含硅聚合物中小分子扩散行为的分子模拟

选择PCFF和COMPASS分子力场对橡胶态聚合物PDMS 和玻璃态聚合物PS1体系进行模拟。COMPASS力场模拟得到的体系密度,O2和N2在PDMS与PS1中扩散系数更接近实验值。在模型大小一定时,Group-based求和法中截断距离越长,耗用机时越长,但对计算结果改进不大;截断距离为1.3 nm时计算结果最好。Ewald方法耗时多而对计算结果却无明显改进。体系大小对扩散系数的计算值影响甚微。体积越小的分子,在聚合物中运动的范围越大,扩散系数越大。氧气和氮气分子在PDMS与PS1中运动轨迹不同,在PS1中氧气运动范围远大于氮气,而在PDMS中氧气运动范围稍大于氮气。小分子运动轨迹基本与聚合物自由体积分布对应,自由体积分数大,扩散系数也大。     

改进的扩散自由体积模型及其在凝胶和固定化细胞中的应用(Ⅰ)模型的建立

利用扩散自由体积模型,通过一定的线性假定将凝胶及固定化细胞中的自由体积与各主要影响因素相联系,得到了能表达诸因素对有效扩散系数影响的改进的扩散自由体积模型.其特点是不仅能反映凝胶总单体浓度、交联度及扩散分子大小的影响,而且可以反映温度及细胞浓度对有效扩散系数的影响.     

改进的扩散自由体积模型及其在凝胶和固定化细胞中的应用(Ⅰ)模型的建立

利用扩散自由体积模型,通过一定的线性假定将凝胶及固定化细胞中的自由体积与各主要影响因素相联系,得到了能表达诸因素对有效扩散系数影响的改进的扩散自由体积模型.其特点是不仅能反映凝胶总单体浓度、交联度及扩散分子大小的影响,而且可以反映温度及细胞浓度对有效扩散系数的影响.     

CO2和O2在聚乳酸/聚偏二氟乙烯共混物中扩散行为的分子动力学模拟研究

采用分子动力学模拟方法研究了CO₂和O₂分子在聚乳酸/聚偏二氟乙烯（PLA/PVDF）共混物中的扩散行为;通过菲克第一定律和Einstein关系式计算了共混物体系模型的自由体积分数以及CO₂和O₂分子在体系中的扩散系数,研究探讨了自由体积分数与探头半径的关系及自由体积分数与扩散系数的关系。结果表明,当PLA/PVDF共混物中PLA和PVDF的质量比为9∶1时,CO₂和O₂气体分子的扩散系数均为最小,共混物阻隔性能最好;共混体系中小分子的动力学半径越小,扩散系数越大;自由体积分数随硬球探头模型中探头半径的增大而减小;不同共混物体系中,自由体积分数的变化趋势与扩散系数一致,与Fox和Flory的自由体积理论相符。     

页岩油在有机质孔隙赋存特征的分子模拟研究

利用分子动力学模拟方法研究了页岩油在页岩纳米有机质孔隙中的赋存特征。在OPLS全原子力场下模拟了353 K、30.7 MPa条件下正辛烷在石墨烯壁面的吸附特征,并分析了不同孔隙尺寸、温度、压力、碳链长度、烷烃极性等5个影响因素对正辛烷在有机质壁面吸附的影响。结果表明,正辛烷在有机质孔隙壁面有4个吸附层,吸附层密度峰值逐渐降低,吸附层厚度为0.4～0.5 nm;沿z方向垂直扩散系数和平行扩散系数均逐渐增大并在孔隙中央处达到稳定,且平行扩散系数大于垂直扩散系数;压力对烷烃分子的吸附量几乎没有影响,孔隙尺寸越大,温度越高,碳链越短,分子极性越低的烷烃分子在纳米有机质孔隙中的吸附态体积分数越小。     

用状态方程改进的高聚物中溶剂扩散系数预测模型

将Simha-Somcynsky状态方程引入Vrentas-Duda自由体积理论模型,提出改进的高聚物-溶剂体系扩散系数模型,计算常压下橡胶态高聚物中有机溶剂扩散系数对浓度和温度的依存关系.利用高聚物结构单元的范德华体积导出高聚物自由体积分数表达式,通过Simha-Somcynsky方程求取高聚物体积以及对溶剂分子扩散有效的自由体积,避免原模型中繁琐的高聚物粘弹性实验测定和回归高聚物自由体积参数,提高了自由体积理论的预测能力.使用改进的模型预测了苯、甲苯、乙苯和三氯甲烷在聚苯乙烯、聚异丁烯和聚醋酸乙烯酯中的自扩散系数和互扩散系数,计算结果表明改进的自由体积模型具有较高的预测精度.     

残留溶剂在PMMA-CA聚合物膜中迁移及影响的多尺度分析

杂质对功能高分子聚合物理化性质的影响具有重要的学术价值与应用意义。今分别通过分子动力学(Molecular Dynamics,MD)及密度泛函(Density Functional Theory,DFT)等方法探索了聚合物玻璃态和橡胶态下溶剂扩散系数的不同以及残留溶剂对聚合物分子解离能的影响。根据自由体积理论,对聚甲基丙烯酸甲酯-丙烯酰胺杯芳烃(PMMA-CA)的玻璃化温度进行了分子动力学(MD)模拟,得到的自由体积与温度的关系曲线显示其玻璃化温度为395K。考察了玻璃态和橡胶态下溶剂扩散系数的不同,MD模拟得到的均方位移(Mean Square Displacement,MSD)曲线显示,聚合物在玻璃态下溶剂的自扩散系数远低于橡胶态下。通过密度泛函方法计算残留溶剂分子对杯芳烃解离能的影响,结果表明膜制备过程中残留的溶剂分子有利于杯芳烃的解离,但其影响比MMA分子共聚要弱得多。     

分子印迹技术手性分离氨基酸衍生物(Ⅱ)—流动相对分子印迹聚合物手性拆分效果的影响

系统研究了乙腈流动相中甲醇、乙酸和水的体积分数变化对分子印迹聚合物手性拆分效果的影响。在流动相乙腈中添加较少量的甲醇或乙酸时〔φ(甲醇)≤8%,φ(乙酸)≤2%〕,随其体积分数的增加,手性分离效果提高;但当其体积分数继续增加,分离效果变差。以水作为添加物质时,当体积分数相对较少〔φ(H2O)≤30%〕,随其体积分数增加,手性分离效果变差;当水体积分数继续增加,拆分效果有所提高,在φ(H2O)=70%时,选择性因子达到1 52。降低流动相的pH值有利于手性拆分。利用梯度洗脱技术可以改善色谱分离中印迹分子洗脱峰的拖尾。     

薄膜扩散梯度系数的研究

薄膜扩散梯度技术是一种新型的原位采集并测量重金属有效态或生物可给性的方法。本实验研究的是不同pH对同种聚醚砜膜的扩散系数的影响以及重复使用次数对同一种聚醚砜膜扩散系数的影响。不同pH对膜扩散系数影响的研究可以看出这种聚醚砜膜的使用范围在pH=2~9,在强碱性条件下会严重影响膜的性能。同一张聚醚砜膜不同实验次数的研究说明此种聚醚砜膜的合理使用次数为1次,重复使用会影响它的扩散性能。     

NEPE推进剂中硝酸酯扩散的分子动力学模拟及实验研究

针对硝酸酯增塑聚醚(NEPE)推进剂中硝酸酯迁移扩散影响装药服役寿命的问题,采用分子动力学模拟与液相色谱实验相结合,开展硝酸酯(NG/BTTN)在NEPE推进剂中扩散机理及扩散系数的理论计算研究,并探讨了温度对NG和BTTN在NEPE推进剂中扩散行为的影响。结果表明,NG/PEG体系中NG分子的空间位置对初始位置的偏离程度相比于BTTN/PEG体系中BTTN分子较大,且BTTN分子在两个温度条件下的扩散系数均小于NG分子;实验计算的NG和BTTN在55℃和65℃下扩散系数的数量级与分子动力学模拟计算结果相同,通过模拟计算得到两种温度下NG分子在共混体系中的扩散系数分别为3.42×10-13 m2/s(65℃)和4.81×10-14 m2/s(55℃),BTTN分子在共混体系中的扩散系数分别为2.93×10-13 m2/s(65℃)和4.25×10-14 m2/s(55℃);随温度升高,硝酸酯分子的扩散系数增大,即迁移性增大,这与分子动力学模拟结果一致。     

Hindered diffusion of asphaltenes through microporous membranes

The relationship between the diffusion coefficient of asphaltenes and pore size was studied experimentally using track-etched mica membranes. The asphaltenes were extracted from Kuwait atmospheric bottoms using criteria of n-pentane insolubility and tetrahydrofuran solubility at 25°C. Data were obtained for asphaltene fractions of narrow size range by using gel permeation chromatography to analyze the diffusion samples. The results show a very strong pore size effect on diffusion coefficient in the range 70–500 Å pore radius for asphaltenes whose GPC-equivalent polystyrene molecular weight is 3000 or greater. By properly accounting for the molecular size of the asphaltene fractions, we are able to obtain good agreement between the measured diffusion coefficients and those predicted from a hydrodynamic theory of hindered diffusion.     

Inspiratory Deposition Efficiency of Ultrafine Particles in a Human Airway Bifurcation Model

The inspiratory deposition efficiency of ultrafine particles in a physiologically realistic bronchial airway bifurcation model, approximating the airway generation 3-4 juncture, was computed for different particle sizes, ranging from 1 to 500 nm, under three different flow conditions, representing resting to heavy exercise breathing conditions. For the smallest particle sizes, say between 1 and 10 nm, molecular diffusion is the primary deposition mechanism, as indicated by the inverse relationship with flow rate, except for the highest flow rate where the additional effect of convective diffusion has to be considered as well. For the larger particle sizes, say above 20 nm, the independence from particle size and dependence on flow rate suggests that convective diffusion plays the major role for ultrafine particle deposition in bifurcations. A semiempirical equation for the inspiratory deposition efficiency, m (D, Q), as a function of diffusion coefficient D and flow rate Q, due to the combined effect of molecular and convective diffusion was derived by fitting the numerical data. The very existence of a mixed term demonstrates that molecular and convective diffusion are not statistically independent from each other.     

3D DOSY-TROSY to determine the translational diffusion coefficient of large protein complexes

The translational diffusion coefficient is a sensitive parameter to probe conformational changes in proteins and protein-protein interactions. Pulsed-field gradient NMR spectroscopy allows one to measure the translational diffusion with high accuracy. Two-dimensional (2D) heteronuclear NMR spectroscopy combined with diffusion-ordered spectroscopy (DOSY) provides improved resolution and therefore selectivity when compared with a conventional 1D readout. Here, we show that a combination of selective isotope labelling, 2D 1H-13C methyl-TROSY (transverse relaxation-optimised spectroscopy) and DOSY allows one to study diffusion properties of large protein complexes. We propose that a 3D DOSY-heteronuclear multiple quantum coherence (HMQC) pulse sequence, that uses the TROSY effect of the HMQC sequence for 13C methyl-labelled proteins, is highly suitable for measuring the diffusion coefficient of large proteins. We used the 20 kDa co-chaperone p23 as model system to test this 3D DOSY-TROSY technique under various conditions. We determined the diffusion coefficient of p23 in viscous solutions, mimicking large complexes of up to 200 kDa. We found the experimental data to be in excellent agreement with theoretical predictions. To demonstrate the use for complex formation, we applied this technique to record the formation of a complex of p23 with the molecular chaperone Hsp90, which is around 200 kDa. We anticipate that 3D DOSY-TROSY will be a useful tool to study conformational changes in large protein complexes.     

The Effect of van der Waals and Viscous Forces on Aerosol Coagulation

An analysis is carried out to determine the combined effect of van der Waals and viscous fluid forces on coagulation of spherical aerosol particles in the free molecular, transition, and continuum regimes. The effect of viscous forces is taken into account by modifying the particle diffusion coefficient. An asymptotic solution is substituted for the classical formulation of viscous forces. The results of free molecular and continuum regimes are then extended to the transition size range by an interpolation formula.     

Solute diffusion in swollen membranes. IX. Scaling laws for solute diffusion in gels

A scaling law was developed for the diffusion coefficient of spheroidal and ellipsoidal solutes in nonporous, equilibrium-swollen hydrogels. The law relates the solute diffusion coefficient to the solute size, the gel mesh size, and the gel equilibrium volume degree of swelling. The law was verified by appropriate data of low and high molecular weight solute diffusion through hydrogels such as swollen networks of poly(vinyl alcohol), poly(2-hydroxyethyl methacrylate), cellulose, and others. An additional scaling law was developed which relates the rate of release of a small or large molecule from an equilibrium swollen hydrogel with time and with morphological characteristics of the polymeric network.     

Measurement of thermal diffusion parameters of polystyrene using a thermal field flow fractionation method

Thermal diffustor parameters such as the thermal diffusion factor and the thermal diffusion coefficient for polystyrene in toluene are measured by using a thermal field flow fractionation (TFFF) method The dependence of these parameters upon temperature concentration and polymer molecular weight is ex-amined. The thermal diffusion coefficien is found to be independent of the molecular weight for sufficiently large polymer molecules but on the other hand the ordinary diffusion coefficient is known to be pronouncedly dependent on the molecular weight. This result indicates that the fractionation effect is primarily governed by the differences in ordinary dif-fusion coefficients.     

凝固浴氨化对PAN湿法纺丝凝固行为的影响

在二甲基亚砜/水(DMSO/H_2O)凝固体系中加入氨水,以pH值控制凝固浴氨化程度,研究了凝固浴氨化对聚丙烯腈(PAN)湿法纺丝凝固行为的影响;采用扫描电子显微镜表征PAN初生纤维的皮层结构,采用卡尔费休水分仪和气相色谱仪研究了氨化对水和DMSO扩散系数的影响。结果表明:当凝固浴pH值为8.0时,PAN初生纤维的皮层最薄;随着凝固浴pH值的增大,水的扩散系数逐渐减小,DMSO的扩散系数(D_(DMSO))先减小后增大,当pH值为8.0时,D_(DMSO)出现最小值;氨化的作用机理是通过氨与水和DMSO分子间的氢键作用来实现的。     

Concentration-dependent molecular diffusion coefficient of gaseous ethane in liquid toluene

We report new experimental data on concentration-dependent molecular diffusion coefficient of ethane in toluene at temperatures ranging from 21 to 125°C and pressures up to 4.14 MPa. An analytical model has also been developed for estimation of the diffusion coefficient utilizing the experimental data of the interface velocity as a result of swelling and the rate of gas dissolution in the liquid phase. It is shown that the diffusion coefficient of ethane in toluene is dependent on the initial mass fraction of the gaseous component in the liquid. In addition, the effect of concentration dependency of the molecular diffusion coefficient on diffusive mass flux is quantified. The results reveal that the assumption of a constant diffusion coefficient introduces ~10–60% error in calculation of diffusional mass transfer flux. The developed methodology finds application in estimation of the concentration-dependent molecular diffusion coefficient of gases in liquids.     

湍动流化床内固体颗粒扩散系数

将高速摄影及基于互相关原理的图像处理技术与颗粒扩散规律的研究进行结合,对湍动流化床中甲醇制烯烃催化剂SAPO-34颗粒的扩散系数进行了实验研究。实验表明,对于Geldart A类的SAPO-34颗粒,颗粒纵向扩散系数在10^-2～10^-1 m²·s^-1量级之间,横向扩散系数在10^-3～10^-2 m²·s^-1量级之间,两者均随流化风速的上升而增大。另外,在相同的流化风速下,粒径较小的颗粒具有更大的扩散系数。该结果对湍动床颗粒运动规律的研究有一定意义。