Nanocrystalline Pentaerythritoltetranitrate using Sol-Gel Process

The secondary explosives developed with reduced particle size tend to be more insensitive for mechanical stimuli and may release energy with faster rate and gaining more importance nowadays. Therefore, aiming to reduce the particle size of one of the popular explosives, viz., pentaerythritoltetranitrate (PETN) to the nanometer range, a method for preparation of nanocrystalline PETN in the silica (SiO2) gel matrix using sol-gel process has been demonstrated. The PETN-SiO2 xerogels were prepared containing PETN content ranging from 50 per cent to 90 per cent (w/w) and the xerogels were characterised using different techniques. An exothermic peak at around 185 oC preceded by an endotherm in thermal analysis accompanied with weight loss in the temperature range from 150 oC to 200 oC   for the xerogel confirmed the presence of PETN in xerogel. Infrared spectra of xerogels showed peaks at around 1285 cm-1 and 1700 cm-1 assigned to O-NO2 and C-O bond representing PETN. Small angle x-ray scattering measurements on xerogels indicated that PETN entered in the pores of silica matrix. Transmission electron microscopy revealed that cystalline PETN    with particle size of around 15 nm dispersed in silica xerogel. The specific surface area for the PETN-SiO2 (90:10) xerogels was found to be 75 m2/g.Defence Science Journal, 2011, 61(6), pp.534-539, DOI:http://dx.doi.org/10.14429/dsj.61.59

Nickel-Catalyzed Carbon–Carbon Bond-Forming Reactions of Unactivated Tertiary Alkyl Halides: Suzuki Arylations

The first Suzuki cross-couplings of unactivated tertiary alkyl electrophiles are described. The method employs a readily accessible catalyst (NiBr[subscript 2]·diglyme/4,4′-di-tert-butyl-2,2′-bipyridine, both commercially available) and represents the initial example of the use of a group 10 catalyst to cross-couple unactivated tertiary electrophiles to form C–C bonds. This approach to the synthesis of all-carbon quaternary carbon centers does not suffer from isomerization of the alkyl group, in contrast with the umpolung strategy for this bond construction (cross-coupling of a tertiary alkylmetal with an aryl electrophile). Preliminary mechanistic studies are consistent with the generation of a radical intermediate along the reaction pathway.National Institute of General Medical Sciences (U.S.) (R01-GM62871)Merck Research Laboratories (Summer Fellowship

FDR-controlled metabolite annotation for high-resolution imaging mass spectrometry

© 2017 Nature America, Inc., part of Springer Nature. All rights reserved.High-mass-resolution imaging mass spectrometry promises to localize hundreds of metabolites in tissues, cell cultures, and agar plates with cellular resolution, but it is hampered by the lack of bioinformatics tools for automated metabolite identification. We report pySM, a framework for false discovery rate (FDR)-controlled metabolite annotation at the level of the molecular sum formula, for high-mass-resolution imaging mass spectrometry (https://github.com/alexandrovteam/pySM). We introduce a metabolite-signal match score and a target-decoy FDR estimate for spatial metabolomics

Catalytic Enantioselective Cross-Couplings of Secondary Alkyl Electrophiles with Secondary Alkylmetal Nucleophiles: Negishi Reactions of Racemic Benzylic Bromides with Achiral Alkylzinc Reagents

We have developed a nickel-catalyzed method for the asymmetric cross-coupling of secondary electrophiles with secondary nucleophiles, specifically, stereoconvergent Negishi reactions of racemic benzylic bromides with achiral cycloalkylzinc reagents. In contrast to most previous studies of enantioselective Negishi cross-couplings, tridentate pybox ligands are ineffective in this process; however, a new, readily available bidentate isoquinoline–oxazoline ligand furnishes excellent ee’s and good yields. The use of acyclic alkylzinc reagents as coupling partners led to the discovery of a highly unusual isomerization that generates a significant quantity of a branched cross-coupling product from an unbranched nucleophile

Sharing and community curation of mass spectrometry data with Global Natural Products Social Molecular Networking

The potential of the diverse chemistries present in natural products (NP) for biotechnology and medicine remains untapped because NP databases are not searchable with raw data and the NP community has no way to share data other than in published papers. Although mass spectrometry techniques are well-suited to high-throughput characterization of natural products, there is a pressing need for an infrastructure to enable sharing and curation of data. We present Global Natural Products Social molecular networking (GNPS, http://gnps.ucsd.edu), an open-access knowledge base for community wide organization and sharing of raw, processed or identified tandem mass (MS/MS) spectrometry data. In GNPS crowdsourced curation of freely available community-wide reference MS libraries will underpin improved annotations. Data-driven social-networking should facilitate identification of spectra and foster collaborations. We also introduce the concept of ‘living data’ through continuous reanalysis of deposited data

FDR-controlled metabolite annotation for high-resolution imaging mass spectrometry

© 2017 Nature America, Inc., part of Springer Nature. All rights reserved.High-mass-resolution imaging mass spectrometry promises to localize hundreds of metabolites in tissues, cell cultures, and agar plates with cellular resolution, but it is hampered by the lack of bioinformatics tools for automated metabolite identification. We report pySM, a framework for false discovery rate (FDR)-controlled metabolite annotation at the level of the molecular sum formula, for high-mass-resolution imaging mass spectrometry (https://github.com/alexandrovteam/pySM). We introduce a metabolite-signal match score and a target-decoy FDR estimate for spatial metabolomics

FDR-controlled metabolite annotation for high-resolution imaging mass spectrometry

© 2017 Nature America, Inc., part of Springer Nature. All rights reserved.High-mass-resolution imaging mass spectrometry promises to localize hundreds of metabolites in tissues, cell cultures, and agar plates with cellular resolution, but it is hampered by the lack of bioinformatics tools for automated metabolite identification. We report pySM, a framework for false discovery rate (FDR)-controlled metabolite annotation at the level of the molecular sum formula, for high-mass-resolution imaging mass spectrometry (https://github.com/alexandrovteam/pySM). We introduce a metabolite-signal match score and a target-decoy FDR estimate for spatial metabolomics

FDR-controlled metabolite annotation for high-resolution imaging mass spectrometry

© 2017 Nature America, Inc., part of Springer Nature. All rights reserved.High-mass-resolution imaging mass spectrometry promises to localize hundreds of metabolites in tissues, cell cultures, and agar plates with cellular resolution, but it is hampered by the lack of bioinformatics tools for automated metabolite identification. We report pySM, a framework for false discovery rate (FDR)-controlled metabolite annotation at the level of the molecular sum formula, for high-mass-resolution imaging mass spectrometry (https://github.com/alexandrovteam/pySM). We introduce a metabolite-signal match score and a target-decoy FDR estimate for spatial metabolomics