介观化学体系中的动力学尺度效应

以生命和表面催化体系为对象,研究了介观化学体系中内涨落对体系非线性动力学行为的调控作用。内涨落可以诱导随机振荡,其强度在体系处于最佳尺度时会出现一个甚至多个极大值,并且在耦合体系中会得到进一步增强,表现为尺度共振效应、尺度选择效应和双重尺度效应,揭示了介观化学体系中尺度效应的新机制。     

介观化学体系中的动力学尺度效应

以生命和表面催化体系为对象,研究了介观化学体系中内涨落对体系非线性动力学行为的调控作用.内涨落可以诱导随机振荡,其强度在体系处于最佳尺度时会出现一个甚至多个极大值,并且在耦合体系中会得到进一步增强,表现为尺度共振效应、尺度选择效应和双重尺度效应,揭示了介观化学体系中尺度效应的新机制.     

介观振荡化学反应体系的内噪声随机共振

用化学Langevin方程研究了内噪声对介观振荡化学反应体系的影响.研究发现,在确定性体系处于定态条件下,内噪声可以导致体系振荡:随着内噪声强度的变化,诱导振荡信号的信噪比通过一个极大值,表明内噪声随机共振的出现;由于内噪声强度随着系统体积的变化而改变,因此,这一现象也证明了系统尺度共振,即最佳尺度效应的存在.     

卤化银成像体系中的纳米化学*

纳米化学研究的对象是尺寸在1 ~100nm的化学实体,它构成了一个介乎微观相和宏观相之间的介观相 (mesoscopic phase),介观相不仅反映了化学实体在尺寸上从微观向宏观的过渡,而且表现了一系列特殊的效应和功能。本文探讨了纳米化学对卤化银成像体系的冲击和卤化银成像过程的研究对纳米化学的发展所做出的贡献。     

介观生化反应的随机和混合模拟算法

随着细胞等介观体系中研究的深入,介观生化反应的模拟方法日益引起人们的关注。一方面,这类体系中涨落效应显著,化学反应本质上是随机的离散过程,经典的确定性模拟方法不再适用,需要使用随机模拟方法;另一方面,这种体系中子反应的速率和反应物的分子数目可能有显著差别,存在多尺度特性,使一般随机算法的模拟效率极低,对反应的准确高效模拟提出了新的要求。本文简述了Gillespie提出的一系列基本随机算法,综述了近年来发展的针对反应多尺度特性的改进随机算法和混合算法,介绍了各类算法的特点、实现的技术问题及相对其他算法和实际生物信号描述表现出的优缺点。     

理论化学与下世纪“化学学科重组”前瞻

本文展望了理论化学的发展趋势并预言了下个世纪“化学学科的重组”。作者建议了现代化学的定义：化学是研究从原子,分子片,分子,超分子,生物大分子到分子的各种不同尺度和不同程度的聚集态的合成和反应,分离和分析,结构和形态,物理性能和生物活性及其规律和应用的科学． 根据这个定义,从化学的研究对象不同,在２１ 世纪化学分支学科可能发生重组,因此化学可以划分为如下八个层次：１） 原子层次的化学; ２） 分子片层次的化学; ３） 分子层次的化学; ４） 超分子层次的化学; ５）生物与分子层次的化学; ６） 宏观聚集态化学; ７） 介观聚集态化学和８） 复杂分子体系的化学     

化学Lorenz模型中混沌的介观动力学

用系综模拟方法研究了化学Lorenz模型中混沌的介观动力学. 通过对主方程的随机模拟, 分析了盒频率(bin frequency)以及涨落和协方差在不同参数区的时间演化行为. 系综模拟分析在比通常宏观方程描述更为基本的层次上, 展示了确定性混沌的介观动力学图景. 对主方程也用累积展开法进行了分析.     

纳米尺度钯粒子表面一氧化碳氧化反应内噪声随机共振

在随机模型的基础上, 运用化学Langevin 方程、Poisson近似和精确随机模拟方法, 研究了内噪声对纳米(nm)尺度钯(Pd)粒子表面上一氧化碳(CO)催化氧化反应的影响. 在这类介观体系中, 由于显著内噪声的存在, 化学反应速率振荡具有随机性. 研究发现, 对于给定的CO偏压, 随着内噪声强度的改变, 随机振荡强度经过一个极大值, 从而证明了内噪声随机共振的存在. 这一现象表明, 合适的内噪声有利于反应速率振荡. 这种内噪声随机共振行为对外界参数(如CO偏压)具有稳定性(robust).     

磺化聚苯乙烯有序孔水凝胶的制备及其模板效应

有序大孔聚苯乙烯材料通过胶体晶模板技术合成, 再经过磺化处理制备得到有序大孔水凝胶体系. 研究了其化学组成和形态. 以溶胶/凝胶制备有序无机材料如二氧化钛对凝胶进行复型, 证明了有序大孔凝胶的形态特征, 同时显示了有序大孔水凝胶作为新型模板制备形态可控的介观尺度有序无机材料的潜力.     

介观尺度多孔材料的电子显微学结构解析

孔径在介观尺度的多孔材料由于其规整的孔道结构、大比表面积、特殊的空间限域效应使其在吸附、分离、催化、传感、载药、能源等领域都具有广阔的应用前景. 深入解析材料的结构特征不仅是理解其物理化学性能和应用的关键, 也是研究材料的形成机理及新材料制备的重要反馈和支持. 电子显微学以电子为探针, 通过电子衍射和高分辨像对材料结构展开探索, 可以研究更小尺寸晶体的结构, 揭示局部结构信息如缺陷及共生等, 对介观尺度多孔材料的结构解析至关重要. 对近年来通过电子显微学方法解析的介观尺度多孔材料工作进行了综述, 主要针对有序介孔材料以及有序大孔材料展开, 归纳了不同结构类型的介观尺度多孔材料所适用的电子晶体学方法, 在此基础上提出电子显微学在介观尺度孔材料结构解析上的优势、不足和未来发展的方向, 以及将电子显微学用于其它材料结构解析的可行性.     

Theoretical study on the effects of internal noise for rate oscillations during CO oxidation on platinum(110) surfaces

Very recently, the effects of internal molecular noise in mesoscopic chemical reaction systems have gained growing attention. Using a mesoscopic stochastic model, the effect of internal noise for rate oscillation during CO oxidation on Pt(110) surface is studied analytically. In a parameter region outside but close to the supercritical Hopf bifurcation, a stochastic normal form is obtained from the chemical Langevin equation. By stochastic averaging procedure, the system is simplified and solvable. Noise-induced oscillation and internal noise coherent resonance (which is related to an optimal system size), observed from simulations, are well reproduced by the theory. The theoretical analysis helps to clearly figure out when and how the internal noise affects the system's oscillating dynamics.     

耦合生物细胞体系中内噪声对检测弱刺激的积极作用

By constructing a mesoscopic stochastic model for intracellular calcium oscillations in coupled cell system, we investigated the influence of internal noise on the detection of weak stimulation using the chemical Langevin equation (CLE). We found that an optimal cell size V existed for a coupled cell chain length N and an optimal value of N existed for a given cell size V. At these values, the collective calcium oscillations showed the best performance, indicating the occurrence of“system size resonance (SSR)”or“internal noise stochastic resonance (INSR)”. And such a phenomenon was robust to the coupling strength. Living cells may have learned to exploit the internal noise to detect weak stimulation via the mechanism of INSR, and then encode information to specifically regulate distinct cellular functions. It is interesting to note that the optimal cell size is always present at V抑103 μm3, which is close to the real living cell size in vivo. Since the internal noise in living systems can not be ignored and the systems may often encounter weak stimulations, our findings might have significance for stimulation detecting processes in living systems.     

Internal noise stochastic resonance in CO oxidation on nm-sized palladium particles

The constructive roles of noise and disorder in nonlinear system have been extensively studied in the last two decades. Among them the most well known phenomenon is stochastic resonance[1], which demon-strates that noise can help a nonlinear system to det…     

自催化三分子模型内噪声随机共振

The stochastic resonance in chemical reaction systems has recently attracted growing attentions. Using chemical Langevin equation,the effect of internal noise has been studied on the dynamical behavior of a single and a one-way coupled cubic autocatalator. For the single system,it is found that the internal noise can induce sustained oscillations,and the signal-to-noise ratio（SNR）undergoes a maximum with the variation of the system size. For the coupled system,the SNR passes through a maximum with changing coupling strengths as well as with changing system sizes,which demonstrates the occurrence of the internal noise stochastic resonance（INSR）and optimal size effect. In the presence or absence of influx into the system,the coupling enhanced or suppressed INSR is found in the coupled system. All cells of the coupled system appear to exhibit INSR at an approximately equal size at a suitable coupling strength,implying that the optimal system size and coupling strength can make the system reach an optimal chemical reaction state.     

Internal noise coherent resonance for mesoscopic chemical oscillations: a fundamental study.

The effect of internal noise for a mesoscopic chemical oscillator is studied analytically in a parameter region outside, but close to, the supercritical Hopf bifurcation. By normal form calculation and a stochastic averaging procedure, we obtain stochastic differential equations for the oscillation amplitude r and phase theta that is solvable. Noise-induced oscillation and internal noise coherent resonance, which has been observed in many numerical experiments, are reproduced well by the theory.     

Multiscale coupling of mesoscopic- and atomistic-level lipid bilayer simulations

A multiscale method is presented to bridge between the atomistic and mesoscopic membrane systems. The atomistic model in this case is the united atom dimyristoylphosphatidylcholine membrane system, although the method is completely general. Atomistic molecular dynamics provides the expansion modulus which is used to parametrize a mesoscopic elastic membrane model. The resulting elastic membrane model, including explicit mesoscopic solvent, shows appropriate static and dynamic undulation behaviors. Large membranes of approximately 100 nm in length can then be easily simulated using the mesoscopic membrane system. The critical feedback from the mesoscopic system back down to the atomistic-scale system is accomplished by bridging the stress (or surface tension) of a small region in the mesoscopic membrane to the corresponding atomistic membrane system. Because of long length-scale modes of membranes such as undulation and buckling, the local tension responds differently from the frame tension, when subjected to external perturbations. The effect of these membrane modes is shown for the stress response of a local membrane region and therefore the atomistic membrane system. In addition, certain equilibrium static and dynamic properties of stand-alone and multiscale coupled systems are presented for several different membrane sizes. Although static properties such as two-dimensional pair-correlation function and order parameters show no noticeable discrepancy for the different systems, lipid self-diffusion and the rotational relaxation of lipid dipoles have a strong dependence on the membrane size (or long-wavelength membrane motions), which is properly modeled by the present multiscale method.     

Discrete models for chemically reacting systems

Nonequilibrium spatially distributed chemically reacting systems are usually described in terms of reaction-diffusion equations. In this article, a hierarchy of discrete models is studied that show similar spatio-temporal structure and can be used to explore the complex phenomena occurring in these systems. We consider cellular automaton models where space, time and chemical concentrations are discrete and the dynamics is embodied in a simple updating rule, coupled map lattices where space and time are discrete variables but chemical concentrations are continuous and the dynamics is given by a nonlinear function and, lastly, lattice gas cellular automaton models that view the system on a microscopic or mesoscopic level where space, time and particle velocities are discrete.