近壁模型高分子链的计算机模拟

采用简立方格点上的普通无规行走 (NRW)和自避行走 (SAW )为模型链 ,研究了不可穿透的刚性壁附近高分子的构象性质 ,得出近壁链的构象熵和尺寸随一端点与壁之间距离z0 的变化 .所用的计算机模拟技术包括精确计数和MonteCarlo模拟 .数值结果表明 ,近壁链的构象熵降低遵循一种简单规律 ,即当链长愈长或一端愈接近于壁时 ,与长度相同的自由链相比 ,链因壁限制所致构象熵的降低愈大 .当链十分接近于壁时 ,其均方末端距〈R2 〉(尤其是与壁垂直的分量〈R2z〉)大于自由链的相应值 ;随z0 增大 ,〈R2 〉及〈R2z〉开始减小 ,通过某一极小值 ,然后上升 ;当z0 →∞时 ,趋于自由链的极限值 .换言之 ,近壁模型链的线团经历一个收缩再逐渐扩张的过程     

端基附壁模型聚合物环形链的构象统计理论

环形链定义为两个端基均附壁的线形聚合物链所得的环 .采用精确计数和蒙特卡罗模拟方法 ,研究了自回避行走 (SAW)模型表示的环形链的构象 ,求得构象数和均方回转半径随链长的变化 .对于二维和三维SAW环形链 ,精确计数的最大链长分别为N =2 9和 1 9.用标度理论处理了数值结果 ,所得的标度指数和其他参数与理论预示值进行了比较 .模拟结果表明 ,SAW环形链限制壁平行方向的尺寸大于垂直方向的尺寸 ,与SAW尾形链尺寸的变化正好相反 .     

端基附壁高分子链的构象统计理论——Ⅱ.SAW尾形链

研究了SAW尾形链,采用精确计数和Monte Carlo模拟方法求得d维(d=2,3)SAW尾形链的构象数C_1~d和均方末端距[h_1~d(N)]~2及其分量随链长N的变化关系.发现它们与自由SAW链一样都服从标度律,从模拟数据拟合求出了这些SAW尾形链的临界指数.还表明短链SAW在壁的法向与NRW尾形链一样有所伸展,均方末端距的法向分量几乎是平行分量的2倍;但随N→∞,链自回避效应对壁的作用有所屏蔽,这与NRW尾形链有明显不同.     

二维正方形格点上自踪迹规避链的临界指数

用实空间中的重整化群理论 ,对二维正方形格点上的高分子模型自踪迹规避链进行了求解 .求得自踪迹规避链的相关长度指数νSAT为 0 759,格点的等效配位数 μSAT为 2 96 8     

受限于平行界面之间高分子链力学行为的研究

采用PERM(pruned-enriched-rosenbluth method)算法,和简立方格点上的自避行走模型,研究了受限于平行界面之间的星型高分子链和线型高分子链的力学行为,并将两种结果进行了比较.模拟结果表明,如果界面对高分子链存在吸附作用,界面之间距离D的增大需要外力的作用;如果界面对链没有吸附作用,则D的增大是一个自发的过程,无需外力的作用.随着界面间距D的增大,通过计算星型链和线型链的均方回转半径〈S2〉和形状因子〈δ*〉,研究了链尺寸和形状的变化情况.另外,为了更细微地了解星型链和线型链的结构及力学行为,还研究了受限高分子链在平行界面之间的轨链(train)、环链(bridge)和尾链(tail).     

酶解法制备方格星虫多肽及其抗氧化作用研究

采用木瓜蛋白酶酶解制备方格星虫多肽,通过单因素实验研究了加酶量、酶解温度、酶解时间、酶解pH值和料液比等因素对羟自由基清除率的影响。通过正交试验确定了木瓜蛋白酶对方格星虫最佳的酶解工艺条件为:加酶量300 U/g,酶解温度50℃,酶解时间60 min,酶解液pH值7.0,料水比1∶3。在此条件下酶解方格星虫获得多肽的羟自由基清除率为95.42%,表明方格星虫酶解物具有较明显的抗氧化能力。由高效体积排阻色谱(HPSEC)法测得方格星虫多肽的分子量为5868。     

二维三角格子上高分子动态 Monte Carlo模拟的协同运动算法

在动态Monte Carlo模拟的协同运动算法中,几个相邻的链节可以同时运动,这可以理解为高分子链中张力的作用引起的协同运动。将这一算法用于二维三角格子模型上RW链和SAW链的模拟。结果表明RW链的动力学行为符合Rouse理论,说明说明该算法可以用于高分子动力学研究,其优点是不需要使用键长涨落模型。     

金刚石格点上自避行走尾形链的构象统计理论

研究了金刚石格点上自避随机行走（ＳＡＷ）尾形链，采用精确计数和ＭｏｎｔｅＣａｒｌｏ模拟方法求得该ＳＡＷ尾形链的构象数Ｃ（Ｄ）１（Ｎ）和均方末端距［ｈ（Ｄ）１（Ｎ）］２及其分量随链长Ｎ的变化关系．发现它们与自由ＳＡＷ链一样都服从标度律，从这些量的计算机实验数据拟合求出了金刚石格点上ＳＡＷ尾形链的临界指数和格点指数．计算结果还表明短链ＳＡＷ在壁的法向与ＮＲＷ尾形链一样有所伸展，均方末端距的法向分量几乎是平行分量的２倍；但随Ｎ→∞，链自回避效应对壁的作用有所屏蔽．这些都与简立方格子模型上得到的结果一致．     

海藻酸钠水溶液的Sol-Gel转变与凝胶化点的决定

测定了 4个分子量和分子量分布不同、M G不同的海藻酸钠试样在不同浓度下的恒温 (2 5℃ )动态粘弹谱 ,发现 4个试样随溶液浓度升高都会发生溶胶 凝胶 (Sol gel)转变 .实验结果表明 ,该转变符合Winter和Chambon的凝胶化点临界状态的松弛模量G(t)方程 ,由tanδ不依赖于ω的判据求出了海藻酸钠水溶液随浓度变化发生Sol gel转变、出现物理凝胶化的凝胶化点溶液浓度cgel和临界指数n .cgel=7 6wt%～ 8 0wt% ,基本与分子量无关 ;分子量较高的 3个试样的n =0 32～ 0 38,而分子量低的试样的n =0 6 1.该结果表明 ,物理凝胶化主要是由大分子重复单元间的相互作用决定 ,分子链越长则凝胶化点的交联结构越完善     

简立方格点自避行走所模拟的高分子链吸附和塌缩

采用复合Markov链法 ,针对简立方格点上的自避行走模型 ,研究了同时具有对壁的吸附作用ε1 和最近邻相互作用ε2 的高分子链的热力学性质 .相互作用能量参数ε1 和ε2 分别联系于参数α和 β .令链长N=10 0 ,由这种MonteCarlo方法可得出链的自由能FN(α ,β) ,热容2 FN(α ,β) /2 α和2 FN(α ,β) /2 β ,吸附点平均数〈m〉/N ,最近邻相互作用对平均数〈n〉/N和均方末端距对壁的垂直分量RZ2 .除已有方法由热容数据可绘出α β相图外 ,建议由结构参数〈m〉/N ,〈n〉/N和RZ2 绘制相图 ,并发现二者基本一致 .所得相图表明 ,存在 4个相区 ,分别是解吸 膨胀相 (DE) ,吸附 膨胀相 (AE) ,解吸 紧密相 (DC)和吸附 紧密相 (AC) .在伸展区和塌缩区 ,随着吸附作用的增强 ,会出现吸附相转变 .在解吸区和吸附区 ,随着自相互作用的增大 ,也将出现塌缩相转变 .相图出现了两个三相点 ,即AE AC DC三相点和AE DE DC三相点     

COMPUTER SIMULATION OF A SINGLE POLYMER CHAIN IN DIFFERENT SOLVENTS

In the present paper, the behavior of a single polymer chain under various solvent conditions was modeled by self-avoiding walks (SAW) with nearest neighbors attraction Δε on a simple cubic lattice. Determination of the θ-condition wasbased on the numerical results of the mean square radius of gyration and end-to-end distance. It was found that at the θtemperatue Δε/kT equals -0.27. The exponents a in the Mark-Houwink equation with different interaction parameters areconsistent with the results of experiments: under θ-condition, a = 0.5, and for a good solvent α= 0.74-0.84, respectively.     

Conformational statistics of polymer chain terminally attached to wall (II)

The SAW tail chains were studied. The permitted conformational number and the mean square end-to-end distance as a function of the chain length N for such a model tail chain were obtained by computer simulations, including the exact enumeration and Monte Carlo method. These two basic quantities obeyed the relations deduced from the scaling law. The critical exponents and the lattice indexes were given by fitting the data of the computer experiments. It has been shown that there is a certain extension in the size of the SAW tail chains as well as the NRW tail chains in the direction normal to the wall. The normal component of the mean square end-to-end distance is almost twice as large as the parallel component of the short chain SAW. However, as N →∞, the effect of the wall on the chain conformation becomes a little weak because of the self-avoiding behavior for the model. That is quite different from the case of the NRW tail chain. Project supported by the National Natural Science Foundation of China     

Modeling of monolayer adsorption of hydrogen on ZSM‐5 zeolite by lattice density functional theory

The adsorption isotherms of hydrogen on microporous zeolite ZSM‐5, at supercritical conditions, have been modeled using the monolayer lattice density functional theory (LDFT) models, where the simple cubic lattice, face‐centered cubic lattice, body‐centered cubic lattice and tetragonal lattice structures are assumed for the arrangements of the adsorption sites inside pores based on the size and shape of the zeolite. The results indicate that the monolayer LDFT models appear to be effective in describing hydrogen adsorption on zeolite ZSM‐5 at supercritical conditions, and the calculated adsorption isotherms agree well with the experimental isotherms measured previously. The layer density of adsorbed phase is presented versus the bulk density and temperature. It is found that the densities of adsorbed phase on adsorbent surface are much higher than the bulk density for temperature range under study. However, in the core region, the layer densities are close to the bulk density. The monolayer adsorption is suitable for hydrogen on ZSM‐5 zeolite. Copyright © 2013 John Wiley & Sons, Ltd.     

Dynamic Elasticity of Cubic Diamond

Previously, the structure of the carbon allotrope glitter has been disclosed, and a theory accompanying the structural report as to its bulk modulus at pressure predicted it would be among the hardest materials possible. The dynamic elasticity theory developed in that paper, involving the forces generated in elastic chemical bond deformations resulting from applied mechanical forces, is here applied to the cubic diamond lattice. Stresses, both lateral and axial, contribute to the bulk modulus of cubic diamond at pressure. The ultimate strength of the cubic diamond lattice, in the approximations of the dynamic elasticity theory presented in this paper, is estimated to be in excess of 1 TPa, at modest bond length deformations of about 0.1 ?, and when including the zero pressure bulk modulus B ₀ in the computation. In particular, the dynamic elasticity model predicts the hardest direction of cubic diamond will be for an isotropic mechanical force applied along 〈111〉 directions of the structural unit cell.     

DYNAMIC MONTE CARLO STUDY ON THE CORRELATION BETWEEN SHAPE AND SIZE OF LINEAR POLYMER CHAINS

The correlation between shape and size of linear chains on the simple cubic lattice is investigated using a dynamicMonte Carlo technique. A positive correlation between the asphericity parameter A and the square of the end-to-end distanceR~2, as well as that between A and the square of the radius of gyration S~2, is found for both RW and SAW chains, indicatingthat a chain conformation of small size is usually more spherical than one of large size. The result can explain why the shapeof the SAW chain deviate much more from a sphere than that of the RW chain, and can also explain the similar dependenceof size and shape on chain stiffness and on the distance of the first bead of a chain from an infinitely large flat surface.     

Polymer collapse, protein folding, and the percolation threshold

We study the transition of polymers in the dilute regime from a swollen shape at high temperatures to their low-temperature structures. The polymers are modeled by a single self-avoiding walk (SAW) on a lattice for which l of the monomers (the H monomers) are self-attracting, i.e., if two nonbonded H monomers become nearest neighbors on the lattice they gain energy of interaction (epsilon = -/epsilon/); the second type of monomers, denoted P, are neutral. This HP model was suggested by Lau and Dill (Macromolecules 1989, 22, 3986-3997) to study protein folding, where H and P are the hydrophobic and polar amino acid residues, respectively. The model is simulated on the square and simple cubic (SC) lattices using the scanning method. We show that the ground state and the sharpness of the transition depend on the lattice, the fraction g of the H monomers, as well as on their arrangement along the chain. In particular, if the H monomers are distributed at random and g is larger than the site percolation threshold of the lattice, a collapsed transition is very likely to occur. This conclusion, drawn for the lattice models, is also applicable to proteins where an effective lattice with coordination number between that of the SC lattice and the body centered cubic lattice is defined. Thus, the average fraction of hydrophobic amino acid residues in globular proteins is found to be close to the percolation threshold of the effective lattice.     

Finite-size scaling analysis on the phase transition of a ferromagnetic polymer chain model

The finite-size scaling analysis method is applied to study the phase transition of a self-avoiding walking polymer chain with spatial nearest-neighbor ferromagnetic Ising interaction on the simple cubic lattice. Assuming the scaling M2(T,n) = n(-2beta/nu)[phi0 + phi1n(1/nu)(T-T(c)) + O(n(2/nu)(T-T(c))2)] with the square magnetization M2 as the order parameter and the chain length n as the size, we estimate the second-order phase-transition temperature T(c) = 1.784 J/k(B) and critical exponents 2beta/nu approximately 0.668 and nu approximately 1.0. The self-diffusion constant and the chain dimensions (R2) and (S2) do not obey such a scaling law.