半连续乳液聚合动力学模型

介绍半连续乳液聚合动力学模型的研究进展及建模方法，归结出３种形式模型，基础模型，具体模型与通用模型，指出通常从一些假定出发，根据质量平衡，能量平衡反应机理建立模型方程，通过模型参数估计，已有模型参数的利用及模型变量的求取，使用数值方法求解模型。     

新烟碱类化合物药效构象的分子对接研究

从烟碱型乙酰胆碱受体(nACHR)-烟碱(nicotine)复合体晶体模型出发, 采用SYBYL 6.92软件包中FlexX分子对接模块对新烟碱类化合物的3种已上市化合物吡虫啉、噻虫啉、烯啶虫胺和3种吡虫啉的结构衍生物同受体蛋白作用的精确模型进行了研究. 通过全局搜索方法构建配体的构象库进行对接, 依据构象间RMS值对结果进行分类结合CScore打分函数数据对对接结果进行筛选, 最终给出合理的新烟碱类化合物-烟碱型乙酰胆碱受体的药效作用构象模型: 配体吡啶环上氮原子通过水分子同受体Leu102, Met114形成氢键并且咪唑环或噻唑环上亲水侧链同受体CYS187或SER186形成氢键, 疏水侧链同疏水部位A (TYR164, TRP53, TYR89以及TYR185残基), 或疏水部位B (TYR132, CYS187和CYS188)相互作用. 此模型同早先有关文献报道的试验结果部分吻合, 充分表明了其合理性. 同时依据本构象模型, 在新烟碱类化合物结构方面提出了一些改良建议并为研究其高选择性指出方向.     

The combined statistical and kinetic modeling of gel/sol partition in free-radical copolymerization of vinyl/divinyl monomers

A general model of the gel/sol partition in the free-radical copolymerization of vinyl/divinyl monomers was developed, combining the statistical and kinetic modeling. It is emphasized that properties of the primary chains born at some conversion are effected by their partner primary chains. It was concluded that the present model had overcome some shortcomings in Flory's and Tobita's model and facilitated taking the influence of kinetics into account, and was shown to be rather general for the free-radical copolymerization of vinyl/divinyl monomers. © 1996 John Wiley & Sons, Inc.     

Structure of the virus capsid protein VP1 of enterovirus 71 predicted by some homology modeling and molecular docking studies

The homology modeling technique has been used to construct the structure of enterovirus 71 (EV 71) capsid protein VP1. The protein is consisted of 297 amino acid residues and treated as the target. The amino acid sequence identity between the target protein and sequences of template proteins 1EAH, 1PIV, and 1D4M searched from NCBI protein BLAST and WorkBench protein tools were 38, 37, and 36%, respectively. Based on these template structures, the protein model was constructed by using the InsightII/Homology program. The protein model was briefly refined by energy minimization and molecular dynamics (MD) simulation steps. The protein model was validated using some web available servers such as ERRAT, PROCHECK, PROVE, and PROSA2003. However, an inconsistency between the docking scores and the measured activity was observed for a series of EV 71 VP1 inhibitors synthesized by Shia et al. (J Med Chem 2002, 45, 1644) and docked into the binding pocket of the protein model using the DOCK 4.0.2 program. The protein model with an EV 71 VP1 inhibitor docked and engulfed was then refined further by some MD simulation steps in the presence of water molecules. The docking scores obtained for these inhibitors after such a MD refinement were well correlated with the activities. The structure-activity relationships for the ligand-protein model system was also analyzed using the GRID-VOLSURF programs and the corresponding noncrossvalidated and crossvalidated (by leave-one-out) r2 and q2 were 0.99 and 0.61, respectively. The hydrophobic nature of the binding pocket of the protein model was also examined using the GRID21 program. The possibility of improving the potency of the current series of EV 71 VP1 inhibitors was discussed based on all the studies presented.     

正癸烷着火及燃烧的化学动力学模型

构建了一个包含46组分和167反应的描述正癸烷着火与燃烧过程的化学反应动力学机理模型, 该机理是在通过路径分析和灵敏度分析对Peters 机理(118组分和527反应)进行较大程度简化的基础上, 对低温着火和火焰传播速度影响较大的部分基元反应进行修正和改进后得到的. 与文献给出的实验结果对比表明, 该机理不仅比现有的机理具有较少的组分数和基元反应数, 而且能够更准确地预测正癸烷低温和高温条件下的着火延迟时间和火焰传播速度. 该机理为进一步实现总包简化机理与计算流体力学(CFD)的耦合计算奠定了基础.     

Simple model for the instabilities in the aggregation of silica sols in a sol-gel process

A simple kinetic model based on the Prigogine's Brusselator model was used to explain some unstable non-linear oscillations found in the particle size profile of sols in a sol-gel process. These oscillations were explained, in some previous papers, by using the stability criterion from the non-linear irreversible thermodynamics; it is the excess entropy production that characterizes the stability of a system and the occurrence of new structures. In the solgel reaction considered here, one of the steps is auto-catalytic; this fact produces local gradients in the concentration of one of the chemical components, forming a wide variety of new unstable structures. With this model we obtained a relationship for the reaction constants that determines the unstable character of the reaction, and the dependence of the frequency of oscillations on the reactant concentrations. The dependence of the oscillation frequency on water and ethanol concentrations obtained from the experimental data, were well explained by using this model.     

Thermal stabilities of some benzaldehyde 2,4-dinitrophenylhydrazones

The thermal stability of some benzaldehyde 2,4-dinitrophenylhydrazones has been studied using DSC technique. The crystalline solids are thermally stable and start to decompose after melting. Non-isothermal DSC curves, recorded at several heating rates, were used to evaluate the melting properties and the kinetics of thermal decomposition. Both isoconversional and model fitting methods were used for the evaluation of the kinetic parameters. Based on the results of the model free method, a kinetic model was derived and the kinetic parameters were obtained by means of a multivariate non-linear regression. A good agreement between the experimental and fitted data was found.     

Modeling of the conformational behavior of polyvinylchloride

The conformational behavior of polyvinylchloride was modeled by calculations of different conformers, rotational barriers, and rotation-energy profile diagrams of some model compounds, such as 1,3-dichloropropane, 1,3,5-trichloropentane, 1,3,5,7-tetrachloroheptane, 2,4-dichloropentane and 2,4,6-trichloropentane using the PCILO-and MM2-methods. These calculations allow some assertions about the conformational behavior of PVC. It was found that already a simple increment system derived from the model molecules is able to describe the conformational behavior of the larger molecules in question. There is a qualitative agreement of PCILO- and MM2-results in respect of the energetic order of the calculated conformers.     

Use of Capillary Electrophoresis in the Study of Interaction between dsDNA and Drug Molecules

The advantages of berberine such as the anticancer1, antiinflammatory2 and no side effects of camptothecin1, have promoted the research in the mechanism of berberine with macrobiomolecules. In general, three different points of view have been presented on…     

Molecular entity vacancy model

A novel molecular entity vacancy model was proposed to describe thermodynamic properties in a multicomponent solution system using its binary interaction parameters only. A derivation of the model for its general expression has been shown in detail. Under some special conditions, this model may be reduced to Flory–Huggins equation, Wilson equation and non-random two liquids (NRTL) equation as well as molecular interaction volume model (MIVM), respectively, and can be verified by Gibbs–Duhem equation, and can express thermodynamic properties of partially miscible systems. The predicted activities are in good agreement with experimental data of some liquid alloys. The results show that the model is of better predictability and reliability because it has a certain physical basis.     

Study of the mechanism of the photoisomerization and photooxidation of bilirubin using a model for the phototherapy of hyperbilirubinemia

Liquid chromatography was employed for a study of photochemical degradation of bilirubin in the complex with human albumin, using a model system in the presence of riboflavin. The concentrations of bilirubin, the photoisomers and biliverdin were monitored. The reaction mechanism was verified using a quantified mathematical model and was represented by a reaction scheme. Photoisomerization is the initial process, followed by photooxidation to degradation products of the tetrapyrrole skeleton, with formation of biliverdin as an intermediate. The blood of newborns that were irradiated for treatment of hyperbilirubinemia was studied for the sake of comparison. The effect of some biochemically important substances was followed, in view of possible inhibition of the processes. The experimental results demonstrate that riboflavin acts as a catalyst, even at the concentrations typical for its occurrence in blood. The results are discussed from the point of view of the mechanism of bilirubin degradation during phototherapy.     

Note on calculations by hypervirial relations and sufficient conditions for these relations: Box potential and harmonic oscillator models

The calculations by the diagonal and the off-diagonal hypervirial relations and by the sufficient conditions for these relations have been performed for the one-dimensional box potential and the harmonic oscillator models. In the case of the box potential model, the variation method gave the unsymmetrical wave functions for trial functions though it gave the best energies, but some of these hypervirial calculations gave the symmetrical functions and therefore they showed the exact expectation values of x, though they did not give the best energies. On the contrary, in the case of the harmonic oscillator model such a discrepancy for wave function and excitation energy did not happen. For the box potential model the expectation values of some operators were evaluated and compared with the results by the exact solution and the variation method. A weakness of the off-diagonal hypervirial calculation was pointed out and the removal of this weakness was tried. The effectiveness of these calculations were investigated.     

磺酰脲类除草剂的三维药效团模型

磺酰脲类除草剂是七十年代末期[1，2]开发的一类超高效除草剂，杀草谱广，用量极低．它通过抑制植物体内乙酰乳酸合成酶（ALS，acetolactatesynthase）的活性[3]，破坏支链氨基酸缬氨酸、亮氨酸和异亮氨酸的合成，造成杂草的死亡．本文从三维角度出发，利用先进的三维分子设计软件APEX（ActivityPredictionExpertSystem）－3D[4]，建立破酸豚类除草剂药效团模型（biophoremodel），辅助设计、筛选活性化合物；再由药效团构造出模拟ALS酶活性位点（activesites）的空间结构，以该模拟结构为基点，以期设计出全新结构的ALS酶抑制剂的…     

Evaluation of a mathematical model using experimental data and artificial neural network for prediction of gas separation

In recent times, membranes have found wide applications in gas separation processes. As most of the industrial membrane separation units use hollow fiber modules, having a proper model for simulating this type of membrane module is very useful in achieving guidelines for design and characterization of membrane separation units. In this study, a model based on Coker, Freeman, and Fleming＇s study was used for estimating the required membrane area. This model could simulate a multicomponent gas mixture separation by solving the governing differential mass balance equations with numerical methods. Results of the model were validated using some binary and multicomponent experimental data from the literature. Also, the artificial neural network （ANN） technique was applied to predict membrane gas separation behavior and the results of the ANN simulation were compared with the simulation results of the model and the experimental data. Good consistency between these results shows that ANN method can be successfully used for prediction of the separation behavior after suitable training of the network     

A kinetic study of synthesis of amoxicillin using penicillin G acylase immobilized on agarose

We presenta kinetic model for the synthesis of amoxicillin from p-hydroxyphenylglycine methyl ester and 6-aminopenicillanic acid, catalyzed by penicillin G acylase immobilized on agarose, at 25°C. Michaelis-Menten kinetic parameters (with and without inhibition) were obtained from initial velocity data (pH 7.5 and 6.5). Amoxicillin synthesis reactions were used to validate the kinetic model after checking mass transport effects. A reasonable representation of this system was achieved under some operational conditions, but the model failed under others. Nevertheless, it will be useful whenever a simplified model is required, e.g., in model-based control algorithms for the enzymatic reactor.     

Modal dynamics of proteins in water

We studied a dynamical model for the motion of the large scales of proteins in water. The model was obtained by projecting the (averaged) Newton equations onto some set of harmonic modes. We compared the statistics of the so‐obtained trajectories with those obtained by standard techniques, and concluded that our dynamical model is able to fairly reproduce the average properties of the large‐scale motion of the protein, and at the same time allow time steps one order of magnitude larger than the standard ones. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 1274–1282, 2000     

解读纳滤:一种具有纳米尺度效应的分子分离操作

纳滤膜是20世纪80年代末期发展起来的一种广泛用于液体分离的新型分离膜。早期研究中,先后提出的基于筛分效应的细孔模型,基于静电效应的电荷模型,以及同时考虑上述两种效应的静电位阻模型和道南位阻模型等为人们更好地理解纳滤膜分离机理和指导纳滤膜过程应用发挥了十分重要的作用。然而由于这些具有“疏松型反渗透膜”特点的纳滤膜没有相应的膜性能预测评价软件,使得针对具体应用过程的纳滤膜的大规模标准化应用受到了一定的制约。为此,结合上述模型,根据一些特定实验拟合确定混合盐体系同号离子间的竞争作用和异号离子间的调节作用,提出了一个适于混合盐体系的纳滤膜分离性能评价模型,促进了纳滤膜技术在水处理过程的大规模推广。最近,根据纳滤膜对离子选择性分离性能及其伴随的动电性质的细致而深入的实验研究,发现仅考虑筛分效应和静电效应并不能完全合理地解释纳滤膜的分离性能,且在动电性质的解析上也存在一定缺陷,进而对纳滤膜纳米级孔径引起的特殊效应和溶液体系中复杂相互作用引起的荷电性质变化有了更为深刻的认识和理解,提出并定量分析了离子透过纳滤膜时存在的介电排斥效应。     

The bending recovery of polymer films. I. A phenomenological model

When a flat film is bent to some fixed curvature, held at this state for some time, and then released, its curvature is usually observed to drop instantaneously to some finite value and then gradually decrease with time. This phenomenon, generally referred to as bending recovery, has been modeled by simple extension of the classical plate-bending theory to linear-viscoelastic materials. The model assumes that the relaxation spectra in tension and compression are dissimilar but are interrelated through a simple temporal shift. Experimental data, including instantaneous recovery at ambient and elevated temperatures as well as recovery over extended times, have been generated for four films with widely different relaxation characteristics. The data are in reasonable agreement with predictions of the model if a constant value of the compressive shift parameter (see text) is used for all materials. The model indicates that the bending recovery of a polymer film is intimately related to its relaxation spectrum and can be effectively manipulated by changes in temperature and winding time.