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911.
采用大功率高重复频率准分子激光溅射热解石墨靶制备了类金刚石碳膜, 研究了实验条件对类金刚石膜光学性能的影响, 发现氢可以提高膜中sp3键的含量和膜的光学透过率. 在实验参数范围内, 膜的光学性能随着氢压的增加而提高. 根据类金刚石膜的反应沉积机理对上述结果进行了分析、解释. 相似文献
912.
An atom‐economic Pd0‐catalyzed synthesis of a series of pinacol‐type indolylboronates 3 from the corresponding bromoindole substrates 2 and pinacolborane (pinBH) as borylating agent was elaborated. The optimal catalyst system consisted of a 1 : 2 mixture of [Pd(OAc)2] and the ortho‐substituted biphenylphosphine ligand L‐3 (Scheme 4, Table). Our synthetic protocol was applied to the fast, preparative‐scale synthesis of 1‐substituted indolylboronates 3a – h in the presence of different functional groups, and at a catalyst load of only 1 mol‐% of Pd. 相似文献
913.
In an effort to develop an efficient synthetic method of highly diastereoselective (2′R)- and (2′S)-2′-deoxy[2′-2H]guanosines, chemoenzymatic conversion was investigated. The synthesis of (2′R > 98% de)-2′-deoxy[2′-2H]guanosine was achieved by biological transdeoxyribosylation using (2′R > 98% de)-2′-deoxy[2′-2H]uridine, 2,6-diaminopurine, and Enterobacter aerogenes AJ-11125, followed by treatment with adenosine deaminase. (2′S > 98% de)-2′-Deoxy[2′-2H]guanosine was synthesized from (2′S > 98% de)-2′-deoxy[2′-2H]uridine and 2,6-diaminopurine using thymidine phosphorylase and purine nucleoside phosphorylase instead of E. aerogenes AJ-11125. 相似文献
914.
Density functional theory (DFT) calculations are used to study the strength of the CH…O H‐bond in the proton transfer reaction of glycine. Comparison has been made between four proton transfer reactions (ZW1, ZW2, ZW3, SCRFZW) in glycine. The structural parameters of the zwitterionic, transition, and neutral states of glycine are strongly perturbed when the proton transfer takes place. It has been found that the interaction of water molecule at the side chain of glycine is high in the transition state, whereas it is low in the zwitterionic and neutral states. This strongest multiple hydrogen bond interaction in the transition state reduces the barrier for the proton transfer reaction. The natural bond orbital analysis have also been carried out for the ZW2 reaction path, it has been concluded that the amount of charge transfer between the neighboring atoms will decide the strength of H‐bond. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 相似文献
915.
在氨水介质中及加热条件下,痕量铜(Ⅱ)对H2O2氧化天青Ⅱ的褪色反应具有强烈的催化作用.探讨了最佳实验条件,据此建立了催化动力学光度法测定痕量铜(Ⅱ)的新方法.在选定的实验条件下,非催化反应与催化反应的吸光度差值△A与铜(Ⅱ)离子的质量浓度在16~56 μg/L范围内有良好的线性关系,检出限为9.36×10-11 g/mL.并且测定了催化反应的动力学参数,反应为准一级反应.在75℃下的表观速率常数为K'=4.04×10-3 8-1,表观活化能为74.54 kJ/mol.方法用于人发中痕量铜(Ⅱ)的测定,回收率在99.7%~100.0%之间. 相似文献
916.
The title compound [NdK(btec)(H2O)2]n 1 was synthesized via the hydrothermal reaction of Zn(OAc)2·H2O, Nd(NO3)3 and KOH with 1,2,4,5-benzenetetra-carboxylic acid (H4btec), and characterized by elemental analysis and infrared spectra.The crystal of 1 crystallizes in monoclinic, space group P21/c with a = 8.9023(3), b = 7.8954(1), c = 17.6249(5)A, β = 91.857(1)o, V = 1238.16(6) -3, Z = 4, C10H6KNdO10, Mr = 469.49, Dc = 2.519 g/cm3, F(000) = 900 and μ(MoKα) = 4.585 mm-1.The final R = 0.0404 and wR = 0.0832 for 2197 observed reflections with I > 2σ(I) and R = 0.0431 and wR = 0.0854 for all data.X-ray diffraction reveals that the btec ligand serves as a (16-bridging ligand to link the Nd(III) and K(I) atoms into a three-dimensional coordination polymer.Photoluminescent investigation shows that the title compound displays strong emission in the blue region, which may be attributed to an intraligand emission state. 相似文献
917.
918.
W. Zielenkiewicz I. V. Terekhova A. Marcinowicz M. Koźbial J. Poznanski 《Journal of Thermal Analysis and Calorimetry》2008,93(2):365-372
Interactions of native and modified α- and β-cyclodextrins with nicotinic acid, pyridoxine and pyridoxal were studied by isothermal
titration calorimetry, solution calorimetry, and 1H NMR spectroscopy at 298.15 K and pH 6.8. Weak 1:1 complex formation was found only between α-cyclodextrin and nicotinic
acid. The stability constant and corresponding thermodynamic parameters of complex formation (Δc
G, Δc
H and Δc
S) were calculated using the calorimetric data. The 1H NMR data indicate the shallow insertion of the carboxylic group of the nicotinic acid molecule into α-CD cavity. For all
other compounds the weak interactions, not accompanied by complex formation, were characterized by the enthalpic virial coefficients
calculated on the basis of McMillan-Mayer approach. The obtained thermodynamic parameters were analyzed in the terms of influence
of the solutes’ structure on the selectivity of intermolecular host-guest interactions. 相似文献
919.
A study of the vibrational behavior of five saturated monoacid triacylglycerides is performed by Raman spectroscopy at various temperatures in two separate spectral ranges: 1780–1700 and 3100–2650 cm−1. The samples are studied in polycrystalline phase at room temperature, in isotropic liquid phase, and in polycrystalline phase after cooling from the isotropic liquid phase. The CO stretching mode of these triglycerides changes significantly according to the temperature: we observe three components, or an unresolved doublet, or a resolved doublet. The I(2845)/I(2880) ratios (in the C–H stretching spectral region) of the different saturated monoacid triglycerides vary also according to the temperature. The study of these two indicators (the CO stretching mode and the I(2845)/I(2880) ratio) has permitted us to determine the polymorphic forms of the studied triglycerides. 相似文献
920.
用密度泛函UB3LYP/6-311++G**方法计算研究了气相中CrO2+ (2A1/4A")活化甲烷C—H键的微观机理, 找到了四条反应通道. 对其中涉及的两态反应(TSR)进行了分析, 并对影响反应机理和反应速率的势能面交叉现象(potential energy surfaces crossing)进行了详细讨论, 进而运用Hammond假设和Yoshizawa等的内禀坐标单点垂直激发计算的方法找出了一系列势能面交叉点[crossing points (CPs)], 并作了相应的讨论. 进一步用碎片分子轨道理论[fragment molecular orbital (FMO)]对TS1中的轨道相互作用进行了分析, 解释了CrO2+活化甲烷C—H键的机理. 相似文献