Potentials of mean force for hydrophobic interactions between hydrocarbons in water solution: dependence on temperature,solute shape,and solute size

We carried out molecular dynamics (MD) simulations with the AMBER force field for four pairs of spherical dimers of different size (neopentane, bicyclooctane, adamantane, and fullerene‐C₆₀) using the TIP3P model of water as solvent. For comparison, we performed MD simulations for a linear molecule of n‐pentane at the same conditions. To assess the entropy contribution to the Gibbs free energy, MD simulations were run at three different temperatures of 273 K, 323 K, and 348 K, respectively, using umbrella‐sampling/the WHAM method. The stability of dimers is described by a potential of mean force (PMF). The shape of PMF curves for hydrophobic interactions is characteristic, and entails a contact minimum, a solvent‐separated minimum, and a desolvation maximum. The depth and position of the contact minimum for each pair change with the size of the nonpolar particle, and are consequently shifted to a larger distance for larger molecules. Additionally, the Lennard–Jones contribution to the PMF increases simultaneously with an increase in particle size. For a linear dimer, the contact minimum is shifted to a shorter distance than it is for spherical systems with the same number of carbon atoms. The contact minima on PMF curves increase with temperature, suggesting that the association entropy is positive. Dimensionless PMF curves showed a low dependency (near contact minima regions) on temperature, as the association entropy is low. Copyright © 2014 John Wiley & Sons, Ltd.     

k‐Version of finite element method in 2‐D polymer flows: Oldroyd‐B constitutive model

In this paper, a new mathematical framework based on h, p, k and variational consistency (VC) of the integral forms is utilized to develop a finite element computational process of two‐dimensional polymer flows utilizing Oldroyd‐B constitutive model. Alternate forms of the choices of dependent variables in the governing differential equations (GDEs) are considered and is concluded that u, v, p, τ choice yielding strong form of the GDEs is meritorious over others. It is shown that: (a) since, the differential operator in the GDEs is non‐linear, Galerkin method and Galerkin method with weak form are variationally inconsistent (VIC). The coefficient matrices in these processes are non‐symmetric and hence may have partial or completely complex basis and thus the resulting computational processes may be spurious. (b) Since the VC of the VIC integral forms cannot be restored through any mathematically justifiable means, the computational processes in these approaches always have possibility of spurious solutions. (c) Least squares process utilizing GDEs in u, v, p, τ (strong form of the GDEs) variables (as well as others) is variationally consistent. The coefficient matrices are always symmetric and positive definite and hence always have a real basis and thus naturally yield computational processes that are free of spurious solutions. (d) The theoretical solution of the GDEs are generally of higher order global differentiability. Numerical simulations of such solutions in which higher order global differentiability characteristics of the theoretical solution are preserved, undoubtedly requires local approximations in higher order scalar product spaces . (e) LSP with local approximations in spaces provide an incomparable mathematical and computational framework in which it is possible to preserve desired characteristics of the theoretical solution in the computational process. Numerical studies are presented for fully developed flow between parallel plates and a lid driven square cavity. M1 fluid is used in all numerical studies. The range of applicability of the Oldroyd‐B model or lack of it is examined for both model problems for increasing De. A mathematical idealization of the corners where stationary wall meets the lid is presented and is shown to simulate the real physics when the local approximations are in higher order spaces and when h_d→0. For both model problems shear rate is examined in the flow domain to establish validity of the Oldroyd‐B constitutive model. Copyright © 2006 John Wiley & Sons, Ltd.     

Balancing Ligand Flexibility versus Rigidity for the Stepwise Self-Assembly of M12L24 via M6L12 Metal–Organic Cages

Non-covalent interactions are important for directing protein folding across multiple intermediates and can even provide access to multiple stable structures with different properties and functions. Herein, we describe an approach for mimicking this behavior in the self-assembly of metal–organic cages. Two ligands, the bend angles of which are controlled by non-covalent interactions and one ligand lacking the above-mentioned interactions, were synthesized and used for self-assembly with Pd²⁺. As these weak interactions are easily broken, the bend angles have a controlled flexibility giving access to M₂( L1 )₄, M₆( L2 )₁₂, and M₁₂( L2 )₂₄ cages. By controlling the self-assembly conditions this process can be directed in a stepwise fashion. Additionally, the multiple endohedral hydrogen-bonding sites on the ligand were found to play a role in the binding and discrimination of neutral guests.     

Anisotropic Nucleation,Growth and Ripening under Stirring—A Phenomenological Model

The anisotropic formation of elongated metal-oxide aggregates in water under intensive stirring is analyzed. It is treated in terms of anisotropic ballistically mediated aggregation kinetics in open systems. The basic kinetic equations describing the stages of homogeneous nucleation, independent growth, and ripening of the aggregates are formulated for the open system under the external influence with the stirring intensity as the main parameter governing the process. The most significant elongation of the aggregates is shown to evolve at the ripening stage.     

Augmented Lagrangian-based preconditioners for steady buoyancy driven flow

In this paper, we apply the augmented Lagrangian (AL) approach to steady buoyancy driven flow problems. Two AL preconditioners are developed based on the variable’s order, specifically whether the leading variable is the velocity or the temperature variable. Correspondingly, two non-augmented Lagrangian (NAL) preconditioners are also considered for comparison. An eigenvalue analysis for these two pairs of preconditioners is conducted to predict the rate of convergence for the GMRES solver. The numerical results show that the AL preconditioner pair is insensitive with respect to the mesh size, Rayleigh number, and Prandtl number in terms of GMRES iterations, resulting in a significantly more robust preconditioner pair compared to the NAL pair. Accordingly, the AL pair performs much better than the NAL pair in terms of computational time. For the AL pair, the preconditioner with velocity as the leading variable gives slightly better efficiency than the one with temperature as the leading variable.     

加速器驱动次临界系统——先进核燃料循环的选择

加速器驱动次临界系统(Accelerator Driven Sub-critical System,ADS)是利用加速器产生的高能强流质子束轰击重核时产生的外源中子,来驱动次临界堆芯中裂变材料发生的持续的链式反应,使得长寿命放射性核素最终变为非放射性的或短寿命的核素,并维持反应堆运行,因而具有该系统所固有的安全性。ADS的中子能谱硬,通量大,能量分布宽,嬗变长寿命核素能力强,可大幅降低核废料的放射性危害,实现核废料的最少化,被国际公认为是核废料处理最有前景的技术途径。文章介绍了ADS研究的国家需求,概述了ADS技术原理及挑战,同时介绍了中国科学院战略性先导科技专项(A类)“未来先进核裂变能——ADS嬗变系统”这一研究课题实施进展情况,并对未来发展进行了展望。     

高校实验教学立体化创新模式的探索与实践

本文在创新的"长效驱动机制"和"目标利益激励机制"下,就如何让教师创新积极性与学生创新积极性相结合,探索和实践将实验教学课与通识选修课相结合的立体化创新模式,以期达到让创新人才培养在教育中驻足,提高学生创新素质和创新能力。     

High Temperature Expansion for a Driven Bilayer System

Based directly on the microscopic lattice dynamics, a simple high temperature expansion can be devised for non-equilibrium steady states. We apply this technique to investigate the disordered phase and the phase diagram for a driven bilayer lattice gas at half filling. Our approximation captures the phases first observed in simulations, provides estimates for the transition lines, and allows us to compute signature observables of non-equilibrium dynamics, namely, particle and energy currents. Its focus on non-universal quantities offers a useful analytic complement to field-theoretic approaches.     

微重力下变内角毛细驱动流研究

本文研究了在满足Concus-Finn条件时,微重力环境下内角沿容器轴线变化时的毛细驱动流问题,建立了变内角的毛细流动控制方程,获得了变内角流动的近似解析解,并与FLOW-3D软件的数值模拟结果进行了对比验证. 计算结果表明,随着时间的增大,近似解析解与数值解的相对误差越来越小,在6 s以后,相对误差不超过5%. 论文研究了不同结构参数对内角毛细流动的影响规律,得出液体前缘位置和液面高度均随内角、接触角、内角斜率和内角幂指数的增大而减小的结论. 在不同时刻,液体的液面高度随着时间的增大而增大,但在初始时刻存在一个常高度,该高度不随时间的变化而变化. 在空间流体管理时,可以根据本文的工作进行容器设计和选择适合的溶液. 关键词： 变内角 毛细驱动流 近似解析解 前缘位置