半刚性高分子链螺旋结构诱导纳米棒的有序结构

在自然界中, 螺旋结构广泛存在. 在熵的驱动下, 高分子链能在某些特殊情形下形成螺旋结构. 采用分子动力学方法研究了高分子链诱导纳米棒的自组装行为, 发现纳米棒/高分子链体系的构象与纳米棒的数量、高分子链的刚性等密切相关. 当纳米棒与高分子链之间存在适度吸附能时, 纳米棒能够形成三种完全不同的构象, 特别是在半刚性高分子链诱导下纳米棒能够形成线型排列. 研究结果对新型材料制备具有一定指导意义.     

自驱动杆状粒子在半柔性弹性环中的集体行为

在生物体系的活性系统中,杆状粒子在弹性半柔性边界中的受限行为极为常见.本文研究了二维情况下,自驱动杆状粒子受限在半柔性弹性环中的集体行为.改变系统的粒子数及噪声强度,系统显示明显的自驱吸附有序态、无序态及中间的过渡态.通过表征弹性环内部粒子的径向极性大小和空间分布的非球度性对这些状态进行了刻画.进一步对弹性环中心附近粒子密度的分析,发现环中心气态粒子分布存在一个与边界高密度区域共存的饱和平台,出现类似吸附转变的粒子分布.在过渡区间,体系内存在较大的涨落会导致弹性环出现异常形变.非对称的粒子分布对弹性环整体的迁移具有重要贡献,系统在过渡区间能获得相对较强的定向迁移.     

外力驱动作用下高分子链在表面吸附性质的计算机模拟

采用退火法模拟研究受外力F驱动的高分子链在吸引表面的吸附特性.通过高分子链的平均表面接触数〈M〉与温度T之间的关系计算临界吸附温度T_c,并发现T_c随着F的增加而减小;进而通过高分子链的均方回转半径分析外力驱动作用对高分子链构象的影响,并从回转半径极小值或者垂直外力方向的y和z分量的变化交叉校验临界吸附点T_c.模拟计算了处于吸附状态的高分子链随着外力F的增加是否会发生吸附状态到脱附状态的相变以及发生相变所需施加的外力是否由温度所决定.模拟结果表明:两种不同温度下高分子链的吸附性质和构象性质受外力驱动作用而产生不同现象,在温度区间T*_cTT_c时会发生脱附现象,而在TT*_c时不会发生脱附现象.     

熵驱动下柱状高分子刷螺旋结构的研究

自然界中广泛存在螺旋结构,在特定情形下熵能驱动高分子链形成螺旋结构.本文采用分子动力学方法研究柱状高分子刷吸附在无限长圆柱表面时的构象行为.发现其构象与嫁接支链条数、柱状高分子刷与圆柱表面之间的吸附能密切相关.在较弱的吸附能下,具有较多支链条数的柱状高分子刷能形成完整的螺旋结构,其本质就是熵驱动下形成的螺旋结构.该研究有助于加深对生物大分子螺旋结构的理解.     

甘氨酸在纳米碳管中的吸附及性质的分子模拟

采用分子力学、分子动力学方法模拟研究了甘氨酸分子在单壁纳米碳管中的吸附和扩散行为 ,并对甘氨酸分子在纳米碳管中的构象和能量进行了优化 .模拟计算结果表明 ,甘氨酸在纳米碳管中的构象发生了伸缩和扭转 ,这种构象的改变将会导致氨基酸生物性能的改变 ;纳米碳管对氨基酸分子具有较强的吸附作用 ,其中纳米碳管和甘氨酸分子之间的π -π相互作用增加了纳米碳管对氨基酸的吸附能 .模拟过程中氨基酸分子和纳米碳管之间的运动会保持很强的协同效应 ,使模拟体系构型在能量上处于最稳定的状态     

反相微乳液模板原位聚合制备纳米氯化银/聚甲基丙烯酸甲酯及其结构表征

用甲基丙烯酸甲酯 (MMA)作油相 ,反相胶束微乳液作为模板 ,制备了纳米氯化银 (AgCl)粒子 ,再进行原位聚合制备了纳米氯化银 /聚甲基丙烯酸甲酯 (AgCl/PMMA)复合材料 .透射电镜 (TEM )分析表明 ,纳米AgCl的尺寸为 2 0～ 80nm .扫描电镜 (SEM )测试表明纳米AgCl粒子均匀地存在于PMMA基材中 .红外分析证明 ,胶束中水和表面活性剂AOT的羰基在MMA聚合后微观环境发生变化 ,纳米粒子同聚合物之间有吸附行为 .动态力学 (DMTA)分析复合材料 ,发现纳米AgCl粒子与聚合物之间存在强烈相互作用 ,形成了中间相层 (interphaselayer) ,改变了聚合物的动态力学性能 .     

蠕虫状链模型在高分子物理研究中的应用

蠕虫状链模型可以更好地描述非柔性高分子的空间链构象统计,因此被公认为是更加接近真实高分子的粗粒化高分子链模型.本文从蠕虫状链模型的物理特点出发,简单回顾了该模型在自洽场理论方法中的发展历程,着重从三个研究方向总结了近年来蠕虫状链模型在高分子物理研究中的应用:高分子液晶相结构及其转变的研究;几何表面对高分子体系的影响;蠕虫状嵌段共聚物自组装.最后,针对现有理论的发展现状,对未来基于该模型的场论模拟方法的发展方向提出了展望.     

一种用于现场快速检测的SERS基底的制备

利用化学自组装方法,首先在色谱玻璃小瓶的内壁吸附上一层PDDA阳离子聚电解质,然后通过静电吸附作用将带有负电荷的银纳米粒子组装到内壁;比较了不同色谱瓶作为吸附银纳米粒子的载体的优缺点;用紫外-可见吸收光谱监测吸附到玻璃瓶内壁的银纳米粒子的表面等离子体共振峰,跟踪银纳米粒子的组装情况;利用对-巯基苯胺作为探针分子研究了基底的表面增强拉曼散射(SERS)活性。结果表明：所制备的SERS小瓶基底具有良好的SERS活性,并且使用简单,保存时间长,适合SERS现场快速检测的需要。     

自驱动颗粒体系中的熵力

在许多纳米复合材料体系中熵力(entropy force)是普遍存在的,但由于熵力的存在会导致纳米颗粒的凝聚从而降低其许多性能,因此在大多数情况下熵力的存在对体系并无益处,所以研究如何减小熵力对体系的影响是非常重要的.不带角速度的自驱动粒子在熵力作用下会集聚在纳米颗粒(或者纳米棒)周围,这会对纳米颗粒(或者纳米棒)产生很大的相互作用力.对于纳米颗粒,在不带角速度的自驱动粒子体系中存在着非常大的排斥力.而对于纳米棒,由于纳米棒内外的不对称性,使得两个纳米棒之间会产生吸引-排斥转变,同时这个吸引-排斥转变与纳米棒之间的距离有关.当自驱动粒子加上一个自转角速度ω之后,熵力的作用就大大减弱,纳米颗粒不再集聚.研究结果有助于对非平衡态下纳米颗粒(或纳米棒)之间熵相互作用力的认识.     

多价态高分子链在受体平面上的超选择性吸附

利用三维朗之万动力学模拟研究了多价态高分子链在受体平面上的吸附行为。其在受体平面上的吸附具有超选择性,随着高分子链上配体浓度的增大,发生超选择性吸附时的平面受体浓度范围变窄;而超选择性吸附最显著时的平面受体浓度,即最佳平面受体浓度随着链上配体浓度的增大而减小。对处于吸附态的多价态高分子链的构象性质进行了系统地研究,发现链的平衡回转半径R_g及其水平分量R_g},随着平面受体浓度的增大都存在极大值。其平衡回转半径R_g与其链长N间的标度指数表明当平面受体浓度的增大时,处于吸附态的链构象介于二维链构象和三维链构象之间;随着平面受体浓度的进一步增大,吸附在平面上的多价态高分子链发生轻微的塌缩     

Statistical mechanics of semiflexible polymers

We present the statistical-mechanical theory of semiflexible polymers based on the connection between the Kratky-Porod model and the quantum rigid rotator in an external homogeneous field, and treatment of the latter using the quantum mechanical propagator method. The expressions and relations existing for flexible polymers can be generalized to semiflexible ones, if one replaces the Fourier-Laplace transform of the end-to-end polymer distance, 1/(k ²/3 + p), through the matrix , where D and M are related to the spectrum of the quantum rigid rotator, and considers an appropriate matrix element of the expression under consideration. The present work provides also the framework to study polymers in external fields, and problems including the tangents of semiflexible polymers. We study the structure factor of the polymer, the transversal fluctuations of a free end of the polymer with fixed tangent of another end, and the localization of a semiflexible polymer onto an interface. We obtain the partition function of a semiflexible polymer in half space with Dirichlet boundary condition in terms of the end-to-end distribution function of the free semiflexible polymer, study the behaviour of a semiflexible polymer in the vicinity of a surface, and adsorption onto a surface.Received: 23 March 2004, Published online: 23 July 2004PACS: 36.20.-r Macromolecules and polymer molecules - 61.41. + e Polymers, elastomers, and plastics - 82.35.Gh Polymers on surfaces; adhesion     

Harmonically Confined, Semiflexible Polymer in a Channel: Response to a Stretching Force and Spatial Distribution of the Endpoints

We consider an inextensible, semiflexible polymer or worm-like chain which is confined in the transverse direction by a parabolic potential and subject to a longitudinal force at the ends, so that the polymer is stretched out and backfolding is negligible. Simple analytic expressions for the partition function, valid in this regime, are obtained for chains of arbitrary length with a variety of boundary conditions at the ends. The spatial distribution of the end points is also analyzed.     

Force-induced desorption and unzipping of semiflexible polymers

The thermally assisted force-induced desorption of semiflexible polymers from an adhesive surface or the unzipping of two bound semiflexible polymers by a localized force are investigated. The phase diagram in the force-temperature plane is calculated both analytically and by Monte Carlo simulations. Force-induced desorption and unzipping of semiflexible polymers are first order phase transitions. A characteristic energy barrier for desorption is predicted, which scales with the square root of the polymer bending rigidity and governs the initial separation process before a plateau of constant separation force is reached. This leads to activated desorption and unzipping kinetics accessible in single molecule experiments.     

Off-lattice Monte Carlo simulation of supramolecular polymer architectures

We introduce an efficient, scalable Monte?Carlo algorithm to simulate cross-linked architectures of freely?jointed and discrete wormlike chains. Bond movement is based on the discrete tractrix construction, which effects conformational changes that exactly preserve fixed-length constraints of all bonds. The algorithm reproduces known end-to-end distance distributions for simple, analytically tractable systems of cross-linked stiff and freely jointed polymers flawlessly, and is used to determine the effective persistence length of short bundles of semiflexible wormlike chains, cross-linked to each other. It reveals a possible regulatory mechanism in bundled networks: the effective persistence of bundles is controlled by the linker density.     

Stretching of semiflexible polymers with elastic bonds

A semiflexible harmonic chain model with extensible bonds is introduced and applied to the stretching of semiflexible polymers or filaments. The semiflexible harmonic chain model allows to study effects from bending rigidity, bond extension, discrete chain structure, and finite length of a semiflexible polymer in a unified manner. The interplay between bond extension and external force can be described by an effective inextensible chain with increased stretching force, which leads to apparently reduced persistence lengths in force-extension relations. We obtain force-extension relations for strong- and weak-stretching regimes which include the effects of extensible bonds, discrete chain structure, and finite polymer length. We discuss the associated characteristic force scales and calculate the crossover behaviour of the force-extension curves. Strong stretching is governed by the discrete chain structure and the bond extensibility. The linear response for weak stretching depends on the relative size of the contour length and the persistence length which affects the behaviour of very rigid filaments such as F-actin. The results for the force-extension relations are corroborated by transfer matrix and variational calculations.PACS: 87.15.-v Biomolecules: structure and physical properties - 87.15.Aa Theory and modeling; computer simulation - 87.15.La Mechanical properties     

Semiflexible polymers in shear flow

The dynamics of semiflexible polymers under the influence of shear flow is studied analytically. Power laws are derived for various conformational and dynamical quantities which are in agreement with experimental findings. In particular, the tumbling motion is analyzed and expressions are provided for the probability distributions of the orientation angles and the tumbling time. The calculations explain the similarities in the behavior of flexible and semiflexible polymers as well as free-draining and nondraining systems.     

Polymer-like Behavior of Inorganic Nanoparticle Chain Aggregates

Studies of the behavior of nanoparticle chain aggregates (NCA) have shown properties similar to those of molecular polymers. Like polymer chains, NCA tend to gather up and become more compact when heated. Under tensile stress, folded chain segments pull out and the NCA elongates. When the tension is relaxed, the chains contract. The stretching of NCA may contribute to the ductility of compacts made from nanoparticles, a subject of current research interest. In a well established technological application, carbon black and pyrogenic silica NCA produce remarkable increases in elastic modulus and tensile strength when added to commercial rubber. This may be due to the mechanical interaction between the polymer chains and NCA. However, basic mechanisms of NCA elasticity differ from those of molecular polymers. The alignment of chain segments when the NCA are subjected to tension probably results from rotation and translation at grain boundaries between neighboring nanocrystals. The elastic properties depend on the van der Waals forces between segments of the chain that fold to minimize surface free energy. Under tension, these segments pull out, but tend to reform when the tension is relaxed. The processes that lead to NCA formation and control the strength of interparticle bonds are briefly reviewed.     

Diffusion and segmental dynamics of double-stranded DNA

Diffusion and segmental dynamics of the double-stranded lambda-phage DNA polymer are quantitatively studied over the transition range from stiff to semiflexible chains. Spectroscopy of fluorescence fluctuations of single-end fluorescently labeled monodisperse DNA fragments unambiguously shows that double-stranded DNA in the length range of 10(2) - 2 x 10(4) base pairs behaves as a semiflexible polymer with segmental dynamics controlled by hydrodynamic interactions.     

Semiflexible polymers in straining flows

We introduce a model for semiflexible polymer chains based on the integral of an appropriate Gaussian process. The stiffness is characterized physically by adding a bending energy. The degree of stiffness in the polymer chain is quantified by means of a parameter and as this parameter tends to infinity, the limiting case reduces to the Brownian model of completely flexible chains studied in earlier work. The calculation of the partition function for the configuration statistical mechanics (i.e., the distribution of shapes) of such polymers in elongational flow or quadratic potentials is equivalent to the probabilistic problem of finding the law of a quadratic functional of the associated Gaussian process. An exact formula for the partition function is presented; however, in practice, this formula is too complicated for most computations. We therefore develop an asymptotic expansion for the partition function in terms of the stiffness parameter and obtain the first-order term which gives the first-order deviation from the completely flexible case. In addition to the partition function, the method presented here can also deal with other quadratic functionals such as the “stochastic area” associated with two polymer chains.