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71.
Ning Li Chunhui Deng Ning Yao Xizhong Shen Xiangmin Zhang 《Analytica chimica acta》2005,540(2):317-323
In the study, we developed a simple, rapid, sensitive, and inexpensive method for determination of the disease biomarkers of acetone, hexanal and heptanal in human blood. For the first time, derivatization of carbonyls with O-2,3,4,5,6-(pentafluorobenzyl)hydroxylamine (PFBHA) was combined with headspace single-drop microextractin (HS-SDME) and gas chromatography-mass spectrometry (GC–MS) and applied to the analysis of acetone, hexanal, and heptanal in human blood. At first, acetone, hexanal and heptanal in blood were derivatized with PFBHA and formed oximes in several seconds. Sequentially, the oximes were headspace extracted and concentrated by a microdrop solvent. Finally, the extracted oximes were analyzed by GC–MS. HS-SDME conditions and method validations were studied. Due to needing of only 2 μl organic solvent, short extraction time of 8 min, and simple operation, derivatization-HS-SDME was shown to be a rapid, simple, and inexpensive technique for analysis of acetone, hexanal, and heptanal in human blood. Moreover, it had low detection limit values from 0.24 to 0.62 nM, and good reproducibility (R.S.D. less than 12%). 相似文献
72.
73.
The first implementation of the intrinsic reaction coordinate (IRC ) method within the density functional theory (DFT ) framework is presented. The implementation has been applied to four different types of chemical reactions represented by the isomerization process, HCN ? HNC (A); the SN2 process, H? + CH4 ? CH4 + H? (B); the exchange process, H˙ + HX ? HX + H˙ (X ? F,Cl) (C); and the elimination process, C2H5Cl ? C2H4 + HCl (D). The present study presents for each process optimized structures and calculated harmonic vibrational frequencies for the reactant(s), the transition state, and the product(s) along with the IRC path connecting the stationary points. The calculations were carried out within the local density approximation (LDA ) as well as the LDA/NL scheme where the LDA energy expression is augmented by Perdew's and Becke's nonlocal (NL ) corrections. The LDA and LDA/NL results are compared with each other as well as the best available ab initio calculations and experimental data. For reaction (D), ab initio calculations based on MP 2 geometries and MP 4SDTQ energies have been added due to the lack of accurate published post-HF calculations on this process. A detailed discussion is provided on the efficiency of the IRC algorithms, the relative accuracy of the DFT and ab initio schemes, as well as the reaction mechanisms of the four reactions. It is concluded that the LDA/NL scheme affords the same accuracy as does the MP 4 method. The post-HF methods seem to overestimate activation energies, whereas the corresponding LDA/NL estimates are too low. The LDA activation energies are even lower than the LDA/NL counterparts. The incorporation of the IRC method into the DFT framework provides a promising and reliable tool for probing the chemical reaction path on the potential energy surfaces, even for large-size systems. IRC calculations by ab initio methods of an accuracy similar to the LDA/NL scheme, such as the MP 4 scheme, are not feasible. © John Wiley & Sons, Inc. 相似文献
74.
75.
Using ClO2 as chemiluminescence (CL) oxidant, a novel homogeneous CL system in neutral and near neutral aqueous solution is proposed in this paper. ClO2 could oxidize sulfite in pH 5.0–8.5 acetate buffer to produce CL emission, and pipemidic acid could sensitize the CL system. The ClO2–SO32−–pipemidic acid reaction was used as a model CL system and explored the possibility of highly active and eco-friendly ClO2 being used as CL oxidant in neutral and near neutral aqueous solution. Combined with flow-injection analysis, the proposed CL system was applied to the automated dissolution testing of pipemidic acid tablet. Compared with the common strong acidic or strong basic CL system, this proposed CL owns its advantages. 相似文献
76.
Song C Wang D Gu G Lin Y Yang J Chen L Fu X Hu Z 《Journal of colloid and interface science》2004,272(2):340-344
Silver-coated poly(methyl acrylic acid) (PSA) core-shell colloid particles were prepared by an in situ chemical reduction method. Crystalline silver/titania composite hollow spheres were obtained by coating the as-prepared PSA/silver particles with an amorphous titania layer and subsequently calcining in Ar atmosphere. SEM and TEM investigation indicated that the size of the as-prepared PSA/silver and PSA/silver/TiO(2) core-shell particles and silver/titania composite hollow particles was fairly uniform and the wall thickness of the hollow spheres was in the range of 40-80 nm. UV-vis absorption spectra were recorded to investigate their optical properties. 相似文献
77.
A piezoelectric response model on the population growth of microorganism is proposed. This model is based on a novel population growth model, which has a more obvious ecological meaning and the fact that the series piezoelectric quartz crystal (SPQC) sensor responses to conductivity changes of the medium during the growth of the microorganism. From the response model four parameters can be obtained including the maximum specific growth rate mu(m), saturated population size N(m), and two constants C and K(1). The influence of the parameters on the response curve is discussed in which the influences of mu(m) and N(m) are more obvious. With the proposed model the quantitative determination of bacteria may be more accurate than the frequency detection time (FDT) method. Then the growth of Escherichia coliform (E. coli) monitored with a SPQC sensor is compared with the simulated growth curve obtained by the proposed model and a good agreement is obtained. 相似文献
78.
A novel photothermal phase-shift spectroscopy configuration based on the retro-reflected beam interference has been developed and its operational principle is described. The weak absorption measurement ability of this technique is experimentally proven with a water/ethanol solution of standard Pyronine G dye and the limit of detection is found to be 1.8 x 10(-6) absorbance. Potential applications of the technique are discussed. 相似文献
79.
对新型的代铬刷镀层Ni-Fe-W-P-S进行了耐腐蚀性能机理的分析研究。用扫描电镜(SEM)、透射电镜(TEM)、扫描隧道显微镜(STM)、X射线衍射及电子能谱(XPS)等的分析表明,基体组织为非品结构是代铬刷镀层优异耐腐蚀性的主要原因. 相似文献
80.
Ch. V. Subba Reddy Y. Y. Qi W. Jin Q. Y. Zhu Z. R. Deng W. Chen Sun-il Mho 《Journal of Solid State Electrochemistry》2007,11(9):1239-1243
Molybdenum trioxide (MoO3) xerogel films modified with poly(vinyl alcohol)+poly(vinyl pyrrolidone) (PVP+PVA) polyblends were obtained by ion-exchange
method with sol-gel technique. Investigations were conducted using X-ray “diffractometry”, Fourier transform infrared spectroscopy,
and cyclic voltammetry. The results show that the H atoms in polyblend are H-bonded with the O atoms in the Mo=O bonds of
MoO3 xerogel, which effectively shield the electrostatic interaction between MoO3 interlayer and Li+ ions when MoO3 xerogel is modified by the intercalation of (PVP+PVA). The reversibility of the insertion/extraction of Li+ ions is greatly improved by the modification with polyblend of MoO3 nanocomposite films. MoO3 and (PVP+PVA)
x
MoO3 (x = 0, 0.5) nanobelts were obtained by a simple hydrothermal process from MoO3 sol. The electrochemical cells with configuration Li/(LiPF6+EC+DMC)/MoO3 modified by (PVP+PVA) were fabricated and their discharge profiles studied. 相似文献