逆体积排阻层析法测定层析介质的孔径分布

针对层析介质的孔径分析,基于刚性球状分子进入柱状孔的假设,分别采用高斯正态分布和对数正态分布描述孔径分布,利用简化的单孔分配因子模型,建立了孔径分布函数和分配因子Kd的关联,通过体积排阻层析实验测定系列标准物的Kd,从而拟合得到孔径分布信息,建立了逆体积排阻层析法。以葡聚糖作为分子大小的标准物,测定了5种典型层析介质(SP Sepharose FAST FLOW、Q Sepharose FAST FLOW、ToyopearlDEAE-650M、Streamline DEAE和Sephadex G-150)的Kd,计算和比较了不同介质的孔径分布,分析了介质的可吸附孔表面积等结构参数,证实了逆体积排阻层析法分析层析介质孔径分布的可行性和实用性。     

ISEC法在评价色谱介质孔径结构方面的应用

层析是生物大分子分离纯化的一种重要手段,层析介质作为层析过程的关键的一部分受到了广泛的关注。层析介质的孔径结构对其分离纯化的效果有着显著的影响,因此探究层析介质的孔径结构至关重要。介绍了测定色谱介质孔径结构常用的方法,如：压汞法、氮气吸附法、小角X射线散射法、电镜扫描法（SEM和TEM）和逆体积排阻色谱法(ISEC)。重点阐述了ISEC法的基本原理和常用的探针类型,总结了ISEC法应用中的优点及不足,介绍了ISEC法的发展历史及其在国内外的研究现状。     

水泥浆体中可蒸发水的1H核磁共振弛豫特征及状态演变

利用低场质子核磁共振方法研究了硬化水泥浆体中可蒸发水的横向弛豫特征及其状态演变.结果表明:随着龄期的增长,可蒸发水的弛豫时间分布逐渐趋向于短弛豫时间,主峰平均弛豫时间降低,凝胶水相对含量不断增大,毛细水含量降低.由于浆体内部水化产物的填充使得孔结构细化,可蒸发水集中在小孔隙中,并主要以凝胶水的形式存在.     

超大孔聚苯乙烯微球固定蛋白质

采用琼脂糖对孔径为300~500 nm的超大孔聚苯乙烯(MPS)微球进行亲水化修饰,并在修饰后的表面上偶联病毒蛋白颗粒(RV),用于蛋白质的分离纯化实验. 结果表明,经过修饰的MPS层析介质具有优异的流体力学性能,层析过程的最高流速可达1120 cm/h,对病毒蛋白颗粒的固定量为0.638 mg/g,是商品化介质Sepharose 4FF的2倍. 采用RV-MPS介质对病毒蛋白颗粒抗体进行了分离纯化,收率为29.22%,高于Sepharose 4FF的18.92%.     

逆体积排阻色谱法在评价色谱介质孔径结构方面的应用

介绍了影响层析介质分离纯化效果的结构参数。总结了测定色谱介质孔径结构常用的方法,如压汞法、氮气吸附法、小角X射线散射法、电镜观察法(SEM和TEM)和逆体积排阻色谱法(ISEC)。介绍了ISEC的基本原理及其涉及到的探针类型。对ISEC相关理论,尤其是溶质半径、色谱理论和体积排阻色谱法(SEC)随机理论进行了重点阐述。比较了ISEC的优缺点。介绍了ISEC在评价介质孔径结构中的应用,对ISEC的应用前景进行了展望。     

精密单丝滤布透水速率与截留精度的研究

为进一步了解液固分离用织造滤布的过滤性能,以液固分离用新型过滤介质精密单丝滤布为研究对象,对滤布结构、开孔大小、丝径、孔隙率等因素对透水速率的影响进行了理论分析与讨论;并采用国际标准规定的鼓泡孔径、透水速率和截留精度的测试方法,对几种精密单丝滤布的孔径大小、透水速率、截留精度、透水阻力、孔隙度、分离效率进行了实验测定;同时介绍了不同孔隙度及截留精度的测定方法和结果,并对截留精度经验计算进行了实验验证,对正确选择与科学使用过滤介质单丝滤布提供有益的参考。     

非织造过滤介质孔径及截留性能的研究

对应用于液固分离和气固分离的非织造过滤介质的孔径和截留性能测试方法做了研究,指出采用气体流量法进行孔径性能测试,可同时得到非织造过滤介质的最大孔径、平均孔径及孔径分布,全面表征了其孔径性能;并对用于液固和气固分离2个不同领域的非织造过滤介质采用不同的方法做了截留性能测试。同时,对比非织造过滤介质的孔径和截留性能,对二者之间的关联做了探索,为实际工业过程中非织造过滤介质的选用和评价提供了指导。     

氮气吸附法和压汞法测定Al2O3载体孔结构

作为催化剂载体的活性氧化铝,其孔径分布主要集中在中孔范围内,压汞法和氮气吸附法是测定多孔材料比表面积、孔径及其分布的经典方法,采甩压汞仪和比表面积、孔径测定仪对活性氧化铝载体孔结构进行测定。氮气吸附法采用BET原理进行比表面积测定,采用BJH原理进行孔径分布和孔容的测定,压汞法采用Wasburn公式测定比表面、孔径分布和孔容。对两种方法实验结果进行了讨论,认为氮气吸附法更适合氧化铝载体孔结构的测定。     

复乳法制备大孔琼脂糖分离介质与疫苗结合性能研究

大孔分离介质在分离纯化特别是超大生物分子分离纯化领域具有十分重要的应用意义。受材料性质和制备技术所限制,大孔分离介质以聚合物材料最为常见,针对琼脂糖的大孔分离介质较为少见。通过复乳法制备大孔琼脂糖微球,研究制备条件对微球形貌与成孔情况以及粒径与分布等的影响,发现该微球具备微米级超大孔结构,且制备条件对孔道结构的影响呈现一定规律,琼脂糖溶液浓度、内/外油相与水相比例、初乳转速和成球转速等都对成孔性至关重要。激光共聚焦显微镜实验结果表明,衍生后的大孔琼脂糖分离介质对乙肝表面抗原具有良好的结合能力,使其能够完全进入微球内部。与传统琼脂糖介质相比,大孔琼脂糖介质能够更快速、充分结合大分子疫苗,在超大分子分离纯化领域应用前景广阔。     

基于逾渗理论的多孔过滤介质孔径分布估计方法

结合逾渗理论和网格模型,建立了过滤系数与过滤介质孔径分布的联系方程。利用此方程结合过滤实验数据获得过滤介质孔径分布的统计参数,同时与其他方法获得孔径分布参数以及其他文献中的数据进行比较,并利用计算机模拟过滤过程验证了获得的孔径分布参数,结果表明基于逾渗理论的过滤模型用于孔径分布参数的估计是比较准确和有效的。     

Internal Structure of Porous Silica: A Model System for Characterization by Nuclear Magnetic Resonance

Nuclear magnetic resonance (NMR) relaxation methods have been used to investigate the internal structure of porous silica gelled from colloidal silica and potassium silicate mixtures. These materials possess a narrow pore size distribution with average pore diameter ranging from 470 to 2400 Å (47 to 240 nm) as determined from mercury intrusion porosimetry. NMR relaxation measurements were performed on deionized water impregnated into the pore space. These results determine the distribution of local surface-to-volume ratios and show that all of the silica samples are very uniform on a length scale greater than 5 μ. NMR relaxation measurements performed on silica samples partially filled with water provide a precise confirmation of the theoretical model upon which the NMR pore structure analysis is based. Measurements of the relaxation strength at the water—silica interface were found to depend systematically on the initial composition of the material. The self-diffusion coefficient of water, saturated in the pore space, is reduced by 14% from its bulk value.     

Pore size distribution from challenge coreflood testing by colloidal flow

The transport of colloidal and suspension particles and the resultant particle retention occur in a wide range of porous media. The micro scale pore throat size distribution is an important characteristic of porous media, allowing for evaluation of important transport properties. An effective method based on micro scale modelling for the determination of overall pore throat size distribution (PSD) by injection of colloidal particle suspensions into engineered porous media with monitored inlet and breakthrough particle concentrations is developed. The treatment of inlet and outlet colloidal particle concentrations obtained in coreflooding results in a good agreement between the modelling and experimental data. Yet, some deviation was observed between the obtained PSD and that calculated by the Monte Carlo simulation based on the Descartes’ theorem.     

NMR diffusion and relaxation studies during cement hydration—A non-destructive approach for clarification of the mechanism of internal post curing of cementitious materials

Internal post-curing of hardening cement pastes by addition of alginate spheres, which contain 98% of water, is studied by non-destructive ¹H NMR measurements of transverse relaxation time and self-diffusion. The onset and amount of water transition from the alginate gel used as additive with temporary delayed release of water to cement pastes was observed continuously during the dormant and accelerated period of cement hydration. During hydration, the water transition from the alginate into the cement matrix as well as the development of pore size is monitored quantitatively by studying the time dependence of characteristic peaks in the transverse relaxation time distribution. Comparison between samples without and with internal post curing shows that the addition of alginate gel does not influence the pore size in the micropore region. NMR diffusion studies demonstrate that the physically bound pore water has sufficient mobility to ensure homogeneous distribution of water from the alginate source into the surrounding cement matrix during the dormant and accelerated period.     

Characterization of fluid distributions in porous media by NMR techniques

Nuclear magnetic resonance (NMR) spin-lattice relaxation measurements are used to investigate pore structures and fluid phase distributions in porous media. A new method for estimating relaxation time distribution functions from measured relaxation data is presented using a B-spline basis to represent the distribution function and Tikhonov regularization to stabilize the estimation problem. Surface relaxivity, which is required to convert relaxation time distributions to pore-size distributions of fluid phase distributions at partial saturations, is determined using pore volume-to-surface-area ratios estimated by NMR diffusion measurements. This approach was validated by analyzing certain model porous media with known pore volume-to-surface-area ratios. The method is demonstrated by determining pore-size and fluid phase distributions of sandstone and carbonate samples, as well as by comparing the pore-size distributions of chalk samples obtained by this methodology with those estimated by mercury porosimetry.     

APPLICATION OF THE PRECONDITIONED CONJUGATE GRADIENTS METHOD IN THE SIMULATION OF RELATIVE PERMEABILITY PROPERTIES OF POROUS MEDIA

A model that is after the determination of the relative permeability characteristics of porous media is presented. It is part of a general model that deals with the simulation of capillary phenomena and immiscible fluid flow behaviour in porous media. The relative permeability characteristics in a water wet porous medium are simulated with the use of three-dimensional (3-D) network models of pore structure with pore body and pore throat size distributions. The major assumption involved is that a cubic network of pore bodies connected by pore throats with pore body and pore throat size distribution respectively, is a realistic representation of the pore structure of a porous medium. The physical laws that apply in real media are simulated in the network analysis, and the computed results are compared with experimental findings. A new algorithm was developed that leads to the solution of a large set of linear equations, with a sparse and positive definite coefficient matrix. Results obtained with the application of the Preconditioned Conjugate Gradients method and numerical aspects of the simulation are presented and discussed. Comparison of this method with other available numerical methods is also made. It is concluded that the Preconditioned Conjugate Gradients method is advantageous for large networks with regards to time of solution, convergence, and accuracy. The validity of the algorithm is tested against other methods in the literature.     

三种混合模式色谱填料色谱性能的比较

以γ-缩水甘油醚氧丙基三甲氧基硅烷为中间活化剂,将3-氨基吡啶、2-巯基苯并咪唑和2-巯基-1-甲基咪唑3种杂环配基键合到粒径为5 μm、孔径为30 nm的球形硅胶上,制备3种高效疏水电荷诱导色谱填料。利用溶菌酶、牛血清白蛋白和免疫球蛋白G作为模型蛋白,考察其在3种不同配基色谱柱上的保留行为和分离行为。比较了3种不同性质的模型蛋白在不同色谱柱上的色谱性能的异同。发现以2-巯基-1-甲基咪唑为配基的色谱柱具有良好的pH控制色谱行为和良好的分离性能,初步验证了高效疏水电荷诱导色谱的分离模式及潜在应用。     

Synthesis,gas adsorption and reliable pore size estimation of zeolitic imidazolate framework-7 using CO2 and water adsorption

Reliable estimation of the pore size distribution(PSD) in porous materials such as metal–organic frameworks(MOFs) and zeolitic imidazolate frameworks(ZIFs) is crucial for accurately assessing adsorption capacity and corresponding selectivity. In this study, the so-called zeolitic imidazolate framework-7(ZIF-7) is successfully synthesized via relatively fast and convenient microwave technique. The morphology and structure of the obtained MOF were characterized by XRD, SEM and N_2 and CO_2adsorption/desorption isotherms at 77 K and0 °C respectively. Then, to determine the PSD of the fabricated MOF, carbon dioxide isotherms are experimentally measured at various temperatures up to atmospheric pressure. Afterward, the experimental CO_2 isotherms data are utilized in two recently proposed in-house algorithms of SHN1 and SHN2 to extract the true PSD of manufactured ZIF-7. The obtained results revealed that median pore diameter of the fabricated ZIF-7 is estimated around 0.404 nm and 0.370 nm by using CO_2 isotherms at 273 K and 298 K respectively. These values are in good agreement with the real pore diameter of 0.42 nm. Moreover, experimental data of water adsorption isotherms over four different MOFs, borrowed from literature, are employed to illustrate further effectiveness of the above algorithms on successful determination of the corresponding pore size distributions. All predicted PSDs are proved to be in good agreement with those obtained from independent methods such as topology and morphology studies.