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51.
52.
Andreoli R Manini P Poli D Bergamaschi E Mutti A Niessen WM 《Analytical and bioanalytical chemistry》2004,378(4):987-994
A new and simple method for the determination of fat-soluble vitamins (retinol, alpha-tocopherol, and beta-carotene) in human serum was developed and validated by using liquid chromatography-tandem mass spectrometry with atmospheric pressure chemical ionization (LC-APCI-MS-MS). Different solvent mixtures were tested to obtain deproteinization and extraction of the analytes from the matrix. As a result, a volume of 240 microL of a 1:1 (v/v) ethanol/ethyl acetate mixture added to 60 microL of serum was found to be suitable for both protein precipitation and antioxidants solubilization, giving the best recovery for all three analytes. Deproteinized samples (20 microL) were injected after dilution, without the need for concentration or evaporation to dryness and reconstruction of the sample. Vitamins were separated on a C-8 column using a 95:5 (v/v) methanol/dichloromethane mixture and ionized in the positive-ion mode; detection was performed in the selected-reaction monitoring mode. Linearity of the LC-APCI-MS-MS method was established over 5 orders of magnitude for retinol and alpha-tocopherol, whereas in the case of beta-carotene it was limited to 4 orders. Lower limits of quantitation were 1.7, 2.3, and 4.1 nM for retinol, alpha-tocopherol, and beta-carotene, respectively. Serum concentrations of retinol, alpha-tocopherol, and alpha+beta-carotene determined in a group of healthy volunteers were 2.48, 38.07, and 0.50 microM, respectively, in samples collected in winter ( n=122) and 2.69, 45.88, and 0.90 microM during summer ( n=66). 相似文献
53.
Ernst Berger David W. T. Griffith Gerhard Schuster Stephen R. Wilson 《Mikrochimica acta》1988,95(1-6):239-241
The use of an integrating sphere for the measurement of absorption spectra of thin films is described. The thin film (for example a rare gas matrix) is grown directly on the inside surface of the sphere. Multiple reflections inside the integrating sphere lead to significant enhancement of weak absorptions of the film, increasing the sensitivity of such measurements. 相似文献
54.
Potential curves for proton transfer in [H5O2]+ and for the dissociation of one OH bond in [H3O]+ were calculated by both ab initio and semi-empirical LCAO MO SCF CI methods. The energy barrier of the symmetric double minimum potential in [H5O2]+ is very sensitive to electron correlation. At an OO distance of 2.74 Å it decreases from the HF value of 9.5 kcal/mole to about 7.0 kcal/mole. The results of the semi-empirical calculations agree well with the ab initio data as long as only relative effects are regarded. The partitioning of correlation energy into contributions of individual electron pairs is very similar for proton transfer in [H5O2]+ and for the dissociation of one OH bond in [H3O]+. In this example the proton transfer appears as a superposition of two “contracted ionic dissociation” processes. An interpretation of the behaviour of correlation during these processes is presented. 相似文献
55.
Ab initio calculations on formaldehyde/Li+ complexes are presented. The most stable arrangement is characterized by an energy of interaction of 43.2 kcal/mole, C2v symmetry and an oxygen—lithium distance of ROLi = 1.77 Å. A detailed analysis of the electron density function gives proof of the electrostatic nature of the complexes H2O/Li+ and H2Co/Li+ and shows extensive mutual polarization. The failure of the semi-empirical method to predict the changes in electron density at the Li+ cation correctly is explained. 相似文献
56.
Wilfried A. Knig Detlef Icheln Torsten Runge Ingo Pforr Adolf Krebs 《Journal of separation science》1990,13(10):702-707
Transferring the site of specific substitution of dipentylated cyclodextrins with methyl or acyl residues from the secondary 3-hydroxyl group to the primary 6-hydroxyl group was expected to provide new information on the mechanism of chiral recognition. The 3-position points towards and the 6-position points away from the cyclodextrin cavity which via inclusion complex formation is supposed to play a major role in chiral separation. The “inverse” 6-O-acyl-2,3-di-O-pentyl-cyclodextrins displayed almost no enantioselectivity but the corresponding 6-O-methyl derivatives are a versatile supplement to the chiral capillary GC phases nowadays available. Among the compounds that could be enantiomerically resolved are alcohols, amino acids, alkyl halides, bicyclic ethers, acetals, olefins, other hydrocarbons and chiral pharmaceuticals. 相似文献
57.
New Ternary Clathrate Compounds in the Systems Barium–Indium/Zinc/Cadmium–Germanium: Zintl Compounds with Phase Width? By systematic investigations in the systems barium–indium/zinc/cadmium–germanium we found a couple of new electrovalent ternary compounds with A8X46 clathrate (I) type structures. They crystallize cubically in space-group Pm3n. For Ba8In16Ge30 (a = 1 075.8 pm), Ba8Zn8Ge38 (a = 1 082.0 pm) and Ba8Cd8Ge38 (a = 1 096.0 pm) the structures were verified by X-ray single crystal diffraction data. According to valence and bounding distances the new clathrates should be Zintl compounds. Measurements of the temperature dependence of the electrical resistivity proved, that they are indeed semiconductors. A part of the 2B/3B metal atoms can be substituted by germanium. Charge balance will be retained by creation of vacancies in the A8X46 type structures. By phase analysis the limits of the composition range were determined as Ba8In4Ge9[]3Ge30 (a = 1 084.9 pm), Ba8Zn4Ge10[]2Ge30 (a = 1 073.6 pm) and Ba8Cd4Ge10[]2Ge30 (a = 1 082.0 pm). 相似文献
58.
The intermolecular cyclotrimerisation of terminal and internal alkynes can be catalysed by simple cobalt complexes such as a CoBr2(diimine) under mild reaction conditions when treated with zinc and zinc iodide with high regioselectivity in excellent yields. 相似文献
59.
A series of isomers of bis(N-methylpyrrolidine)-C(60) 2 (Prato bisadducts) was prepared by the 1,3-dipolar cycloaddition of N-methylazomethine ylide to C(60). Six isomers were separated and characterized by ESI-MS, UV/vis, and (1)H and (13)C NMR spectroscopy. The structures of these bisadducts were assigned based on (1) comparison of their molecular symmetries with their (1)H and (13)C NMR spectra, (2) comparison of their UV/vis spectra with those of corresponding Bingel-Hirsch bisadducts, and (3) the order of deshielding of the methylene and N-methyl (1)H NMR resonances. Prato bisaddition is less chemoselective than Bingel-Hirsch bisaddition to C(60). 相似文献
60.
New Ternary Phosphides and Arsenides of Cesium and Element of the 8th Transition Metal Group In the ternary systems Cesium/8th transition metal group/5th main group some new compounds were found and investigated. By single crystal measurements CsRh2P2 was found to crystallize in the space group 14/mmm with the lattice constants a = 390.11 pm and c = 1429.36 pm. The new compounds with the formula CsM2X2 (M = Fe, Co, Ru, Rh, Ir; X = P or As) crystallize in the ThCr2Si2-type structure, compounds of the formula Cs2MX2 (M = Ni, Pd, Pt; X = P or As) can be placed in a line with the K2PdP2-type structure. 相似文献