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41.
V. Balaram S. L. Ramesh K. V. Anjaiah 《Fresenius' Journal of Analytical Chemistry》1995,353(2):176-182
ICP-MS has been used for the determination of over 30 geochemically significant trace elements (Sc, V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Cs, Ba, Hf, Ta, Pb, Th, U and REEs) in anorthosites and related rock reference samples. Open acid digestion, pressure decomposition using HF, HNO3 and HClO4, and a fusion method using lithium metaborate and subsequent dissolution in dil. HNO3 were adopted for the decomposition of these rock samples before analysis. The dissolution problems and interference effects are discussed. Rh and Bi were used as internal standards. The first set of data on several rare earths and other trace elements in the Russian anorthosite reference sample, MO-6 are presented along with data on other samples. The data are compared with the available data. The results obtained with different dissolution methods were found to be in good agreement for the majority of the trace elements. The accuracy and precision achieved (better than 6% RSD in most cases) suggested that the data obtained by ICP-MS for such samples are best suited for geochemical interpretations. 相似文献
42.
43.
L-histidine substitutes cyano groups of K4Fe (CN)6 at pH 7·0 on irradiation with ultraviolet light. The reaction follows first order kinetics with reference to K4Fe(CN)6 and zero order with reference to histidine. The kinetic data shows the primary process to be aquation of Fe(CN) 6 4? while the final product is formed through a rapid dark reaction of histidine with Fe(CN)4 (H2O) 2 2? to give the product K2Fe(CN)2(histidine)2. The final product has been subjected to chemical and infrared spectral analysis. 相似文献
44.
The overall objective of this investigation is to achieve high‐performance membranes with respect to flux and rejection characteristics, with an interplay of blending polymers having desired qualities. Thus, cellulose diacetate and polyethersulfone as candidate materials, in the presence of polyethylene glycol 600 as a pore forming agent, were blended in 100/0, 95/5, 90/10, 85/15, 80,20 and 75/25% compositions using N,N′‐dimethylformamide as solvent and membranes were prepared by the phase inversion technique. Polymer blend composition, additive concentration, and casting and gelation conditions were standardized for the preparation of asymmetric membranes with various pore statistics and morphology. These blend membranes were characterized for compaction in ultrafiltration experiments at 414 kPa pressure in order to attain steady state flux and is reached within 4–5 hr. The pure water flux was measured at 345 kPa pressure and is determined largely by the composition of polyethersulfone and additive concentration. The flux was found to reach the highest values of 66.5 and 275 1/(cm2 hr) at 0 and 10 wt% additive concentrations respectively, at 25% SPS content of the blend. Membrane hydraulic resistance derived by measuring water flux at various transmembrane pressure and by using an algorithm was found to be inversely proportional to pure water flux. Water content is estimated by simple drying and weighing procedures and found proportional to pure water flux for all the membranes. The molecular weight cut‐offs (MWCOs) of different membranes were determined with proteins of different molecular weights and found to vary from 20–69 kDa (globular proteins) depending on the PEG and SPS content in the casting dope. Skin surface porosity of the membranes were analyzed by scanning the frozen membrane samples using scanning electron microscopy (SEM) at different magnifications. The surface porosity is in direct correlation to the MWCO derived from solute retention experiments. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
45.
Polymers are an integral part of our daily life. Hence, there are constant efforts towards synthesizing novel polymers with unique properties. As the composition and packing of polymer chains influence polymer''s properties, sophisticated control over the molecular and supramolecular structure of the polymer helps tailor its properties as desired. However, such precise control via conventional solution-state synthesis is challenging. Topochemical polymerization (TP), a solvent- and catalyst-free reaction that occurs under the confinement of a crystal lattice, offers profound control over the molecular structure and supramolecular architecture of a polymer and usually results in ordered polymers. In particular, single-crystal-to-single-crystal (SCSC) TP is advantageous as we can correlate the structure and packing of polymer chains with their properties. By designing molecules appended with suitable reactive moieties and utilizing the principles of supramolecular chemistry to align them in a reactive orientation, the synthesis of higher-dimensional polymers and divergent topologies has been achieved via TP. Though there are a few reviews on TP in the literature, an exclusive review showcasing the topochemical synthesis of polymers with advanced structural features is not available. In this perspective, we present selected examples of the topochemical synthesis of organic polymers with sophisticated structures like ladders, tubular polymers, alternating copolymers, polymer blends, and other interesting topologies. We also detail some strategies adopted for obtaining distinct polymers from the same monomer. Finally, we highlight the main challenges and prospects for developing advanced polymers via TP and inspire future directions in this area.This perspective showcases the potential of topochemical polymerization as an effective tool for synthesizing polymers with advanced molecular and supramolecular structures. 相似文献
46.
Moriarty RM Rani N Enache LA Rao MS Batra H Guo L Penmasta RA Staszewski JP Tuladhar SM Prakash O Crich D Hirtopeanu A Gilardi R 《The Journal of organic chemistry》2004,69(6):1890-1902
A general and novel solution to the synthesis of biologically important stable analogues of prostacyclin PGI(2), namely benzindene prostacyclins, has been achieved via the stereoselective intramolecular Pauson-Khand cyclization (PKC). This work illustrates for the first time the synthetic utility and reliability of the asymmetric PKC route for synthesis and subsequent manufacture of a complex drug substance on a multikilogram scale. The synthetic route surmounts issues of individual step stereoselectivity and scalability. The key step in the synthesis involves efficient stereoselection effected in the PKC of a benzoenyne under the agency of the benzylic OTBDMS group, which serves as a temporary stereodirecting group that is conveniently removed via benzylic hydrogenolysis concomitantly with the catalytic hydrogenation of the enone PKC product. Thus the benzylic chiral center dictates the subsequent stereochemistry of the stereogenic centers at three carbon atoms (C(3a), C(9a), and C(1)). 相似文献
47.
Ramesh C. Kapoor Raj N. Mehrotra Shared K. Vajpai Purnima Chaudhary 《Transition Metal Chemistry》1991,16(1):65-70
Summary The kinetics of the OsVIII-catalysed oxidation of glycols by alkaline hexacyanoferrate(III) ion exhibits zerothorder dependence in [Fe(CN)
6
3–
] and first-order dependence in [OsO4]. The order with respect to glycols is less than unity, whereas the rate dependence on [OH–] is a combination of two rate constants; one independent of and the other first-order in [OH–]. These observations are commensurate with a mechanism in which two complexes, [OsO4(H2O)G]– and [OsO4(OH)G]2–, are formed either from [OsO4(H2O)(OH)]– or [OsO4(OH)2]2– and the glycol GH, or by [OsO4(H2O)2] and [OsO4(H2O)(OH)]– and the glycolate ion, G–, which is in equilibrium with the glycol GH through the reaction between GH and OH–. Hence there is an ambiguity about the true path for the formation of the two OsVIII-glycol complexes. A reversal in the reactivity order of glycols in the two rate-determining steps, despite the common attack of OH– ion on the two species of OsVIII-complexes, indicates that the two complexes are structurally different because S changes from the negative (corresponding to k11) to positive (related to k2). 相似文献
48.
Three spectrophotometric methods are described for determining flucythrinate, based on formation of coloured compounds when one of the hydrolysed products of flucythrinate is condensed with 2,4-dinitrophenylhydrazine (2,4-DNPH), 4-nitrophenylhydrazine (4-NPH) or 2,4,6-trinitrophenylhydrazine (2,4,6-TNPH) in the presence of methanolic potassium hydroxide. These coloured compounds absorb strongly at 465 nm (2,4-DNPH), 540 nm (4-NPH) and 485 nm (2,4,6-TNPH). The methods are applicable over the range 0.1-8.0 mug/ml for 2,4-DNPH, 0.5-6.5 mug/ml for 4-NPH and 0.1-6 mug/ml for 2,4,6-TNPH. The methods are rapid, sensitive and selective and can be used for microdetermination of flucythrinate in a commercial formulation, water, grains and crop samples. 相似文献
49.
Propargyloxycarbonyl chloride, 1, has been used to protect the hydroxyl and amino functionalities of amino alcohols and aminophenols in one pot using triethylamine or pyridine as a base. The increased reactivity of benzyltriethylammonium tetrathiomolybdate, 2, toward propargyl carbonates over propargyl carbamates is studied in detail and has been exploited further to develop an orthogonal protection strategy for the hydroxyl and amino functionalities. For example, 2-amino-1-butanol, 6a, was treated with 1 to get the N,O-diPoc compound 7a in 90% yield, which when treated with 1.1 equiv of 2 at room temperature removes the Poc group attached to oxygen while leaving the one attached to nitrogen intact to yield compound 8a in 85% yield. This particular observation offers a new protecting strategy where an amine and an alcohol group can be protected simultaneously in one pot, and in a later synthetic step, if the alcohol group has to be deprotected selectively, it can be achieved with 1 equiv of 2. 相似文献
50.
Maya Ramesh 《Journal of organometallic chemistry》2004,689(8):1425-1430
The molecular box [CpCo(CN)3]4[Cp*Ru]4 (Co4Ru4) reacts readily with a variety of monocations to form M⊂Co4Ru4+ (M=K+, Cs+, Rb+). Ion competition experiments, monitored by ESI-MS, show that the molecular box binds the smaller K+ more rapidly than Cs+, but that thermodynamically Co4Ru4 prefers the larger ion. The rates of ion-insertion for K+ and Cs+ into Co4Ru4 were found to qualitatively follow second order kinetics with K+, 300 M−1 s−1 and Cs+, 36 M−1 s−1. The ratio kK/kCs qualitatively matched the ESI-MS results from ion competition experiments. The rates of ion-insertion into Co4Ru4 were found to depend on the counter anions. In particular, RbBF4 reacted with Co4Ru4 more slowly than did RbOTf. The slower rates allowed us to establish second order kinetics. 1H NMR studies reveal that the Cp signal for Co4Ru4 is very sensitive to the presence of entering ions, e.g., Rb+, whereas the corresponding Cp signal for Rb⊂Co4Ru4+ was insensitive to the presence of Rb+. The molecular structures of [Co4Ru4] · 6MeCN, [K⊂Co4Ru4]BF4 · 7MeCN, [Cs⊂Co4Ru4]BF4 · 6MeCN and [Tl⊂Co4Ru4]BF4 · 6MeCN, determined by X-ray diffraction, showed that although the compounds crystallized in the same space group I23, a correlation exists between the Ru-N/Co-C bond distances and the size of the interstitial ion. 相似文献