NPE在有序介孔炭上的吸附行为研究

采用有序介孔硅为硬模板制备了具有不同孔径的有序介孔炭(OMCs). 氮气吸附测试表明, 有序介孔炭具有丰富的介孔表面和集中的介孔分布. 以壬基酚聚氧乙烯醚(NPE)为探针分子, 研究了大分子酚类在有序介孔炭上的吸附行为. 吸附研究表明, NPE在有序介孔炭上的吸附满足Langmuir吸附模型. 孔结构分析表明, 大于1.5 nm的孔的表面积是决定NPE吸附量的关键因素, 而有序介孔炭的最可几孔径决定吸附速率的大小. 与吸附量相比, 吸附速率更容易受环境温度的影响. 动力学研究表明, NPE在有序介孔炭上的吸附满足准二级动力学方程.     

NPE在有序介孔炭上的吸附行为研究

采用有序介孔硅为硬模板制备了具有不同孔径的有序介孔炭(OMCs). 氮气吸附测试表明, 有序介孔炭具有丰富的介孔表面和集中的介孔分布. 以壬基酚聚氧乙烯醚(NPE)为探针分子, 研究了大分子酚类在有序介孔炭上的吸附行为. 吸附研究表明, NPE在有序介孔炭上的吸附满足Langmuir吸附模型. 孔结构分析表明, 大于1.5 nm的孔的表面积是决定NPE吸附量的关键因素, 而有序介孔炭的最可几孔径决定吸附速率的大小. 与吸附量相比, 吸附速率更容易受环境温度的影响. 动力学研究表明, NPE在有序介孔炭上的吸附满足准二级动力学方程.     

放射性核素在固-液界面上的吸附：模型及其应用

放射性核素在固-液界面上的吸附行为是其在低浓度下物理化学行为研究的重要内容之一。本文综述了固-液界面吸附研究方面取得的主要进展,总结了放射性核素在固-液界面的吸附动力学、热力学模型,重点讨论了表面配位模型和亚稳态理论在固-液界面吸附行为研究中的应用和发展,较为详细地概括了部分先进光谱技术、理论计算方法和模型模拟手段等在...     

H2, O2和CO在有机分子和聚合物上吸附的CNDO/2研究

应用CNDO/2法研究了H2, O2和CO在吡咯和由吡咯单元构成的模型大分子上的吸附行为, 讨论了被吸附分子相对于杂环烃的不同吸附取向的影响, 优化了各个体系相对于能量的分子间距, 考察了相互作用能领事于分子间距和吡咯基单元的数目, 得到了一系列与相关实验相互印证的有用的规律。     

二维大分子的构象及凝聚态调控

近年来,二维大分子蓬勃发展,已经成为继经典线形与支化拓扑大分子之后的一个重要分支.二维大分子不但补全了经典高分子科学中缺失的二维分子维度,而且成为具有广泛且重要应用前景的材料新体系,将延续高分子科学在国民经济生产生活中的重要作用.类比成熟的线形高分子系统,深入理解二维大分子的构象与凝聚态并建立精确的材料结构调控方法是其发展的基础,目前仍然处于起步阶段.本文以我们课题组的研究工作为主线,以氧化石墨烯为二维大分子理想模型,总结了二维大分子构象行为与凝聚态结构调控的研究思路与进展.简要回顾了二维大分子构象的研究历史,介绍了构象行为规律、液晶凝聚态以及固态凝聚结构调控方法的系列新进展,并对未来二维大分子构象及凝聚态研究进行了展望,为二维大分子及材料的发展提供了新思路.     

叶腊石对水溶液中铀的吸附研究

开展铀吸附研究,特别是铀在黏土矿物上的吸附行为研究,对处置库安全评价十分必要.叶腊石是自然界常见的黏土矿物,但是对叶腊石和铀相互作用的研究还较少.本文采用批式实验的方法研究了pH、离子强度等对铀在叶腊石上吸附行为的影响,还探讨了该吸附反应的热力学和动力学特性.结果表明,铀在叶腊石上的吸附受pH影响较大,受离子强度影响较小.铀在叶腊石上的吸附过程符合准二级动力学方程,Freundlich模型可以更好地拟合铀在叶腊石上的吸附行为.叶腊石吸附铀是一个自发进行的吸热反应.     

分子动力学模拟在分散剂/表面活性剂在煤颗粒表面吸附机理方面的研究进展

本研究从力场、几何优化、牛顿运动方程、周期性边界条件、系宗、控温控压方法、步长步数等方面简述了分子动力学模拟的基本原理。目前,煤大分子的构建方法有三种：经典模型、自主构建模型和含氧官能团修饰的石墨烯层模型。分子动力学模拟中,吸附构型的图像信息可以直接观察分散剂/表面活性剂在煤颗粒表面的吸附情况及吸附历程,而密度分布曲线、均方根位移、吸附能等定量结果可以揭示分散剂/表面活性剂的吸附机理。分子动力学模拟与实验方法相结合可以从微观和宏观两个角度揭示分散剂/表面活性剂在煤颗粒表面吸附模式,将为分散剂和浮选剂的开发和应用提供重要的理论支撑。     

多孔苯乙烯-二乙烯基苯共聚物微球的磺化及其对牛血清蛋白的吸附

在不同反应温度下对多孔苯乙烯-二乙烯基苯共聚物微球进行磺化亲水性修饰,采用扫描电镜与氮气吸附法,研究多孔微球的孔结构。结果显示,磺化反应修饰后,微球的孔容与比表面积变小,且随着磺化温度升高,比表面积与孔容递减。交换容量则随着磺化温度升高而递增。用牛血清蛋白作为模型蛋白质,研究了亲水性修饰后的多孔苯乙烯-二乙烯基苯共聚物微球对蛋白质大分子吸附性能的影响。实验结果表明,牛血清蛋白在磺化微球上的吸附主要由孔容与比表面积决定,孔容与比表面积越大,蛋白质吸附量也越大。吸附速率表现为疏水作用快于静电作用。吸附动力学研究表明,Kannan-Sundaram模型可较好地描述牛血清蛋白的吸附动力学行为。     

耦联一级随后化学反应的准可逆表面体系循环伏安法数字模拟研究

用数字模拟方法研究了耦联一级不可逆随后化学反应的可逆、准可逆及不可逆表面吸附体系的循环伏安响应.建立了有关数字模型.模拟计算得到不同无量纲动力学参数时电流函数-电位极化曲线.给出了测定电荷传递速率常数k和随后反应速率常数中k₁的方法.并研究了对甲氧基偶氮苯在酸性介质中的伏安响应,结果尚好.     

超高交联吸附树脂对气体中三氯乙烯的吸附研究

研究了超高交联吸附树脂NDA-201对气体中三氯乙烯(TCE)的静态吸附行为.分别采用Langmuir、Freundlich和Dubimn-Astakov模型方程对吸附平衡数据进行了拟合分析,并探讨了吸附机理.实验结果表明,Dubinin-Astakov方程能较好地拟合吸附平衡数据,表明微孔填充在吸附过程中起着很重要的作用.此外,研究了气体中TCE在NDA-201上的动态吸附行为,并用半经验方程Yoon-Nelson模型对穿透曲线进行拟合,实验数据与模拟值吻合良好.     

Computational screening of biomolecular adsorption and self‐assembly on nanoscale surfaces

The quantification of binding properties of ions, surfactants, biopolymers, and other macromolecules to nanometer‐scale surfaces is often difficult experimentally and a recurring challenge in molecular simulation. A simple and computationally efficient method is introduced to compute quantitatively the energy of adsorption of solute molecules on a given surface. Highly accurate summation of Coulomb energies as well as precise control of temperature and pressure is required to extract the small energy differences in complex environments characterized by a large total energy. The method involves the simulation of four systems, the surface‐solute–solvent system, the solute–solvent system, the solvent system, and the surface‐solvent system under consideration of equal molecular volumes of each component under NVT conditions using standard molecular dynamics or Monte Carlo algorithms. Particularly in chemically detailed systems including thousands of explicit solvent molecules and specific concentrations of ions and organic solutes, the method takes into account the effect of complex nonbond interactions and rotational isomeric states on the adsorption behavior on surfaces. As a numerical example, the adsorption of a dodecapeptide on the Au {111} and mica {001} surfaces is described in aqueous solution. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Modulation of proteins adsorption onto the surface of chitosan complexed with anionic copolymers. Real time analysis by surface plasmon resonance

The interpolyelectrolyte complex formation between chitosan and anionic polyacrylic derivatives, bearing sulfonic moieties, as well as the protein adsorption onto the chitosan/polyacrylic complexes were studied by surface plasmon resonance (SPR) optical biosensor. This unique technique allows a real time monitoring of different surface molecular interactions with very high sensitivity. The acrylic macromolecules are two families of copolymers of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) and, respectively, 2-hydroxyethylmethacrylate (HEMA) and N,N'-dimethylacrylamide (DMAA). The complexation process was evaluated through the SPR measurements resulting from the flowing of polyacrylic aqueous solution over the sensor previously coated with chitosan. The SPR was able to differentiate strong ionic bonds from other weak and reversible interactions. By means of the coated sensors (uncomplexed and the whole series of complexed chitosan), SPR cold be used for a simple "in vitro" protein adsorption analysis, by flowing aqueous solutions of albumin and fibrinogen. While both proteins were adsorbed on the uncomplexed chitosan, the complexed coatings exhibited different and very promising behaviors. In particular, they showed no adsorption or only selective adsorption of albumin.     

Probing gas adsorption in MOFs using an efficient ab initio widom insertion Monte Carlo method

We propose a novel biased Widom insertion method that can efficiently compute the Henry coefficient, K_H, of gas molecules inside porous materials exhibiting strong adsorption sites by employing purely DFT calculations. This is achieved by partitioning the simulation volume into strongly and weakly adsorbing regions and selectively biasing the Widom insertion moves into the former region. We show that only few thousands of single point energy calculations are necessary to achieve accurate statistics compared to many hundreds of thousands or millions of such calculations in conventional random insertions. The methodology is used to compute the Henry coefficient for CO₂, N₂, CH₄, and C₂H₂ in M‐MOF‐74(M = Zn and Mg), yielding good agreement with published experimental data. Our results demonstrate that the DFT binding energy and the heat of adsorption are not accurate enough indicators to rank the guest adsorption properties at the Henry regime. © 2016 Wiley Periodicals, Inc.     

Patterns of the adsorption of bovine serum albumin on carboxymethyl dextran and carboxymethyl cellulose films

Patterns of the adsorption of bovine serum albumin on carboxymethyl dextran and carboxymethyl cellulose films are studied by means of microcontact printing, atomic force microscopy, and quartz crystal microbalance. It is shown that both the charge of polysaccharide macromolecules and the technique for deposition of their films onto the surface (via adsorption from a solution or covalent cross-linking) are factors that determine the degree of nonspecific adsorption of the protein on such films.     

Adsorption of large macromolecules on fine colloidal particles

A simple model of adsorption of large macromolecules on ultra-fine colloidal particles is presented. The basic assumption of the model is that the number of particles attached to a single molecule is a random quantity. Both the reversible and irreversible polymerparticle binding is considered. Also, effects of the non-ideal mixing of polymer solution with suspension and of the polymer/particle size ratio on the shape of the adsorption isotherm are examined. The predictions of the model are confronted with experimental results of the study on the adsorption of very high molecular weight polyacrylamide on fine AgI colloidal particles.     

Relaxation phenomena of polyethyleneimine molecules within saturated homogeneous and heterogeneous layers adsorbed at a silica/water interface

Surface area exclusion chromatography was used to investigate the adsorption characteristics of the highly branched polyethyleneimine (PEI) molecule and of a related molecule resulting from the grafting of PEI with C12 to C22 alkyl chains. The interfacial relaxation and surface affinity of the two polymers was determined in homogeneous and heterogeneous layers. The presence of hydrophobic moieties within the branched morphology of the grafted PEI molecule was found to modify the adsorption histogram as compared to bare PEI and to lead to greater interfacial stability. The relaxation of the bare and grafted macromolecules proved to be of equal extent but to develop at different rates within homogeneous layers. In heterogeneous layers composed of the two polymers, the slower relaxation of the grafted macromolecules decreased the rate of relaxation of the bare molecules, while the faster relaxation of the bare molecules strongly increased the rate and extent of the relaxation of the grafted macromolecules. The same technique was then used to determine the mode of establishment of the layers. The polymer coating profiles on successive glass fiber filters of the chromatography column were found to depend on the sequence of injection of the two polymers. Simultaneous and sequential adsorption processes were analyzed on the basis of the random sequential adsorption of macromolecules.     

核磁共振中多量子相干扩散行为的理论表述和计算机模拟

Self-diffusion is one of the most fundamental motions of particles in liquid. Nuclear magnetic resonance （NMR）provides a convenient and noninvasive means for accurately measuring the self-diffusion coefficient of molecules in solution. The theoretical expressions of apparent diffusion rates of MQCs are given and computer simulation based on the method to measure the self-diffusion coefficient by NMR was discussed and the random walk model of particles is used to simulate the apparent diffusion behaviors of intra-molecular and inter-molecular multiple-quantum coherences（MQCs）. The results of computer simulation agree well with theoretical predictions.     

Thermodynamic and structural properties of confined discrete-potential fluids

The thermodynamic and structural behaviors of confined discrete-potential fluids are analyzed by computer simulations, studying in a systematic way the effects observed by varying the density, temperature, and parameters of the potentials that characterize the molecule-molecule interactions. The Gibbs ensemble simulation technique for confined fluids [A. Z. Panagiotopoulos, Mol. Phys. 62, 701 (1987)] is applied to a fluid confined between two parallel hard walls. Two different systems have been considered, both formed by spherical particles that differ by the interparticle pair potential: a square well plus square shoulder or a square shoulder plus square well interaction. These model interactions can describe in an effective way pair potentials of real molecular and colloidal systems. Results are compared with the simpler reference systems of square-shoulder and square-well fluids, both under confinement. From the adsorption characterization through the use of density profiles, it is possible to obtain specific values of the interparticle potential parameters that result in a positive to negative adsorption transition.     

Analogy in the adsorption of random copolymers and homopolymers at solid-liquid interface: a Monte Carlo simulation study

The adsorption of random copolymers at solid-liquid interface from a nonselective solvent has been studied by Monte Carlo simulation in a cubic lattice. The polymeric molecules are modeled as self-avoiding linear chains composed of two types of segments A and B. The effects of copolymer composition (A/B ratio), segment-surface interaction, and bulk concentration are examined on the thermodynamic and structural adsorption properties including surface coverage, adsorption amount, adsorption layer thickness, and microscopic density distribution. At a given newly introduced effective adsorption energy, random copolymers are found to behave quantitatively as homopolymers regardless of the copolymer composition and surface affinity. This remarkable analogy provides an efficient way in predicting the adsorption of random copolymers from homopolymers.     

Influence of the microstructure of acrylic acid-n-butyl acrylate copolymers prepared by pseudoliving radical polymerization by the reversible addition-fragmentation chain transfer mechanism on their surface activity in aqueous solutions

The influence of the microstructure of acrylic acid-n-butyl acrylate copolymers prepared by pseudoliving radical polymerization by the reversible addition-fragmentation chain transfer mechanism on their surface activity in aqueous solutions was studied. The mechanisms of adsorption of polymer macromolecules on the phase boundary, accounting for the difference in the behavior of the random and block copolymers, were suggested. The dependence of the surface activity on the chain flexibility was elucidated. This dependence is very significant for the random copolymers and insignificant for the block copolymers.