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991.
Keith E. Johnson Richard M. Pagni John Bartmess 《Monatshefte für Chemie / Chemical Monthly》2007,138(11):1077-1101
Summary. A background for studying acids in various solvents is developed, emphasizing the importance of knowing to what extent a solvent
conducts electricity and is therefore ionized, the dissociation equilibria of common molecular solvents and the acidic and
basic species generated by solvent leveling. Acidity measurements in the atypical solvent water are discussed and the common
method of expressing acidity in other systems – by Hammett values – is introduced. Representative examples of reactions involving Br?nsted acids in ionic liquids are presented and attention paid to the questions of speciation and acidity values. It is found that
the gas phase proton affinity of a base is often a better guide to the acidity of its conjugate acid in an ionic liquid than
is the dissociation constant of the said acid in water. 相似文献
992.
How does huperzine A enter and leave the binding gorge of acetylcholinesterase? Steered molecular dynamics simulations 总被引:9,自引:0,他引:9
Xu Y Shen J Luo X Silman I Sussman JL Chen K Jiang H 《Journal of the American Chemical Society》2003,125(37):11340-11349
The entering and leaving processes of Huperzine A (HupA) binding with the long active-site gorge of Torpedo californica acetylcholinesterase (TcAChE) have been investigated by using steered molecular dynamics simulations. The analysis of the force required along the pathway shows that it is easier for HupA to bind to the active site of AChE than to disassociate from it, which for the first time interprets at the atomic level the previous experimental result that unbinding process of HupA is much slower than its binding process to AChE. The direct hydrogen bonds, water bridges, and hydrophobic interactions were analyzed during two steered molecular dynamics (SMD) simulations. Break of the direct hydrogen bond needs a great pulling force. The steric hindrance of bottleneck might be the most important factor to produce the maximal rupture force for HupA to leave the binding site but it has a little effect on the binding process of HupA with AChE. Residue Asp72 forms a lot of water bridges with HupA leaving and entering the AChE binding gorge, acting as a clamp to take out HupA from or put HupA into the active site. The flip of the peptide bond between Gly117 and Gly118 has been detected during both the conventional MD and SMD simulations. The simulation results indicate that this flip phenomenon could be an intrinsic property of AChE and the Gly117-Gly118 peptide bond in both HupA bound and unbound AChE structures tends to adopt the native enzyme structure. At last, in a vacuum the rupture force is increased up to 1500 pN while in water solution the greatest rupture force is about 800 pN, which means water molecules in the binding gorge act as lubricant to facilitate HupA entering or leaving the binding gorge. 相似文献
993.
Xian Zhao Daren Guan Xizhang Yi Guibao Xu Minhua Jiang 《International journal of quantum chemistry》2003,93(5):335-343
A dynamic Lie algebraic (DLA) formulation is applied to the study of nonlinear optical properties of the substituted benzenes. We have described the generation of the dynamic Lie algebra for the model Hamiltonian used in the present study. In terms of these elements of the dynamic algebra we express the evolution operator as a function of the group parameters, which can be determined by means of solving a system of coupled nonlinear differential equations. Thus, in terms of the density matrix operator formalism in statistical mechanics we obtain the statistical averages of the electric polarization and then derive readily an expression for the hyperpolarizability of the paradisubstituted benzenes. Comparisons with experimental observations and other quantum calculations of the hyperpolarizabilities for the paradisubstituted benzenes are made qualitatively and quantitatively. These results imply that the DLA method appears useful in describing the nonlinear optical phenomena in the substituted benzene molecules. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 93: 335–343, 2003 相似文献
994.
The synthesis and anion binding properties of new ruthenium(II) and cobalt(II) phenanthroline complexes, containing two amide
subunits are described. Evidence for anion binding in dimethyl sulfoxide (DMSO) solution was obtained from u.v.–vis titration
experiments. Results indicated that these receptors showed strong affinity for F− and AcO−, and showed weak affinity for OH− and H2PO
4
−
, and showed no affinity for Cl−, Br−, I−. These receptors interacted with various anions examined through hydrogen-bond formation. 相似文献
995.
M. Blaauw I. H. Degenaar J. J. M. de Goeij 《Journal of Radioanalytical and Nuclear Chemistry》2007,271(3):765-770
In order to correct for neutron self-shielding in large-sample prompt gamma NAA, a method has been developed to determine
the macroscopic scattering and absorption cross sections, i.e., Σ
a and Σ
s, using four Cu flux monitors placed around the sample. With Monte Carlo computations, the neutron densities throughout the
sample and the resulting and the corresponding self-shielding factor as calculated from the Σ
a and Σ
s as obtained through the Cu monitors were compared to the true values. The derived Σ
a and Σ
s were found to be sufficiently accurate as long as Σ
t = Σ
a + Σ
s was less than 0.6 cm−1 and Σ
s/Σ
t was greater than 0.1. 相似文献
996.
水中痕量镉的准液膜富集 总被引:4,自引:0,他引:4
准液膜法是在液膜法基础上提出的新分离方法,它保持了液膜法分离富集的高效能,但省去了液膜法的制乳与破乳过程,使操作更为简便易行。本文用此法富集了水及废水中痕量镉,富集倍数可达230倍,镉的回收率在97%以上。 相似文献
997.
Determination of DNA using sodium 9,10-anthraquinone-2-sulfonate as an in situ photochemical fluorescence probe 总被引:2,自引:0,他引:2
Wen-You Li Xiang-Qun Guo Jin-Gou Xu Qing-Zhi Zhu Yi-Bing Zhao 《Analytica chimica acta》1997,340(1-3):291-296
An in situ photochemical fluorescence probe method for the determination of DNA with sodium 9,10-anthraquinone-2-sulfonate (AQS) as a photochemical fluorescence probe was developed. It was based on the conversion of AQS into an intensively fluorescent product by irradiating with UV radiation. The photochemical reaction is retarded by DNA. The determination can be carried out by measuring the fluorescence intensity at a fixed time. The calibration graph was linear in the range 0–80 ng ml−1 calf thymus (CT) DNA (r = 0.9991), the limit of detection was 3.2 ng ml−1 CT DNA (n = 9). The kinetic behaviour of the photochemical reaction and the effects of experimental conditions were investigated and discussed in detail. The results of absorption spectra and competitive binding experiments suggested the interaction between AQS and DNA to be intercalative. 相似文献
998.
Jingqi Guan ShuBo Jing Shujie Wu Haiyan Xu Zhenlv Wang Qiubin Kan 《Reaction Kinetics and Catalysis Letters》2007,90(1):27-33
A series of MoV0.3Tex (x = 0−0.3) mixed oxides were prepared and investigated for the selective oxidation of isobutane. Among them, MoV0.3Te0.23 showed the best methacrolein and methacrylic acid selectivity (as high as 17% and 16%, respectively), and the yield to methacrolein
and methacrylic acid reached 3.6% and 3.5%, respectively, at 21.3% isobutane conversion at 440°C. 相似文献
999.
Based on a recently developed quantum dissipation formulation [R. X. Xu and Y. J. Yan, J. Chem. Phys. 116, 9196 (2002)], we present a reduced Liouville-space approach to evaluate the response and correlation functions of dissipative systems. The weak system-bath interaction is treated properly for its effects on the initial state, the evolution, and the correlation between coherent driving and non-Markovian dissipation. Numerical demonstration shows this correlated effect cannot be neglected even in the calculation of linear response quantities that do not explicitly depend on external fields. Highlighted in this paper is also the proper choice of theory among various formulations in the weak system-bath interaction regime. 相似文献
1000.
“Simple” energetic patterns, where simple means the use of parameters derived only from the stoichiometry of these species,
are relatively rarely discussed in the literature. In addition, entropy studies have been dominated by derivation of the absolute
quantity S° rather than the entropy of formation (TΔf
S
o). Relationships between the entropy of formation and different parameters such as negative value of the charge of the species,
the number of oxygen atoms, the natural logarithm of the molecular weight, the total number of atoms and the number of central
atoms that are gases were recently discussed by us for aqueous polynuclear oxyanions. As shown here hydrogen containing anions
do not follow this pattern. In this study, new approaches for the estimation of the entropy of formation of aqueous hydrogen
containing mono and polynuclear oxyanions are suggested, evaluated and recommended. 相似文献