion solvent evaporation. The nanoprecipitation method showed very less entrapment and polymer solubility in the acetone-water mixture leading to uncontrolled polymer precipitation. The difficulties encountered in the nanoprecipitation method were overcome with the help of the double emulsion (w/o/w) solvent evaporation technique. It has been observed from the results that biodegradable copolymer nanoparticles protect the drug from degradation and also help in controlling the release of encapsulated drug. The properties of nanoparticles can be tailored by varying the composition of mPEG in order to get improved entrapment efficiency and desired drug release. The nanoparticles were assessed for their in vitro cytotoxicity (MTT and FACS) and cellular uptake (fluorescence microscopy) study which showed very promising results. Nanoparticles were also studied for their in vivo release after intravenous administration to Wistar albino rats, which successfully showed controlled drug release for more than 14 days.

Targeted drug delivery in covalent organic nanosheets (CONs) via sequential postsynthetic modification - Mitra, Shouvik; Sasmal, Himadri Sekhar; Kundu, Tanay; Kandambeth, Sharath; Math, Kavya; Diaz Diaz, David; Banerjee, Rahul (Journal of the American Chemical Society, 2017)
Covalent organic nanosheets (CONs) have emerged as a new class of functional two-dimensional (2D) porous organic polymeric materials with a high accessible surface, diverse functionality, and chemical stability. They could become versatile candidates for targeted drug delivery. Despite their many advantages, there are limitations to their use for target specific drug delivery. We anticipated that these drawbacks could be overturned by judicious postsynthetic modification steps to use CONs for targeted drug delivery. The postsynthetic modification would not only produce the desired functionality, it would also help to exfoliate to CONs as well. In order to meet this requirement, we have developed a facile, salt-mediated synthesis of covalent organic frameworks (COFs) in the presence of p-toluenesulfonic acid (PTSA). The COFs were subjected to sequential postsynthetic modifications to yield functionalized targeted CONs for targeted delivery of 5-fluorouracil to breast cancer cells. This postsynthetic modification resulted in simultaneous chemical delamination and functionalization to targeted CONs. Targeted CONs showed sustained release of the drug to the cancer cells through receptor mediated endocytosis, which led to cancer cell death via apoptosis. Considering the easy and facile COF synthesis, functionality based postsynthetic modifications, and chemical delamination to CONs for potential advantageous targeted drug delivery, this process can have a significant impact in biomedical applications.

Targeting RNA G-Quadruplexes for potential therapeutic applications - Pandey,Satyaprakash; Agarwala, Prachi; Maiti,Souvik (Topics in Medicinal Chemistry, 2017)
RNA G-quadruplexes are non-canonical structures formed in G-rich regions of transcriptome. Considerable research points towards the potential role for these dynamic structures in various genes involved in multiple pathways. The ability of these structures to influence important biological processes has been demonstrated in few selected important genes and more recently in a global manner across the transcriptome. RNA G-quadruplexes are implicated in fundamental processes such as translational regulation, alternative splicing, mRNA transport and telomere homeostasis to name a few. The involvement of these structures in key biological processes makes them attractive targets for therapeutic interventions. Here we discuss the structural features of RNA G-quadruplex that make it more monomorphic to develop ligands unlike the polymorphic DNA G-quadruplexes. Furthermore, the role of RNA G-quadruplexes in important genes involved in diseases and disorders such as neurodegeneration, cancer and viral infections has been highlighted. A summary of ligands and their established roles in targeting RNA G-quadruplex structures has been discussed in context of important processes. Moreover, we highlight the need to develop ligands that are highly specific in targeting RNA G-quadruplexes, a new target to restore homeostasis in dysregulated conditions.

Template -free assembly in living bacterial suspension under an external electric field - Samantaray, Kunal; Bhol, Prachi; Sahoo, Bhaban; Barik, Subrat Kumar; Jathavedan, Kiran; Sahu, Bikash Ranjan; Bikash Ranjan; Suar, Mrutyunjay; Bhat, Suresh K.; Mohanty, Priti Sunda (ACS Omega, 2017)
Although template-assisted self-assembly methods are very popular in materials and biological systems, they have certain limitations such as lack of tunability and switchable functionality because of the irreversible association of cells and their matrix components. With an aim to achieve more tunability, we have made an attempt to investigate the self-assembly behavior of rod-shaped living bacteria subjected to an external alternating electric field using confocal microscopy. We demonstrate that rod-shaped living bacteria dispersed in a low salinity aqueous medium form different types of reversible freely suspended structures when subjected to an external alternating electric field. At low field strength, an oriented phase is observed where individual bacterium orients with its major axis aligned along the field direction. At intermediate field strength, bacteria align in the form of one-dimensional (1D) chains that lie along the field direction. Further, at high field strength, more bacteria associate with these 1D chains laterally to form a two-dimensional (2D) array. At higher bacterial concentration, these field-induced 2D arrays extend to form three-dimensional columnar structures. These results are discussed in the context of previously reported studies on bacterial self-assembly.
Keywords: Bacteria; Electric Properties; Self- Assembly

Tf2NH-catalyzed 1,6-conjugate addition of vinyl azides with p-quinone methides: a mild and efficient method for the synthesis of β-bis-arylamides - Rathod, Jayant; Sharma, Brijesh M.; Mali, Pramod S.; Kumar, Pradeep (Synthesis, 2017)
Tf2NH-catalyzed tandem 1,6-conjugate addition/Schmidt type rearrangement using vinyl azides and p-quinone methides to access a variety of β-bis-arylated amides is reported. The method is quick, efficient, mild, and high yielding with broad substrate scope.

Thermomechanical effect in molecular crystals: the role of halogen-bonding interactions - Mittapalli, Sudhir; Perumalla, D. Sravanakumar; Nanubolu, Jagadeesh Babu; Nangia, Ashwini (IUCRJ, 2017)
The design and synthesis of mechanically responsive materials is interesting because they are potential candidates to convert thermal energy into mechanical work. Reported in this paper are thermosalient effects in a series of halogen derivatives of salinazids. The chloro derivative, with higher electronegativity and a weaker inter-halogen bond strength (Cl center dot center dot center dot Cl) exhibits an excellent thermal response, whereas the response is weaker in the iodo derivative with stronger I center dot center dot center dot I halogen bonding. 3,5-Dichlorosalinazid (Compound-A) exists in three polymorphic forms, two room-temperature polymorphs (Forms I and II) and one high-temperature modification (Form III). The transformation of Form I to Form III upon heating at 328-333 K is a reversible thermosalient transition, whereas the transformation of Form II to Form III is irreversible and nonthermosalient. 3,5-Dibromo- (Compound-B) and 3-bromo-5-chloro(Compound-C) salinazid are both dimorphic: the Form I to Form II transition in Compound-B is irreversible, whereas Compound-C shows a reversible thermosalient effect (362-365 K). In the case of 3,5-diiodosalinazid (CompoundD) and 3,5-difluorosalinazid (Compound-E), no phase transitions or thermal effects were observed. The thermosalient behaviour of these halosalinazid molecular crystals is understood from the anisotropy in the cell parameters (an increase in the a axis and a decrease in the b and c axes upon heating) and the sudden release of accumulated strain during the phase transition. The dihalogen salinazid derivatives (chlorine to iodine) show a decrease in thermal effects with an increase in halogen-bond strength. Interestingly, Compound-B shows solid-state photochromism in its polymorphs along with the thermosalient effect, wherein Form I is cyan and Form II is light orange.

Thermo-responsive PNIPAM-metal hybrids: an efficient nanocatalyst for the reduction of 4-nitrophenol - Satapathy, Smith Sagar; Bhol, Prachi; Chakkarambath, Aswathy; Mohanta, Jagdeep; Samantaray, Kunal; Bhat, Suresh K.; Panda, Subhendu K.; Mohanty, Priti S.; Si, Satyabrata (Applied Surface Science, 2017)
Micron size thermoresponsive cross-linked polymeric microgels of poly(N-isopropylacrylamide) (PNIPAM) are used as "microreactor" for embedding metal nanoparticles of different shapes. Using a simple and robust method, we have synthesized various polymer-metal hybrid nanostructures incorporated with Au nanorods (AuNR), Au nanospheres (AuNS) and Ag nanospheres (AgNS). These hybrid nanostructures have been characterized by transmission electron microscope (TEM), UV-vis spectroscopy, dynamic light scattering (DLS) and static light scattering (SLS) followed by their catalytic activity. TEM studies directly confirmed the mondispersity of synthesized hybrid microgels and stability of the embedded metal nanoparticles within the microgels. Optical studies confirmed the presence of respective absorption bands that correspond to AuNS, AgNS and AuNR respectively. Extensive DLS studies demonstrated that although these hybrid microgels preserve their thermoresponsive properties, i.e their hydrodynamic radius decreased with increasing temperature, their thermosensitivity were comparatively lesser than pure PNIPAM microgels. Combining with studies using static light scattering, we further found that AuNS and AgNS were inhomogeneously distributed within microgels where the majority of the nanoparticles present within the loosely cross-linked shell. On the other hand AuNR were distributed more homogeneously within the microgels. Catalytic performance of various nanostructures loaded onto PNIPAM microgel beads were evaluated by studying the catalytic reduction of 4-nitrophenol. Complete catalytic conversion using AgNS occurred in similar to 30 min with a first-order rate constant of 0.159 min(-1) having a 7 min induction period. On the other hand no induction period was observed for AuNS and AuNR and the reaction completed in 3-4 min with a first-order rate constant of 1.607 min(-1) and 1.627 min(-1) respectively. Further, PNIPAM-AuNS and PNIPAM-AuNR possess better catalytic activity as well as recyclability compared to that of PNIPAM-AgNS. (C) 2017 Elsevier B.V. All rights reserved.