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991.
用从头算对丙烯和甲苯2个超共轭体系进行计算,结果表明甲基上氢原子参与超共轭时,其碳氢键键长增大,氢上集居数减少,丙烯、甲苯的甲基旋转势垒为7.61及0.096 kJ/mol.超共轭基作用相当于一带有孤对电子参与共轭之杂原子,超共轭体系不同构型稳定性可用M=sum from i=1 to 3(sinθ_i[sin(θ_i-α)+sinα])来表征。 相似文献
992.
993.
A method has been described for the direct determinations of trace cadmium using derivative atom trapping flame atomic absorption spectrometry with an improved water-cooled stainless steel trapping equipment. The characteristic concentration (gave a derivative absorbance of 0.0044) and detection limit (3sigma) of cadmium were 0.028 and 0.02 ng ml(-1) when collecting for a 1 min, respectively, which were 992 and 145-fold better than those of the conventional flame atomic absorption spectrometry. The detection limit and sensitivity of the proposed method for a 2 min collection time were 1 and 2 orders of magnitude higher than those of conventional flame atomic absorption spectrometry. The present method was applied to the determinations of cadmium in water samples with a recovery range of 91 approximately 111% and a relative standard deviation of 4.7 approximately 5.6%. 相似文献
994.
J C Zhu C H Li Y Liu Z H Zhang A X Hou S S Qu 《Journal of Thermal Analysis and Calorimetry》2006,83(1):181-186
After the occurrence of 'Minamata disease' in 1950,
mercury aroused much more attention, and lots of studies concerned have been
made. The purpose of the present paper is to study the effect of mercuric
chloride on the mitochondria suspension isolated from the liver tissue of Cyprinus carpio from the direct viewpoint of energy
by using the microcalorimetric method. The metabolic thermogenic curves of
the mitochondria suspension at 25°C were obtained, and the mitochondria
metabolic thermokinetic equations were established, from which we obtained
the thermodynamic and thermokinetic parameters: thermogenic rate constant
(k), heat output (Q),
average heat power (Pav),
etc. Experimental results indicated that low concentration of mercuric chloride
(5 nmol Hg2+/(mg protein)) stimulates the thermogenesis
of mitochondria, suggesting a strong effect of uncoupling action, while high
concentration of mercuric chloride (20 nmol Hg2+/(mg
protein)) inhibits the metabolism of mitochondria completely, suggesting a
fatal effect on the phosphorylation system. The effect of Hg2+
on mitochondria is concentration-depended, from which the probable reaction
mechanism of Hg2+ to the mitochondria was proposed.
So the microcalorimetric method can be used in the toxicology research. 相似文献
995.
A sol-gel chemistry-based polymer coating approach was developed for the preparation of a novel polysiloxane-coated silica stationary phase for capillary liquid chromatography. SE-30, a commercial polysiloxane stationary phase used in gas chromatography, was incorporated into the properly designed sol solution. Then the sol-gel mixture was introduced into a silica gel-packed capillary column by pressure. A thin film of sol-gel SE-30-coating is chemically bonded to the surface of silica gel particles by hydrolytic polycondensation under mild conditions without any free radical cross-linking procedures, therefore the sol-gel approach offers a simple and effective pathway to create a hybrid polymer-coated silica stationary phase. Various factors affecting column making were optimized and discussed in this report. The resulting stationary phase showed good permeability, mechanical robustness, high durability to alkaline mobile phase and satisfactory chromatographic performance in separations of polar and non-polar aromatic compounds. Linear solvation energy relationships (LSERs) studies indicate that the stationary phase has a reversed-phased character with SE-30 providing chromatographic functionality. The solute size and the solute hydrogen bond ability are major factors that principally govern the retention of test solutes. 相似文献
996.
Three-dimensional time-dependent quantum wave packet calculation for the O((1)D)+HBr reaction has been carried out using an accurate ab initio global potential energy surface [K. A. Peterson, J. Chem. Phys. 113, 4598 (2000)]. The calculations show that the initial state-selected reaction probabilities are dominated by resonance structures, and the lifetime of the resonance is generally in the subpicosecond time scale. The energy dependence of the reaction cross section is computed, which manifests still resonance structures, and is a decreasing function of the translational energy. The thermal rate constants are also computed, which are nearly independent on the temperature. The calculation results are discussed and compared to similar reaction with deep well. 相似文献
997.
Direct determination of brucine by square wave voltammetry on 4-amino-2-mercaptopyrimidine self-assembled monolayer gold electrode 总被引:1,自引:0,他引:1
4-Amino-2-mercaptopyrimidine self-assembled monolayer (AMP SAMs/Au) was prepared on a gold electrode. The AMP SAMs/Au was characterized by using attenuated total reflection-fourier transform infrared (ATR-FTIR) and A.C. Impedance. The electrochemical behavior of brucine on AMP SAMs/Au was studied by cyclic voltammetry (CV) and square wave adsorptive stripping voltammetry (SWASV). The modified electrode showed an excellent electrocatalytic activity for the redox of brucine. The catalytic current increased linearly with the concentration of brucine in the range of 4.0 x 10(-7) to 2.0 x 10(-4) mol l(-1) by square wave voltammetry response. The detection limit was 6.0 x 10(-8) mol l(-1). 相似文献
998.
Kai Yang Xuan Zhang Enqin Fu Jingui Qin Minoru Kinoshita 《Journal of solid state chemistry》2004,177(11):4300-4304
Two new intercalation compounds were prepared by the reactions of Ni(II) cyclopolyamine complex cations with a preintercalate Mn1−xPS3K2x(H2O)y, respectively, through “ion exchange” process. Their structures were characterized by elemental analysis, X-ray powder diffraction and infrared spectroscopy. The lattice spacing increased 0.567 and 1.093 nm with respect to the pristine MnPS3. Ferrimagnetism of the intercalates was confirmed by SQUID experiment with Tc at 40 and 33 K, respectively. 相似文献
999.
Chitosan samples were irradiated by 60Co γ-rays in the presence of hydrogen peroxide with radiation dose from 10 kGy to 100 kGy. The degradation was monitored by gel permeation chromatography (GPC), revealing the existence of a synergetic effect on the degradation. Structures of the degraded products were characterized with Fourier-transform infrared spectra (FT-IR), ultraviolet-visible spectral (UV-vis) analysis, and X-ray diffraction (XRD). Results showed that the crystallinity of chitosan decreases with degradation, and the crystalline state of water-soluble chitosan is entirely different from that of water-insoluble chitosan. An elemental analysis method was employed to investigate changes in the element content of chitosan after degradation. Mechanism of chitosan radiation degradation with and without hydrogen peroxide was also discussed. 相似文献
1000.
Yu P Lin Y Xiang L Su L Zhang J Mao L 《Langmuir : the ACS journal of surfaces and colloids》2005,21(20):9000-9006
This letter describes the formation and possible electrochemical applications of molecular films of water-miscible imidazolium-based ionic liquids (ILs) on glassy carbon (GC) electrodes. X-ray photoelectron spectroscopy (XPS) and electrochemical results indicate that the water-miscible ILs used in this study can interact with the GC electrode and form molecular films on the electrode surface. The formed molecular films are found to possess striking electrochemical properties such as electrocatalysis toward ascorbic acid (AA) and the capability to facilitate direct electron transfer of horseradish peroxidase (HRP). This demonstration would pave the way for new electrochemical applications of water-miscible ILs and is envisaged to be useful for the investigation of the electrochemical properties of water-miscible ILs in aqueous media provided the same counteranion is used as the supporting electrolyte. 相似文献