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971.
Two methods are proposed, one for the location of saddle points and one for the calculation of steepest-descent paths on multidimensional surfaces. Both methods are based on a constrained simplex optimization technique that avoids the evaluation of gradients or second derivative matrices. Three chemical reactions of increasing structural complexity are studied within the PRDDO SCF approximation. Predicted properties of reaction hypersurfaces are in good overall agreement with those determined by gradient minimization and gradient following algorithms in connection with various ab initio SCF methods. Computational efforts required by the new procedures are discussed. 相似文献
972.
《Electroanalysis》2005,17(9):749-754
A sensitive electrochemical method for the determination of simvastatin (SV) was established, based on the enhanced oxidation of SV at a multi‐walled carbon nanotubes‐dihexadecyl hydrogen phosphate composite modified glassy carbon electrode (MWNTs‐DHP/GCE). The voltammetric studies showed that MWNTs instead of DHP or GCE could effectively catalyze the oxidation of SV. The dependence of oxidation current on SV concentration was explored under optimal conditions, which exhibited a good linear relationship in the range of 1.0×10?7–7.5×10?6 M. The detection limit of SV was also examined and a low value of 5.0×10?8 M was obtained for 5 min accumulation (σ=3). This electrode was applied to the detection of SV in drug forms and the results were in accordance with those obtained by UV spectroscopy. 相似文献
973.
MITIC Snezana ZIVANOVIC Valentina OBRADOVIC Mirjana TOSIC Snezana PAVLOVIC Aleksandra 《中国化学》2007,25(4):531-534
The kinetic method for the determination of phosphate microamounts was described. The developed method is based on catalytic effect of phosphate on sodium pyrogallol-5-sulphonate (PS) by dissolved oxygen. The reaction was followed spectrophotometrically by measuring the rate of change in the values of the absorbance of the oxidation product at 437 nm. The optimum reaction conditions are PS (0.44×10^-3 mol·L^-1) and HClO4 (3.6×10^-6 mol·L^-1) at 25 ℃. Following this procedure, phosphate can be determined with a linear calibration graph up to 0.23 μg·mL^-1. The interference effect of several species was also investigated and it was found that the most common cations and anions did not interfere with the determination. The developed procedure was successfully applied to the determination of phosphate in natural waters and soil. 相似文献
974.
Toxicity to algae is important characteristic of substances from ecologic point of view. The CORAL software (http://www.insilico.eu/coral) gives possibility to build up model of toxicity to algae using data on the molecular architecture and experimental toxicity, without additional data on physicochemical and/or biochemical parameters. Considerable improvement of the model is observed in the case of using the index of ideality of correlation (IIC) in the role of additional criterion of predictive potential. The IIC is calculated with using of the correlation coefficient between experimental and calculated values of endpoint for the calibration set, with taking into account the positive and negative dispersions between experimental and calculated values. The best model calculated with use the IIC is characterized (the validation set) by n?=?50, r2?=?0.947, RMSE?=?0.401 whereas, model calculated without use the IIC is characterized by n?=?50, r2?=?0.805, and RMSE?=?0.539. The suggested models are built up in accordance to five OECD principles. 相似文献
975.
Ab initio UMP2 and UQCISD(T) calculations, with 6-311G** basis sets, were performed for the titled reactions. The results show that
the reactions have two product channels: NH2+ HNCO?NH3+NCO (1) and NH2+HNCO?N2H3+CO (2), where reaction (1) is a hydrogen abstraction reaction via an H-bonded complex (HBC), lowering the energy by 32.48
kJ/mol relative to reactants. The calculated QCISD(T)//MP2(full) energy barrier is 29.04 kJ/mol, which is in excellent accordance
with the experimental value of 29.09 kJ/mol. In the range of reaction temperature 2300–2700 K, transition theory rate constant
for reaction (1) is 1.68×1011–3.29×1011 mL·mol-1·s-1, which is close to the experimental one of 5.0×1011mL·mol-1·s-1or less. However, reaction (2) is a stepwise reaction proceeding via two orientation modes,cis andtrans, and the energy barriers for the rate-control step at our best calculations are 92.79 kJ/mol (forcis-mode) and 147.43 kJ/mol (fortrans-mode), respectively, which is much higher than reaction (1). So reaction (1) is the main channel for the titled reaction. 相似文献
976.
四唑及其衍生物的理论研究Ⅷ: 硝氨四唑衍生物的从头算 总被引:3,自引:0,他引:3
运用从头计算法,在HF/6-31G^*水平下,全优化计算了7种硝氨四唑衍生物的分子几何和电子结构。结果表明,标题物的四唑环近似为平面构型;2H式中性分子的芳香性大于相应的1H式异构体。5-硝氨-1H四唑分子内氢键使硝氨基与环共面;其余标题物中硝氨基与环垂直。不同水平下的总能量计算表明,标题物中电子相关效应显著;1H式中性分子较2H式的能量高,5-硝氨四唑负离子在三个负离子中最稳定。根据电荷分布阐明了四唑环质子化位置和标题物与金属的配位方式。此外还计算了各标题物的红外光谱及热力学性质。 相似文献
977.
以乙醇为溶剂, 钛酸四丁酯为前驱体, 用溶剂热法制备了Ag表面修饰的负载型纳米二氧化钛光催化剂. 利用X射线衍射(XRD)、N2吸附-脱附(BET)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)、紫外-可见(UV-Vis)光谱等技术对其进行了系统的表征, 以亚甲基蓝(MB)溶液的脱色降解为模型反应, 考察了不同Ag含量样品的光催化性能. 结果表明: 用溶剂热法制备的样品中TiO2皆为锐钛矿相, 金属Ag颗粒沉积在TiO2表面, 粒径为2 nm左右, 比表面积较溶胶凝胶法制备的样品大大增加, 最高可达151.44 m2·g-1; UV-Vis光谱和光催化实验表明: Ag修饰使TiO2对光的吸收能力大大增强, 吸收带边红移至可见光区, 亚甲基蓝在该复合材料上的光催化降解反应遵循一级反应动力学模型; 溶剂热法制备样品的光催化性能明显好于溶胶凝胶法制备的样品, 在紫外光和可见光下, Ag摩尔分数为5%的样品表现出最佳的光催化活性. 相似文献
978.
The homotopic method has been used to analyze the kinetic model of three-stageCO oxidation on two nonuniform surface patches conjugated byCO
2 spillover. Diagrams of steady states depending on the portion of surface patchm
1 at various temperatures and pressure ratiosP(O
2)/P(CO) have been constructed. The ratios of different type patches corresponding to the maximum overall reaction rate have been found. 相似文献
979.
Thereza Christina Vessoni Penna Eb Chiarini Adalberto Pessoa Junior 《Applied biochemistry and biotechnology》2003,107(1-3):481-491
Transformed cells of Escherichia coli expressing recombinant green fluorescent protein (GFPuv) were subjected to two methods of extraction: (1) freezing/thawing/sonication
(FTS) cycles prior to the three-phase partitioning (TPP) method, or (2) directly to TPP extraction. The amount of GFPuv released
by the FTS plus TPP method varied: 374μg/mL (first cycle), 93–442 μg/mL (second cycle), 32–359 μg/mL (third cycle), 18–115
μg/mL (fourth cycle). The GFPuv yields by the second method (TPP only) were, 23–54 μg/mL for the first extract and 33–91 μg/mL
for the second. The FTS plus TPP method released similar amounts of GFPuv to that extracted by TPP; and provided a better
mixture elution through the hydrophobic interaction column: 13–63 μg/mL for FTS plus TPP methods, and 2.5–13 μg/mL for TPP.
The results showed that although selective permeation is a more laborious methodology, it was more efficient for obtaining
of GFPuv in relation to the direct extraction of the cells for TPP. 相似文献
980.
Kanibolotsky D. S. Bieloborodova O. A. Kotova N. V. Lisnyak V. V. 《Journal of Thermal Analysis and Calorimetry》2003,71(2):583-591
The enthalpies of mixing of liquid binary Fe-Ge (1765±5 K) and Fe-Si (1750±5 K) alloys were determined using a high-temperature
isoperibolic calorimeter. The thermodynamic properties of Fe-Ge melts were also studied by electromotive force method in the
temperature range of 1250-1580 K. The comparison of our measurement results with literature data has been performed. The extreme
negative values of integral enthalpy of mixing and alternating-sign deviations from Raoult's low for germanium can be explained
by the influence of binary clusters formation.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献