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551.
Pardasani D Palit M Gupta AK Kanaujia PK Sekhar K Dubey DK 《Journal of chromatography. A》2006,1108(2):166-175
Detection and identification of environmental signatures of chemical warfare agents is an important aspect of verification program of Chemical Weapons Convention (CWC). Alkylphosphonic acids (APAs) are ultimate and persistent degradation products of nerve agents. Their identification in a sample submitted for off-site analysis infers possible indication of contamination with nerve agents. This paper describes the development of a new sample preparation method which involves 'in situ derivatization and extraction' (INDEX) of acids from water. Derivatization is performed by alkylation of APAs with alkylbromides in surfactant less microemulsion (SLME). The derivatized analytes were analyzed by gas chromatography coupled with mass spectrometry. The developed method involves simultaneous derivatization (alkylation) and extraction of acidic analytes mediated by surfactant less microemulsion. Various derivatization-extraction parameters such as solvent, reaction time and temperature, base and alkyl bromides were optimized. Pentyl bromide in the presence of potassium carbonate and diisopropylamine at 100 degrees C derivatized the selected acids efficiently. Kinetic data for alkylation of methylphosphonic acids and some carboxylic acids were obtained to assess their relative susceptibility for alkylation in microemulsion. Methylphosphonic acid and isopropyl methylphosphonic acid took 140-150 min to reach completion while carboxylic acids took 100 min to complete the reaction. INDEX could be successfully performed even in the presence of interfering Ca(2+) and Mg(2+) ions. 相似文献
552.
Bansal V Poddar P Ahmad A Sastry M 《Journal of the American Chemical Society》2006,128(36):11958-11963
The syntheses of inorganic materials by biological systems is characterized by processes that occur close to ambient temperatures, pressures, and neutral pH, as is exemplified by biosilicification and biomineralization processes in nature. Conversely, laboratory-based syntheses of oxide materials often require extremes of temperature and pressure. We have shown here the extracellular, room-temperature biosynthesis of 4-5 nm ternary oxide nanoparticles such as barium titanate (BT) using a fungus-mediated approach. The tetragonality as well as a lowered Curie transition temperature in sub-10 nm particles was established, and the ferroelectricity in these particles was shown using Kelvin probe microscopy. 相似文献
553.
Complex thermoacoustic oscillations are observed experimentally in a simple laboratory combustor that burns lean premixed fuel-air mixture, as a result of nonlinear interaction between the acoustic field and the combustion processes. The application of nonlinear time series analysis, particularly techniques based on phase space reconstruction from acquired pressure data, reveals rich dynamical behavior and the existence of several complex states. A route to chaos for thermoacoustic instability is established experimentally for the first time. We show that, as the location of the heat source is gradually varied, self-excited periodic thermoacoustic oscillations undergo transition to chaos via the Ruelle-Takens scenario. 相似文献
554.
Das Pankaj Konwar Dilip Sengupta Pinaki Dutta Dipak K 《Transition Metal Chemistry》2000,25(4):426-429
Rhodium(I) carbonyl complexes [Rh(CO)2ClL] where L = Ph3PO, Ph3PS and Ph3PSe, were synthesized and characterized by elemental analysis, i.r. and by 1H-, 13C- and 31P-n.m.r. spectroscopy. The vBD;(CO) band frequencies in the complexes follow the order: Ph3PO > Ph3PS > Ph3PSe, in keeping with the hard/soft nature of the interactions. The complexes undergo oxidative additions with electrophiles
such as MeI, PhCH2Cl and I2 to give, e.g. [Rh(CO)(COMe)ClIL] which react with PPh3 to give trans-[Rh(CO)Cl(PPh3)2]. The catalytic activity of the [Rh(CO)2ClL] complexes in carbonylation of MeOH is higher than that of the well-known [Rh(CO)2I2]− species.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
555.
556.
Kulbir Sandip Das Tarali Devi Mrigaraj Goswami Mahesh Yenuganti Prabhakar Bhardwaj Somnath Ghosh Subash Chandra Sahoo Pankaj Kumar 《Chemical science》2021,12(31):10605
Nitrate reductases (NRs) are molybdoenzymes that reduce nitrate (NO3−) to nitrite (NO2−) in both mammals and plants. In mammals, the salival microbes take part in the generation of the NO2− from NO3−, which further produces nitric oxide (NO) either in acid-induced NO2− reduction or in the presence of nitrite reductases (NiRs). Here, we report a new approach of VCl3 (V3+ ion source) induced step-wise reduction of NO3− in a CoII-nitrato complex, [(12-TMC)CoII(NO3−)]+ (2,{CoII–NO3−}), to a CoIII–nitrosyl complex, [(12-TMC)CoIII(NO)]2+ (4,{CoNO}8), bearing an N-tetramethylated cyclam (TMC) ligand. The VCl3 inspired reduction of NO3− to NO is believed to occur in two consecutive oxygen atom transfer (OAT) reactions, i.e., OAT-1 = NO3− → NO2− (r1) and OAT-2 = NO2− → NO (r2). In these OAT reactions, VCl3 functions as an O-atom abstracting species, and the reaction of 2 with VCl3 produces a CoIII-nitrosyl ({CoNO}8) with VV-Oxo ({VV O}3+) species, via a proposed CoII-nitrito (3, {CoII–NO2−}) intermediate species. Further, in a separate experiment, we explored the reaction of isolated complex 3 with VCl3, which showed the generation of 4 with VV-Oxo, validating our proposed reaction sequences of OAT reactions. We ensured and characterized 3 using VCl3 as a limiting reagent, as the second-order rate constant of OAT-2 (k2/) is found to be ∼1420 times faster than that of the OAT-1 (k2) reaction. Binding constant (Kb) calculations also support our proposition of NO3− to NO transformation in two successive OAT reactions, as Kb(CoII–NO2−) is higher than Kb(CoII–NO3−), hence the reaction moves in the forward direction (OAT-1). However, Kb(CoII–NO2−) is comparable to Kb{CoNO}8, and therefore sequenced the second OAT reaction (OAT-2). Mechanistic investigations of these reactions using 15N-labeled-15NO3− and 15NO2− revealed that the N-atom in the {CoNO}8 is derived from NO3− ligand. This work highlights the first-ever report of VCl3 induced step-wise NO3− reduction (NRs activity) followed by the OAT induced NO2− reduction and then the generation of Co-nitrosyl species {CoNO}8.Single metal-induced reduction of NO3− → {NO2−} → NO via oxygen atom transfer reaction. 相似文献
557.
Dr. Pankaj Sharma Dr. Monika Sharma Dr. Malcolm Dearg Dr. Martin Wilding Dr. Thomas J. A. Slater Prof. C. Richard A. Catlow 《Angewandte Chemie (International ed. in English)》2023,62(20):e202301239
Despite extensive efforts to develop high-performance H2 evolution catalysts, this remains a major challenge. Here, we demonstrate the use of Cd/Pt precursor solutions for significant photocatalytic H2 production (154.7 mmol g−1 h−1), removing the need for a pre-synthesized photocatalyst. In addition, we also report simultaneous in situ synthesis of Pt single-atoms anchored CdS nanoparticles (PtSA-CdSIS) during photoirradiation. The highly dispersed in situ incorporation of extensive Pt single atoms on CdSIS enables the enhancement of active sites and suppresses charge recombination, which results in exceptionally high solar-to-hydrogen conversion efficiency of ≈1 % and an apparent quantum yield of over 91 % (365 nm) for H2 production. Our work not only provides a promising strategy for maximising H2 production efficiency but also provides a green process for H2 production and the synthesis of highly photoactive PtSA-CdSIS nanoparticles. 相似文献
558.
Michael B. Hicks Keith Mattern Jonathan Fine Shane Grosser Daya Patel Lauren Weisel Pankaj Aggarwal 《Journal of separation science》2023,46(21):2300300
Pharmaceutical development currently relies on quality separation methods from early discovery through to line-of-site manufacturing. There have been significant advancements made regarding the column particle packing, internal diameter, length connectivity, the understanding of the impact key parameters like void volume, flow rate, and temperature all that affects the resultant separation quality, that is, resolution, peak shape, peak width, run time, and signal-to-noise ratio. There is however a strong need to establish better alternatives to large bulky high-performance liquid chromatography racks either for process analytical reaction monitoring or mass spectrometry analysis in establishing product quality. Compact, portable high-pressure liquid chromatography can be a more efficient alternative to traditional ultra-high pressure liquid chromatography and traditional liquid chromatography. The compact versatile instrument evaluated here allows good separation control with either the on-board column with fixed ultra-violet wavelength cartridge or for use with a high-resolution mass spectrometry. Significant space reduction results in greener lab spaces with improved energy efficiency for smaller labs with lower energy demands. In addition, this compact liquid chromatography was used as a portable reaction monitoring solution to compare forced degradation kinetics and assess portable liquid chromatography-mass spectrometry capability for the analyses required for pharmaceutical drug product testing. 相似文献