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31.
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
32.
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
33.
Vigneshwaran N Bijukumar G Karmakar N Anand S Misra A 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(1-2):163-170
This article describes the analysis of autofluorescence of advanced glycation end products of hemoglobin (Hb-AGE). Formed as a result of slow, spontaneous and non-enzymatic glycation reactions, Hb-AGE possesses a characteristic autofluorescence at 308/345 nm (lambda(ex)/lambda(em)). Even in the presence of heme as a quenching molecule, the surface presence of the glycated adduct gave rise to autofluorescence with the quantum yield of 0.19. The specificity of monoclonal antibody developed against common AGE structure with Hb-AGE was demonstrated using reduction in fluorescence polarization value due to increased molecular volume while binding. The formation of fluorescent adduct in hemoglobin in the advanced stage of glycation and the non-fluorescent HbA(1c) will be of major use in distinguishing and to know the past status of diabetes mellitus. While autofluorescence correlated highly with HbA(1c) value under in vivo condition (r = 0.85), it was moderate in the clinical samples (r = 0.55). The results suggest a non-linear relation between glycemia and glycation, indicating the application of Hb-AGE as a measure of susceptibility to glycation rather than glycation itself. 相似文献
34.
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
35.
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
36.
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
37.
A novel series of complexes of the type [M(TML)X2]; where TML is a tetradentate macrocyclic ligand; M = Co(II), Ni(II), Cu(II) or Zn(II); X = Cl−, CH3COO− or NO
3
−
have been synthesized by template condensation of benzil and thiocarbohydrazide in the presence of divalent metal salts in
methanolic medium. The complexes have been characterized with the help of elemental analyses, conductance measurements, molecular
weight determination, magnetic measurements, electronic, NMR, infrared and far infrared spectral studies. Electronic spectra
along with magnetic moments suggest the six coordinate octahedral geometry for these complexes. The low value of molar conductance
indicates them to be non-electrolytes. The biological activities of metal complexes have been tested in vitro against a number of pathogenic bacteria to assess their inhibiting potential. 相似文献
38.
To the best of our knowledge, bioanalytical methods to determine rosiglitazone in human plasma reported in literature use internal standards that are not commercially available. Our purpose was to develop a simple method for the determination of rosiglitazone in plasma employing a commercially available internal standard (IS). After the addition of celecoxib (IS), plasma (0.25 mL) samples were extracted into ethyl acetate. The residue after evaporation of the organic layer was dissolved in 750 microL of mobile phase and 50 microL was injected on to HPLC. The separation was achieved using a Hichrom KR 100, 250 x 4.6 mm C(18) with a mobile phase composition potassium dihydrogen phosphate buffer (0.01 m, pH 6.5):acetonitrile:methanol (40:50:10, v/v/v). The flow-rate of the mobile phase was set at 1 mL/min. The column eluate was monitored by fluorescence detector set at an excitation wavelength of 247 nm and emission wavelength of 367 nm. Linear relationships (r(2) > 0.99) were observed between the peak area ratio rosiglitazone to IS vs rosiglitazone concentrations across the concentration range 5-1000 ng/mL. The intra-run precision (%RSD) and accuracy (%Dev) in the measurement of rosiglitazone were <+/-10.69 and <-12.35%, respectively across the QC levels (50-1000 ng/mL). The extraction efficiency was >80% for both rosiglitazone and IS from human plasma. The lower limit of quantitation of the assay was 5 ng/mL. In summary, the methodology for rosiglitazone measurement in plasma was simple, sensitive and employed a commercially available IS. 相似文献
39.
Dighe Vidya V. Sane Ramesh T. Menon Shashikumar N. Tambe Harsha N. Pillai Sreedevi 《平面色谱法杂志一现代薄层色谱法》2006,19(4):319-323
JPC – Journal of Planar Chromatography – Modern TLC - A normal-phase high-performance thin-layer chromatographic (HPTLC) method has been established for quantitative estimation of... 相似文献
40.
Preconcentration of Cd(II), Cu(II), Mn(II), Ni(II), Pb(II) and Zn(II) in saline matrices on Amberlite XAD-4 resins coated with ammonium pyrrolidine dithiocarbamate (APDC) and piperidine dithiocarbamate (pipDTC) and subsequent determination by inductively coupled plasma atomic emission spectrometry were studied. Parameters such as effect of pH, effect of HNO(3) concentration on elution of metals from resin were studied. The results show that Amberlite XAD-4 coated with APDC was more efficient in the recovery of metal ions compared with Amberlite XAD-4 coated with pipDTC, in the concentration range of 0.1-200 mug l(-1), for 1 g of Amberlite XAD-4 coated resin. The detection limits for Cd(II), Cu(II), Mn(II), Ni(II), Pb(II), Zn(II) are 0.1, 0.4, 0.3, 0.4, 0.6, 0.5 mug l(-1), respectively, for resin coated with APDC and 0.7, 1.0, 0.8, 0.9, 1.7 and 1.2 mug l(-1) for resin coated with pipDTC. The effect of diverse ions on the determination of aforesaid metals was studied. The method was applied for the determination of trace metal ions in artificial sea water and natural water samples. The results were compared with extraction AAS method. 相似文献