Diffusion of Nanoparticles in Semidilute Polymer Solutions: A Multiparticle Collision Dynamics Study

The diffusion of nanoparticles immersed in semidilute polymer solutions is investigated by a hybrid mesoscopic multiparticle collision dynamics method. Effects of polymer concentration and hydrodynamic interactions among polymer monomers are focused. Extensive simulations show that the dependence of diffusion coefficient D on the polymer concentration c agrees with Phillies equation D-exp (-αc^δ) with a scaling exponent δ≈0.97 which coincides with the experimental one in literature. For increasing nanoparticle size, the scaling prefactor α increases monotonically while the scaling exponent always keeps fixed. Moreover, we also study the diffusion of nanoparticle without hydrodynamic interactions and find that mobility of the nanoparticle slows down, and the scaling exponent is obviously different from the one in experiments, implying that hydrodynamic interactions play a crucial role in the diffusion of a nanoparticle in semidilute polymer solutions.     

Polymeric Nanoparticles Stabilized by Surfactants Investigated by Light Scattering,Small-Angle Neutron Scattering,and Cryo-TEM Methods

We have investigated self-organization of polymers with surfactants through solvent shifting process resulting in formation of stable and uniform nanoparticles. We studied polymeric nanoparticles made of poly(methylmethacrylate) and of polystyrene dispersed in water. The dispersion was prepared by a fast mixing of a solution of the polymers with a solution of several ionic and nonionic surfactants in pure water. We observed the formation of well defined nanoparticles by light scattering, small-angle neutron scattering (SANS), and cryogenic transmission electron microscopy (Cryo-TEM) methods. The study shows how nanoparticle properties are changed by the chemical composition of surfactants, molar mass of polymers, concentrations of both components and finally, by variations in method of nanoparticles preparation. Dynamic light scattering (DLS) and static light scattering (SLS) provide the hydrodynamic radii and radii of gyration for selected types of nanoparticles. Cryo-TEM experiments prove that the nanoparticles have good spherical shape. Analysis of SANS data and Cryo-TEM micrographs suggest that the prepared particles are composed of polymer and surfactant that are evenly distributed.     

高分子的良溶剂和不良溶剂的两种定义辩析

介绍了目前国际学术界存在的对高分子溶液体系的溶剂优劣性的两种判断标准 ,即相互作用参数χ=1 /2和χ=0 ,前者基于混合自由能 ,后者基于混合热。作者阐明了其倾向于采用后者的观点 ,而后者在目前国内所有高分子物理学教科书中均未被介绍。     

Diffusion Mode Transition between Gaussian and Non-Gaussian of Nanoparticles in Polymer Solutions

The dynamic density functional theory is applied to study the diffusion of nanoparticles in polymer solutions, in which different diffusion modes have been identified by exploiting the density and free energy evolutions. Under the condition of low polymer concentration, diffusion is controlled by particle free motion with a normal Gaussian type. As the concentration increases, the non- Gaussian behavior can be observed when the particle size is comparable to the correlation length of polymer chain. Particles need to penetrate through a cage and overcome an entropic barrier, where the hopping and the model-coupling diffusion coexist. Further increase of polymer concentration can result in complete restriction of the particle by surrounding polymer segments. In this case, the non-Gaussian process fades away, and particle diffusion is controlled by Rouse dynamics of polymer chains with the generalized Gaussian characteristics.     

Selective Immobilization of Gold Nanoparticles on the Surface of a Photoreactive Polymer

Summary. A photoreactive polymer containing thiocyanate (SCN) groups was employed for the immobilization of gold nanoparticles (AuNP). Upon UV illumination, isothiocyanate (NCS) groups are generated at the surface by photoisomerization. The illuminated areas of the polymer layer containing NCS were selectively modified with 2-aminoethanethiol to give SH terminated thiourea units at the surface. Gold nanoparticles were selectively immobilized in these areas by immersing the polymer surface in a colloidal solution of gold nanoparticles stabilized by citric acid. Depending on the time of immersion, different amounts of gold were deposited on the illuminated areas, while no immobilization of AuNP was observed in the non-illuminated areas. By using photolithographic masks, patterned gold structures (μm scale) were produced on the polymer surface.     

高分子研究中的一个知识问题——柔性链“从线团到小球”的构象变化

一条大分子链由许多小分子通过共价键连接而成.正是这一"连接"导致了大分子一些独特的物理性质及相关问题.本文希望阐明的就是这样一个小分子物理中没有的知识问题:小分子在溶剂中仅有溶或不溶2个状态;而自60年代起,理论学家们就预言一条柔性大分子链在溶解的状态下,其构象随着溶剂性质变差可以从无规线团蜷缩成一个单链小球.为了证明这一构象变化,实验学家们从70年代末起进行了大量的研究,直至90年代初期仍未观察到稳定的单链蜷缩小球.实验上这一长期悬而未解的问题困惑着众多研究者.甚至有理论学家在1993年报道,当今的样品制备和实验手段无法观察到一个热力学稳定的单链蜷缩小球.中国钱人元先生和一些其他研究者自80年代末期也开始关注与单链有关的问题.我们实验室从1993年开始另辟蹊径,通过制备和采用窄分布的热敏性水溶性高分子超长链,终于在1995年利用激光光散射首次观察到理论上预测的"线团到小球"的构象变化.随后,又揭示了变化过程中存在着一个全新的"融化球"构象以及在单链蜷缩小球中并无理论上预计的额外链互穿和打结.从得到的稳定单链蜷缩小球出发,我们又首次在实验上研究了"小球到线团"的过程,意外地观察到其在准理想状态附近滞后于"线团到小球"的构象变化,并证明该滞后可归于链蜷缩过程中形成的额外链内氢键.最后,借用红外纳秒脉冲激光加热的方法研究了"线团到小球"的蜷缩动力学,并发现其包含了在单个高分子链上"成核"和"粗化"先后2个过程.其中,"成核"过程与链长无关.经过近20年的努力,我们终于基本解决了这一近代高分子物理研究中与知识有关的重要问题,揭示了与其相关的一些大分子特有的物理性质.     

良溶剂中接枝型聚两性电解质单链构象的布朗动力学模拟

采用布朗动力学研究了在良溶剂中荷电平衡的接枝聚两性电解质(GPA)的单链构象转变行为,讨论了主链链长、支链数及电荷密度对GPA分子链构象转变的影响.研究发现,随着静电相互作用的增强,GPA分子链构象转变过程由线团、主链与支链间的折叠、链段塌缩和电荷配对形成偶极子与四极子等4个阶段构成.与线型聚两性电解质不同,GPA存在的额外支链间空间排斥与静电排斥作用随着分子结构的变化而改变,并影响构象转变行为.在强静电相互作用下,良溶剂中的GPA链由于溶剂化作用会再伸展,以保证偶极子完全配对成四极子.减小主链长度或电荷密度或增加支链数目都会增大体系的排斥力和主链的刚性,阻滞分子链的塌缩,并使得分子链再伸展的幅度增大.     

Studies on Composites of Nanoparticles and Some Polymers

The metal oxide nanoparticle of Cr₂O₃ was made into a composite with the polymers, which is of novel functions. Surfactants solubilized agents were used to increase compatibility between the two phases. The. application of the new products is described.     

Study on the Conformation of Cyclodecapeptide Loloatin C with Obvious Antibiotic Activity

The conformation of cyclodecapeptide loloatin C with obvious antibiotic activity has been investigated in 2,2,2-trifluoroethanol/sodium acetate buffer solution and then characterized by Fr-IR, CD and NMR spectrum. The results of FT-IR show that there exists β-strand or β-tum secondary structure in the molecule. According to the CD spectrum, the helical turn is dominant but the β-turn structure also exists. Conformation of the whole molecule is probably a helical β-turn.The chemical shifts and coupling constants prove the existence of a β-structure in the regions of Val,Orn2 and Leu3. NOESY data and temperature gradients of amide protons suggest that the molecular conformation is a dumbbell-like structure with the waist located between ornithyl (position 2) and D-phenylalanyl (position 7) and β-turn on both ends.     

聚苯乙烯微球表面的链段堆积状态

聚苯乙烯微球表面的链段堆积状态徐伟，陈殿勇，华中一，吕绪良，胡建华，府寿宽（复旦大学材料科学系，上海，２００４３３）（复旦大学高分子科学系）关键词聚苯乙烯微球，聚合物链段，聚集态，扫描隧道显微镜用微乳液聚合法制备的聚苯乙烯微球与常规聚苯乙烯相比有许多...     

Computer Simulation Study on Adsorption and Conformation of Polymer Chains Driven by External Force

In this work, Monte Carlo simulations are used to study the critical adsorption behaviors of flexible polymer chains under the action of an external driving force F parallel to an attractive flat surface. The critical adsorption temperature T_c decreases linearly with increasing F,indicating that the driving force suppresses the adsorption of polymer. The conformation of polymer is also affected by the driving force.However, the effect of F is dependent on the competition between the driving force and temperature. Under strong force or at low temperature,the polymer is stretched along the direction of the force, while under weak force or at high temperature, the polymer is not stretched. When the force is comparable to the temperature, the polymer may be stretched perpendicular to the driving force, and below T_c, we observe conformational transitions from parallel to perpendicular and again to parallel by decreasing the temperature. We found that the perpendicular stretched conformation leads the polymer chain to synchronously move along the direction of the driving force. Moreover, the conformational transitions are attributed to the competition and cooperation between the driving force and the temperature.     

孤啡肽OFQ的溶液构象研究

应用近代NMR波谱技术对孤啡肽OFQ及其片段OFQ_(8-17)的溶液结构进行了比较 研究,测定了孤啡肽OFQ和片段OFQ_(8-17)在H_2O和TEF/H_2O两种溶剂条件下的2D －DQF－COSY,2D－TOCSY,2D－NOSESY(ROESY)谱,完成了它们氨基酸残基的处旋 系统识别和序列特异性归属,获得分子中质子化学位移的完全归属,根据NOE特征 和主链偶合常数等结构参数确定了它们的特征二级结构,以NOE提供的距离约束, 进行何,分子力学和分子动力学模拟,得到了孤啡肽OFQ在不同溶剂条件下的溶液 结构。在H_2O溶济中,孤啡肽OFQ在G3－F4－T5－G6处形成一复合型转角结构。在 TFE/H_2O溶剂中,OFQ整个分子形成两新性α－螺旋结构。而孤啡肽片OFO_(8-17) 在这两种环境中均为伸展的无规结构。孤啡肽OFQ在类似膜环境(TFE/H_2O)下的α 螺旋结构可能为其活性构象。     

Effect of Macromolecular Crowding on the Conformation of Confined Chain Polymers

Summary: The conformational behavior of flexible linear chain polymers confined in cylindrical pores and slab pores has been studied, employing a hard‐bead chain model and a modification of a recently proposed recoil‐growth bias Monte Carlo methodology, which improves the sampling efficiency in confined environments. It is found that the scaling law that correlates the unconstrained component of the radius of gyration of the polymer with the pore diameter in cylindrical pores is close but neatly different than the de Gennes mean‐field value. The results also indicate that the addition of spherical particles with sizes within the protein limit may be employed to tune the folding of the confined polymer, since in this case the depletion constraints work against the effective stretching forces induced by confinement. Remarkably, the presence of the depleting particles at sufficiently high concentration leads to appreciable changes in the exponents of the conformational scaling laws with respect to the uncrowded system.

Conformational behavior of flexible hard‐bead chain polymers confined in narrow pores.     

在导电高分子薄膜表面沉积密度可控的银纳米粒子

<正>由于导电高分子的导电性和化学性质可以在导体和半导体区间内快速调节[1],因此其复合材料受到了越来越多的关注[2].金属纳米粒子在光电子器件、检测及传感等诸多领域表现出独特的性能[3],在生物技术领域中的重要性尤为突出[4].因此,如果将导电高分子和金属纳米粒子结合在一起,将有利于拓展导电高分子的应用范围.本文研究了银纳米粒子在聚苯胺薄膜表面的沉积行为,分别用原子力显微镜(AFM)和扫描电子显     

反相乳液法氘代聚苯乙烯微孔泡沫的研制

采用反相乳液技术,以自制全氘代苯乙烯为聚合单体,二乙烯苯为交联剂,在探讨反相乳液法聚合反应机理,表面活性剂的作用机理及其用量对乳液稳定性的影响,有机相（O相）芳烃稀释剂及单体的聚集行为与作用机理等的基础上,成功地制得了密度为25－100mg/cm^3,蜂窝直径2－6um,微孔直径0．5－1．2um的氘代聚苯乙烯特种泡沫材料。     

高分子表面活性剂在固/液界面上的吸附形态

采用紫外光谱、XPS研究了羧甲基纤维素型高分子表面活性剂在硅胶 /水界面上的吸附形态 ,结果表明随着高分子表面活性剂溶液浓度增大 ,分子在硅胶表面的吸附由单层逐渐变为多层 ,生成半胶束结构 .     

Studies on the Molecular Chain Conformation Stability of Aminated Konjac Glucomannan

Konjac glucomannan （KGM） was aminated by 2-chloroethyl-amine （CEA） as reagent so as to study the influence of concentration of CEA （based on the amount of KGM）, concentration of NaOH, reaction time and temperature on the extent of amination. And the molecular simulation technology was adopted to analyze the conformation stability of aminate （AKGM）. The results indicate that when the amount of CEA is higher, the extent of amination is higher. The optimum concentration of NaOH, reaction time and temperature are 10% NaOH, 70 ℃ and 45 rain, respectively. IR shows KGM is successfully aminated. The conformation of AKGM is in a random clew-like shape.     

Effect of the Nanoparticle Functionalization on the Cavitation and Crazing Process in the Polymer Nanocomposites

The nanoparticle(NP) functionalization is an effective method for enhancing their compatibility with polymer which can influence the fracture property of the polymer nanocomposites(PNCs). This work aims to further understand the cavitation and crazing process, hoping to uncover the fracture mechanism on the molecular level. By adopting a coarse-grained molecular dynamics simulation, the fracture energy of PNCs first increases and then decreases with increasing the NP functionalization degree α while it shows a continuous increase with increasing the interaction ε_(pA) between polymer and modified beads. The bond orientation degree is first characterized which is referred to as the elongation. Meanwhile, the stress by polymer chains is gradually reduced with increasing the α or the ε_(pA) while that by NPs is enhanced.Furthermore, the percentage of stress by polymer chains first increases and then decreases with increasing the strain while that by NPs shows a contrast trend. Moreover, the number of voids is quantified which first increases and then decreases with increasing the strain which reflects their nucleation and coalescence process. The voids prefer to generate from the polymer-NP interface to the polymer matrix with increasing α o r ε_(pA).As a result, the number of voids first increases and then decreases with increasing α while it continuously declines with the ε_(pA). In summary, our work provides a clear understanding on how the NP functionalization influences the cavitation and crazing process during the fracture process.     

烷基取代聚硅烷共聚物的侧基对螺旋构象的影响

以手性化合物n-癸基-(S)-(+)-2-甲基丁基二氯硅烷(Si1)和非手性化合物n-癸基-2-乙基丁基二氯硅烷(Si2)为单体合成了聚硅烷共聚物[P(Si1-co-Si2)].通过改变Si1和Si2的投料比,聚合得到一系列P(Si1-co-Si2).通过核磁表征P(Si1-co-Si2)为无规共聚物.利用圆二色谱(CD)和紫外吸收光谱研究系列共聚物的手性传递行为.研究发现,Si2的均聚物在其对应的紫外吸收带324 nm处没有CD信号.当加入Si1共聚后,产生CD信号,随着Si1含量的增加,共聚物的CD信号迅速增强,当Si1摩尔分数为2%时可诱导共聚物形成单手螺旋优势构象.当Si1含量达到70%时,信号强度最大.在P(Si1-co-Si2)中Si1含量增加的过程中,共聚物的紫外吸收带同时发生蓝移.当Si1含量达到50%时,分子量较低的样品具有较强的光学活性,并且随着分子量的增大,紫外吸收红移.研究结果初步表明,聚硅烷共聚物的螺旋结构由手性侧基决定,但非手性侧基的奇偶性却没有体现.     

压力诱导溶液中蛋白质构象变化的谱学研究

高压诱导蛋白质发生构象变化,引起蛋白质去折叠,并在某种条件下发生聚集,其结果是蛋白质原有的构造被破坏、发生变性。这些过程与蛋白质本身的结构密切相关。同时,折叠中间体结构的揭示对于研究蛋白质去折叠过程也具有重要意义。本文综述了高压诱导下多种谱学方法用于蛋白质构象变化的研究进展,主要包括高压红外光谱、高压荧光光谱及高压小角X射线扫描等多种技术手段在研究中蛋白质构象变化方面所能提供的重要信息,并对相关领域存在的问题及今后的发展作出展望。