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81.
82.
提出了控制电位电解和恒电流电解两类电解沉积的压电频移分析法测定的理论公式,用实验结果验证了它的正确性. 相似文献
83.
Preparation, 19F NMR Spectroscopic Evidence and Study of the Formation of Metal-Mixed Cluster Anions [(Mo6?nWnCl )F ]2?, n = 0?6 The complete system of metal-mixed octahedral cluster ions [(Mo6?nWnCl)F]2?, n = 0?6, is prepared by tempering Mo powder with WCl6 at 600°C. A mixture containing inclusively the geometric isomers (n = 2, 3, 4) all ten possible species is transferred into the tetra-n-butylammonium salts (TBA)2[(Mo6?nWnCl)F]. In the 19F nmr spectrum the 24 expected signals are observed, assigned on the basis of their chemical shifts, multiplicities and intensities, and confirmed by a 2D-19F-19F COSY spectrum. From the integrated intensities the distribution of the different components is derived revealing a non-statistical formation, in that isomers with Mo…?Mo or W…?W atoms in trans-positions in comparision to those with mixed Mo…?W axes are favoured, and that especially the homoleptic compounds Mo6 and W6 are present to an over-average extent. Evaluation of 19F chemical shifts reveals that F bound to W which is in antipodal position to Mo resonates at higher field compared to F bound to W in a W…?W arrangement, caused by an increased shielding, which is synonymous to a positive antipodal-effect by Mo. Vice versa F bound to Mo with an antipodal W resonates at lower field compared with F bound to Mo in an Mo…?Mo arrangement caused by an increased deshielding and synonymous a negative antipodal-effect by W. The chemical shifts, resulting from antipodal-effects, are different for the compounds within the [(Mo6?nWnCl)F]2? - system. The difference of the antipodal effect of successive substitution products results in characteristic values designated as antipodal shift constants, depending on the kind of substituents, which is valid for other cluster systems, too. 相似文献
84.
Mikhail I. Kodess Marina A. Ezhikova Galina L. Levit Victor P. Krasnov Valery N. Charushin 《Journal of organometallic chemistry》2005,690(11):2766-2768
Experimental conditions for determination of enantiomeric composition of 1-substituted 3-aminocarboranes by 1H and 13C NMR spectroscopy using chiral shift reagent Eu(hfc)3 have been found. 相似文献
85.
Time shift correction in second-order liquid chromatographic data with iterative target transformation factor analysis 总被引:4,自引:0,他引:4
Enric Comas R. Ana Gimeno Joan Ferr Rosa M. Marc Francesc Borrull F. Xavier Rius 《Analytica chimica acta》2002,470(2):607-173
When the generalized rank annihilation method (GRAM) is applied to liquid chromatographic data with diode-array detection, an important problem is the time shift of the peak of the analyte in the test sample. This problem leads to erroneous predictions. This time shift can be corrected if a time window is selected so that the chromatographic profile of the analyte in the test sample is trilinear with the peak of the analyte in the calibration sample. In this paper we present a new method to determine when this condition is met. This method is based on the curve resolution with iterative target transformation factor analysis (ITTFA). The calibration and test matrices are independently decomposed into profiles and spectra, and aligned before GRAM is applied. Here we study two situations: first, when the calibration matrix has one analyte and second, when it has two analytes. When the calibration matrix has two analytes, we selectively determine the time window for the analyte to be quantified. There were considerably fewer prediction errors after correction. 相似文献
86.
The present paper employed density function theory to investigate two reaction pathways for isomerization of enol ester proposed by Yang(path a) and the present authors(path a), respectively. The base catalytic effects of solvent triethylamine on these two reactions were also evaluated. It is demonstrated that path B is more preferable than path a due to low barrier height for the rate-determining step. 相似文献
87.
Viana FA Pouliquen YB Andrade-Neto M Santiago GM Pessoa OD Rodrigues-Filho E Braz-Filho R 《Magnetic resonance in chemistry : MRC》2004,42(8):695-699
A detailed NMR study and full assignments of the 1H and 13C spectral data for two novel triterpenoid saponins isolated from the stem bark of Pentaclethra macroloba (Willd.) Kuntze are described. Their structures were established using a combination of 1D and 2D NMR techniques including 1H,1H-COSY, TOCSY, NOESY, gs-HMQC and gs-HMBC, and also electrospray ionization mass spectrometry and chemical methods. The structures were established as 3beta-O-([O-beta-D-glucopyranosyl-(1-->2)-O-beta-D-glucopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->3)-O-alpha-L-rhamnopyranosyl-(1-->2)]-[O-beta-D-glucopyranosyl-(1-->3)-O-beta-D-glucopyranosyl-(1-->4)])-alpha-L-arabinopyranosylhederagenin (1) and 3beta-O-)[O-beta-D-glucopyranosyl-(1-->2)-O-beta-D-glucopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->3)-O-alpha-L-rhamnopyranosyl-(1-->2)]-[O-beta-D-glucopyranosyl-(1-->3)-O-beta-D-glucopyranosyl-(1-->4)])-alpha-L-arabinopyranosyloleanolic acid (2). 相似文献
88.
The influence of Stokes shift in optosensing was discussed. Then, the current status of large Stokes shift-based optosensing was reviewed here. 相似文献
89.
运用核磁共振手段,揭示了浆体中水的形态及其动态行为,并研究浆体性质与之的关联.实验测得神府煤-石油焦-水浆(CPCWS)中水质子的化学位移与煤焦中煤的百分含量的线性关系.并从NMR测得束缚水的化学位移δb ,导出计算浆体中束缚水百分含量的公式.从CPCWS中水质子的化学位移与浆体表观粘度的相关曲线可确定最佳配比的浆体.测得全焦浆中水质子自旋-晶格驰豫时间T1比全煤浆大42倍,讨论了CPCWS的T1随煤含量的变化趋势.实验表明,T1可作为CPCWS中碳质点的疏水或亲水性以及水分子形态和动态行为的定量表征. 相似文献
90.
本文综述了近年来不对称Diels-Alder反应中手性催化剂研究的进展,对各类手性催化剂的性能和特点作了简要介绍. 相似文献