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991.
The configuration-controlled regime and the diffusion-controlled regime of conformation-modulated fluorescence emission are systematically studied for Markovian and non-Markovian dynamics of the reaction coordinate. A path integral simulation is used to model fluorescence quenching processes on a semiflexible chain. First-order inhomogeneous cumulant expansion in the configuration-controlled regime defines a lower bound for the survival probability, while the Wilemski-Fixman approximation in the diffusion-controlled regime defines an upper bound. Inclusion of the experimental time window of the fluorescence measurement adds another dimension to the two kinetic regimes and provides a unified perspective for theoretical analysis and experimental investigation. We derive a rigorous generalization of the Wilemski-Fixman approximation [G. Wilemski and M. Fixman, J. Chem. Phys. 60, 866 (1974)] and recover the 1/D expansion of the average lifetime derived by Weiss [G. H. Weiss, J. Chem. Phys. 80, 2880 (1984)].  相似文献   
992.
A model based on binary-like collisions is presented to describe the vibrational relaxation of diatomic molecules in a monatomic medium. For N2Ar and COAr, it is shown that the oscillatory motion of host atoms undergoing multiquantrum processes is most important in removing vibrational energy. The translational motion of molecules confined to the cell space also contributes to the energy relaxation by removing the energy mismatch.  相似文献   
993.
The study of rare earth coordination catalysts for polymerization of 1-octene has been successfully carried out for the first time. Some features and kinetic behavior of polymerization of 1-octene by Nd(naph)3–AIEt3 catalyst system in tetrachloro-methane are described. The overall polymerization activation energy Ea measured was 74.5 kJ/mol and the rate equation could be expressed as Rp = kp [Nd] [M] (kp = 3.21 × 10?3 L/mol s, at 50°C). The catalytic activity of various rare earth elements in Ln (naph)3 and ligands in NdL3 for the polymerization was compared. A 1-octene oligomer with double bonds was obtained. It is either a white or pale yellow waxy semi-solid. Its number-average molecular weight is about 103 and the molecular weight distribution is less than 2.  相似文献   
994.
利用水热合成技术成功制备出一种新型多钒硼氧化合物, 用X射线单晶衍射分析技术对其晶体结构和分子结构进行了确定。结果表明在该化合物中多钒硼氧阴离子具有一个新颖的三明治结构。上下两个结构单元都是由六个VO5四角锥交替地通过顺式和反式共边的方式连接起来构成的一个钒氧三角形结构。中间的结构单元是由BO3平面三角形和BO4四面体以共角的方式相互连接形成的一个折叠型的B18O36(OH)6环。三明治结构中层与层之间通过桥氧相连。一个水分子处于它的核心位置上,与每个VO5四角锥中的钒原子都保持几乎相等的距离。该化合物及其晶体中存在着丰富的化学结构和成键信息,同时也有作为氧化还原反应催化剂的潜能。  相似文献   
995.
We have investigated the frequency-dependent interfacial electrical properties of nanocrystalline diamond films that were covalently linked to DNA oligonucleotides and how these properties are changed upon exposure to complementary and noncomplementary DNA oligonucleotides. Frequency-dependent electrical measurements at the open-circuit potential show significant changes in impedance at frequencies of >10(4) Hz when DNA-modified diamond films are exposed to complementary DNA, with only minimal changes when exposed to noncomplementary DNA molecules. Measurements as a function of potential show that at 10(5) Hz, the impedance is dominated by the space-charge region of the diamond film. DNA molecules hybridizing at the interface induce a field effect in the diamond space-charge layer, altering the impedance of the diamond film. By identifying a range of impedances where the impedance is dominated by the diamond space-charge layer, we show that it possible to directly observe DNA hybridization, in real time and without additional labels, via simple measurement of the interfacial impedance.  相似文献   
996.
Tunable VUV laser was used to initiate the ion-molecule reactions in the clusters of ethanol and 1-propanol by photoionization in the region between 10.49 to 10.08 eV. Ionic products were detected by the time-of-flight mass spectrometer. In addition to the protonated clusters from proton transfer reactions, the products corresponding to beta carbon-carbon bond cleavage were found to be one of the major products for small sizes of clusters. A comparison with photoionization of methanol clusters and the results of ab initio calculation has been made.  相似文献   
997.
The electronic singlet vertical excited states of photosynthetic reaction center (PSRC) in Rhodopseudomonas (Rps.) viridis were investigated by ZINDO and INDO/S methods. The effects of the interactions of pigment-pigment and pigment-protein on the electronic excitations were examined. The calculation results showed that the interactions of pigment-pigment and pigment-protein play an important role in reasonably assigning the experimental absorption and circular dichroism (CD) spectra of PSRC in Rps. virids. By comparing the theoretically computed excited states with the experimental absorption and CD spectra, satisfactory assignments of the experimental spectroscopic peaks were achieved.  相似文献   
998.
EDTA—Cu配合物用于还原糖的测定   总被引:2,自引:0,他引:2  
首次报道了应用EDTA(乙二胺四乙酸二钠盐)-铜配合物(EC)测定还原糖的分光光度法,结果表明,pH4~11时EC的最大吸收波长为732nm,在HCO-3CO2-3缓冲介质中,配合物EC的吸光度与还原糖在077~161mg(六碳糖)范围内有很好的线性关系,相关系数大于0998,样品测定回收率在95%~105%之间。该法试剂易得、性质稳定,操作方便,灵敏度较高,取样量少于5mL。  相似文献   
999.
合成了稀土铕、镧与吡啶-2,6二甲酸形成的二元配合物及铕与邻菲罗啉和吡啶-2,6二甲酸形成的三元配合物。经元素分析确定该配合物的组成分别为二元:Na3[Eu(DPC)3]·2H2O,Na3[La(DPC)3]·2H2O;三元:NaEu(DPC)2·phen·4H2O。用核磁共振研究了配体与稀土的配位方式,讨论了诱导效应、屏蔽效应及稀土离子的顺磁性对配合物化学位移和NMR谱图的影响。NMR研究表明,三种配合物具有相似的对称结构和相同的化学位移变化规律。吡啶-2,6二甲酸中的羧酸以单齿配位(整个分子为三齿配位),二元配合物中,铕和镧的配位数均为9,三元配合物中,铕的配位数最低为8。  相似文献   
1000.
曹阳  赵波  左涛 《物理化学学报》1996,12(7):594-597
计算了一系列肉桂酸(苯基丙烯酸)类化合物的二阶非线性光学系数,系统地研究了取代基的电子性质和取代位置对其非线性光学性质的影响,并且探讨了该类化合物的饱和取代效应.研究表明,该类化合物的非线性光学性质与其分子结构有着密切的关系.  相似文献   
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