微孔中简单流体粘度的分子动力学模拟及关联模型

用分子动力学模拟计算了微孔介质中流体氩在不同温度、不同密度和不同孔径下的剪切粘度.并根据Chapman-Enskog关于硬球流体传递性质的理论以及Heyes的关于Lennard-Jones流体粘度的表达式,提出了两个描述微孔介质中流体粘度的模型,该模型可以计算微孔中流体氩在不同状态下的粘度值.通过与计算机模拟值的比较,证明这两个微孔流体粘度模型是可用的.     

Optimization of the abnormal Beckmann rearrangement: application to steroid 17-oximes

A novel and practical procedure was developed for the abnormal Beckmann rearrangement of steroid 17-oximes. Treatment of the 17-oximes with TFA/CH(OMe)(3) in boiling THF for 2 h gives the corresponding 13,17-seco alkene nitrile products in unprecedented high yields (70-92%). Since the alkene nitriles can be subsequently converted into 18-norsteroids, this general method provides a highly efficient route to these biologically important compounds and, by extension, to other structurally related natural products.     

Effects of Self—coiling of Organic Molecules on Intramolecular Exciplex Formation and Fluoresscence Quenching in DX—H2O Solvent System

Effects of self-coiling of organic molecules on intramolecular exciplex formation of compound I,in which the carbazole chromophore and terephthalic acid methylester acceptor group are linked by one (CH2)10 chain,and the decrease of the fluorescence intensities of compounds Ⅱ，Ⅲ，and Ⅳ,in which the carbazole chromophore and 3,5-dinitrobenzoate are connected by one aliphatic chain of (CH2)10 (Ⅱ），（CH2）12（Ⅲ）,or (CH2)4(Ⅳ）,have been studied in the dioxane (DX)-H2O binary system.The results show that self-coiling of organic molecules in DX-H2O facilitates intramolecular exciplex formation of I and induces the decrease of fluorescence intensities of Ⅱ,bacause of the proximity effect brought about by selfcoiling of organic molecules under hydrophobic-lipophilic interaction(HLI) between the excited carbazole chromophore and the acceptor.Since the similar effects are observed even when the concentration of the probes are less than their CAgCs(critical aggregate concentrations )in the DX-H2O mixture with the same φ values,formation of the intermolecular exciplex has been excluded.The effects are found to be strongly depended on φ values,indication that they are mainly driven by HLI.The properties of the acceptors can also affect the intramolecular exciplex formation.With terephthalic acid methylester moiety as the acceptor,the carbazole chromophore exhibits the fluorescence spectra of the exciplex,while with 3,5-dinitrobenzoate moiety as the acceptor,only the fluorescence spectra of excited carbazolyl chromophore are observed.     

Oxidative homolysis of organochromium(III) macrocyclic complexes

Summary Organochromium complexes, [CrRL(H₂O)]²⁺] (L = 1,4,8,12-tetraazacyclopentadecane; R = 1°- or 2°-alkyl, or para-substituted benzyl), are oxidized to [CrRL(H₂O)]³⁺, which rapidly decomposes (k ₃ > 10² s^–1) by homolysis of the Cr-C bond. Rate constants of the oxidation of these complexes by [IrCl₆]^2– range from 2.20 × 10^–1 (R = Me) to 4.60 × 10⁵ (R = 4-MeC₆H₄CH₂)dm³ mol^–1 s^–1. A very negative reaction constant (–4.3) is found for the oxidation of para-substituted benzlchromium(III) complexes which, in conjunction with the results of product analysis, indicates a [Cr^III/R^.] type transition state.     

Fluorescent ratioable recognition of Cu in water using a pyrene-attached macrocycle/γ-cyclodextrin complex

A pyrene-functional fluoroionophore, 1 was used to construct a supramolecular 1/γ-CD complex for Cu²⁺ recognition in water. In aqueous γ-CD solution, 1 exhibits pyrene monomer fluorescence emission at 378 nm and 397 nm, while in the presence of Cu²⁺, it shows a pyrene excimer emission at 452 nm with a decrease in the monomer fluorescence due to the formation of a 1:2 metal-liganded complex. Based on the response characteristics of the supramolecular complex, a fluorescent ratiometric method was performed for the determination of Cu²⁺ concentration in water. With the optimum conditions described, Cu²⁺ in aqueous solution can be determined from 1.2 × 10⁻⁶ to 4.5 × 10⁻⁴ M. The Cu²⁺ selectivity of the complex is excellent, and the excimer fluorescence enhancements are very smaller induced by other heavy metal and transition metal ions.     

Electrostatic recognition and induced fit in the kappa-PVIIA toxin binding to Shaker potassium channel

Brownian dynamics (BD) and molecular dynamics (MD) simulations and electrostatic calculations were performed to study the binding process of kappa-PVIIA to the Shaker potassium channel and the structure of the resulting complex. BD simulations, guided by electrostatic interactions, led to an initial alignment between the toxin and the channel protein. MD simulations were then carried out to allow for rearrangements from this initial structure. After approximately 4 ns, a critical "induced fit" process was observed to last for approximately 2 ns. In this process, the interface was reorganized, and side chains were moved so that favorable atomic contacts were formed or strengthened, while unfavorable contacts were eliminated. The final complex structure was stabilized through electrostatic interactions with the positively charged side chain of Lys7 of kappa-PVIIA deeply inserted into the channel pore and other hydrogen bonds and by hydrophobic interactions involving Phe9 and Phe23 of the toxin. The validity of the predicted structure for the complex was assessed by calculating the effects of mutating charged and polar residues of both the toxin and the channel protein, with the calculated effects correlating reasonably well with experimental data. The present study suggests a general binding mechanism, whereby proteins are pre-aligned in their diffusional encounter by long-range electrostatic attraction, and nanosecond-scale rearrangements within the initial complex then lead to a specifically bound complex.     

Investigation of the interaction between acridine orange and bovine serum albumin

The results from the measurement of the fluorescence spectrum showing the binding characteristics of acridine orange (AO) and bovine serum albumin (BSA) are reported. It was found that the equilibrium constant k=4848.64 l mol⁻¹, and the number of binding sites n=0.82. Based on the mechanism of the Forster energy transference, the transfer efficiency of energy and distance between the acceptor AO and BSA were found. The interaction between AO and BSA have been verified as consistent with the static quenching procedure and the quenching mechanism is related to the energy transfer.     

Semiempirical mo studies on the proton transfer equilibria of amides

Intramolecular proton transfer equilibria of acetamide and methyl carbamate have been studied by AMI MO calculations, and the results are compared with those of the MNDO method. It was found that the two semi- empirical methods predict essentially the same proton transfer mechanism, but MNDO tends to overestimate the activation barriers. Participation of one solvate vater in the proton transfer led to a considerable lovering of the activation barrier, by nearly the same amount, in both methods. One notable conflict between the two methods was that the methoxy-O-protonated form of methyl carbamate, in the gas phase, can be a local energy minimum with MNDO, whereas it leads to dissociation into two species Instead of an optimized structure with AM1. It was concluded that the MNDO method can be useful for this type of process, especially when one is interested in the relative activation barriers only.     

硫氰酸铈(Ⅲ)与三缩四乙二醇配合物[Ce(C_8H_(18)O_5)(NCS)_3(H_2O)]的合成及晶体结构

合成了硫氰酸铈(Ⅲ)与三缩四乙醇配合物[Ce(C_8H_(18)O_5)(NCS)_3(H_(2)O)].晶体结构分析表明,该配合物晶体属三斜晶系,P(?)空间群.晶胞参数:a=0.8816(3)nm,b=1.0465(2)nm,c=1.2490(2)nm,α=86.46(1)°,β=70.90(2)°,γ=66.37(2)°,ν=0.9943nm~(3),Z=2.D_(计算)=1.769cm~(3),最终偏差因子R=0.049.     

A MORPHOLOGICAL STUDY OF POLY（DIVINYLBENZENE-co-ACRYLIC ACID） IN CROSSLINKING PRECIPITATION POLYMERIZATION

Divinylbenzene-80 （DVB-80） and polar monomer acrylic acid （AA） having hydrogen bonding at a total monomer loading of 5 vol% were precipitated-copolymerized in a variety of organic solvents with 2,2＇-azobis（isobutyronitrile） （AIBN） as initiator. The experiments were investigated from a two-dimensional matrix, i.e., the actual crosslinking degree of DVB varying from 0 to 80% and the solvent composition varying from 0 to 100% of toluene mixture with acetonitrile, when the mixture of acetonitrile and toluene was used as the reaction solvent. Under various reaction conditions, six distinct morphologies including soluble polymers, swellable microgels, coagulum, irregular microparticles, and nano-/micrometer microspheres were formed and the structures of these polymer architectures were described. A morphological map was utilized to discuss the effects of both crosslinking degree of DVB and composition of solvent on the transitions between morphology domains. The results demonstrated that the microspheres are formed by an internal contraction due to the marginal solvency of the continuous phase and the crosslinking of the polymer network through the covalent bonding from DVB as well as the interchain hydrogen-bonding between the carboxylic acid units.