Determination of Hydrogen Single Ion Activity Coefficients in Aqueous HCl Solutions at 25°C

The single ion activity coefficients of hydrogen and chloride ions in aqueous HCl solutions have been estimated at 25°C at concentrations up to 1 mol-kg^–1, using potentiometric measurements with ion-selective electrodes and appropriate calibration procedures. Two methods are described for an internal calibration of the electrodes in the extended Debye–Hückel concentration range. The results are compared to the conventional pH calibration with external buffer solutions. Since the latter calibration method does not account for the liquid junction potential E _J which arises at the reference electrode, the resulting activity coefficients are quite different in HCl solutions of higher concentration. These differences between internal and external calibration decrease significantly, when a correction for E _J is introduced into the conventional pH calibration. Hence, in solutions of higher ionic strength the accuracy of the conventional pH electrode calibration using buffer solutions is very limited, when exact H⁺ activities are required. The consistency of the results indicates that the liquid junction potentials in the examined systems calculated by the Henderson/Bates approximation are of reasonable precision.     

非对称核物质中同位旋对称势的动量和密度依赖性

在Brueckner-Hartree-Fock理论框架内, 研究了同位旋非对称核物质中质子和中子单粒子势的动量相关性及其随同位旋非对称度的变化, 在此基础上计算了同位旋对称势, 并讨论了三体核力的影响. 结果表明同位旋对称势对于同位旋非对称度的依赖性很弱, 但对于动量和密度均有较强的依赖性. 当密度固定时, 同位旋对称势随动量增加而减小. 尽管三体核力对于质子和中子单粒子势的动量相关性有较大影响, 但对同位旋对称势的影响很小. 还与目前重离子碰撞输运理论模型中所使用的各种参数化的唯象对称势进行了比较.     

COSMIC(90): An improved molecular mechanics treatment of hydrocarbons and conjugated systems

Summary Four modifications to the COSMIC molecular mechanics force field are described, which greatly increase both its versatility and the accuracy of calculated conformational energies. The Hill non-bonded van der Waals potential function has been replaced by a two-parameter Morse curve and a new H-H potential, similar to that in MM3, incorporated. Hydrocarbon energies in particular are much improved.A simple iterative Hückel pi-electron molecular orbital calculation allows modelling of conjugated systems. Calculated bond lengths and rotational barriers for a series of conjugated hydrocarbons and nitrogen heterocycles are shown to be as accurate as those determined by the MM2 SCF method.Explicit hydrogen-bonding potentials for H-bond acceptor-donor atom pairs have been included to give better hydrogen bond energies and lengths. The van der Waals radii of protonic hydrogens are reduced to 0.5 Å and the energy well depth is increased to 1.0 kcal mol^-1.Two new general atom types, N⁺ _sp ² and O^- _sp ³ , have been introduced which allow a wide variety of charged conjugated systems to be studied. A minimum of parameterisation is required, as the new types are easily included in the Hückel scheme which automatically adjusts bond and torsional parameters according to the defined bond-order relationships.     

温度对荒漠沙蜥在体心脏单相动作电位的影响

采用吸附式电极记录了荒漠沙蜥在不同体温条件下 ,在体心脏的单相动作电位 (MAP:Monophasic Action Potential) .实验温度为 :5℃ ,10℃ ,15℃ ,2 0℃ ,2 5℃ ,30℃和 35℃ 7个温度等级 .结果表明 :(1)在最适温度 (2 0～ 2 5℃ )时 ,荒漠沙蜥心脏单相动作电位的基本波形与高等动物及人类基本相似 ;但也有其特殊性 :动作电位 0期除极期最大幅值为 11.4 2± 2 .5 8m V;复极 2期电位幅值基本保持恒定 ,呈平台期 (PP2 :Plateau Phase2 ) ;在复极 3期末 ,电位基本恢复到 0电位(膜电位为 0 m V) .(2 )随着体温的升高 (5～ 35℃ ) ,荒漠沙蜥心脏单相动作电位时程呈温度依赖性减小 ;0期最大除极速度 (Vmax)呈温度依赖性增加 (5℃为 77.0 8± 4 7.11m V/ms;35℃为 614.63±10 5 . 0 2 m V/ms) ;低于最适温度时 (2 0～ 2 5℃ ) ,在 2相平台期末 ,又出现一次除极电位 (后隆起波 ) .其最大电位为 0 .5 8± 0 .18m V.(3)随着体温的升高 ,荒漠沙蜥心脏单相动作电位复极 1期电位呈温度依赖性降低 (5℃为 2 .2 4± 1.31m V/ms;35℃为 0 .82± 0 .4 9m V/ms) .(4 )心电图 (ECG)的同步记录表明 :心电图中的 QRS波与心脏单相动作电位 0期除极完全相对应 ;T波与动作电位的复极 3期相对应 .     

Rescaled mean spherical approximation structure factor for an aqueous suspension of polystyrene spheres

Rescaled mean spherical approximation (RMSA) has been used to calculate the structure factor for the aqueous suspension of polystyrene macroions with the interaction potential taken according to Derjaguin and Landau (1941) and Verwey and Overbeek (1948) (DLVO) model. The effects of charge over the macroion and size on the surface potential and therefore, the structure factor have been studied. The breakdown of the DLVO potential with an excess charge over the macroion (⩾800e) has been reported. The oscillation in the first peak height of structure factor versus wave vector curve with size has been correlated with the Debye length.     

水合镁离子的分子动力学模拟研究

基于水合离子[M(H2O)m]n+的概念,利用Moldy分子动力学模拟并结合分子内相互作用势MCY来研究水中的镁离子.该模拟系统包括一个二价的镁离子和216个水分子,在温度为330K下,计算了系统内不同原子对之间的径向分布函数(RDF),模拟结果和实验值基本一致.而且从其径向分布函数可看出,镁离子的出现并没有使得镁离子周围的第一水化层水分子和第二水化层水分子之间的距离有明显的减少.     

Nitroxyl free radical binding to Si(1 0 0): a combined scanning tunneling microscopy and computational modeling study

The ultra-high vacuum scanning tunneling microscope (UHV-STM) was used to investigate the addition of the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) radical to the Si(1 0 0) surface. Room temperature studies performed on clean Si(1 0 0)-2 × 1 confirm the proposed binding of the unpaired valence electron associated with the singly occupied molecular orbital (SOMO) of the molecule with a Si dangling bond. A strong bias dependence in the topography of isolated molecules was observed in the range of −2.0 to +2.5 V. Semiempirical and density functional calculations of TEMPO bound to a three-dimer silicon cluster model yield occupied state density isosurfaces below the highest occupied (HOMO) and unoccupied state densities isosurfaces above the lowest unoccupied molecular orbital (LUMO) which trend in qualitative agreement with the bias dependent STM topography. Furthermore, the placement of TEMPO molecules on dangling bonds was controlled with atomic precision on the monohydride Si(1 0 0) surface via electron stimulated desorption of H, demonstrating the compatibility of nitroxyl free radical binding chemistries with nanopatterning techniques such as feedback controlled lithography.     

The role of binder mobility in spontaneous adhesive contact and implications for cell adhesion

The standard view of mechanical adhesive contact is as a competition between a reduction in free energy when surfaces with bonding potential come into contact and an increase in free energy due to elastic deformation that is required to make these surfaces conform. An equilibrium state is defined by an incremental balance between these effects, akin to the Griffith crack growth criterion. In the case of adhesion of biological cells, the molecules that tend to form surface-to-surface bonds are confined to the cell wall but they are mobile within the wall, adding a new phenomenon of direct relevance to adhesive contact. In this article, the process of adhesive contact of an initially curved elastic plate to a flat surface is studied for the case in which the binders that account for adhesion are able to migrate within the plate. This is done by including entropic free energy of the binder distribution in the total free energy of the system. By adopting a constitutive assumption that binders migrate at a speed proportional to the local gradient in chemical potential, the transient growth of an adhesion zone due to binder transport is analyzed. For the case of a plate of very large extent, the problem can be solved in closed form, whereas numerical methods are invoked for the case of a plate of limited extent. Results are presented on the rate of growth of an adhesion zone in terms of system parameters, on the evolution of the distribution of binders and, in the case of a plate of limited extent, on the long-term limiting size of the adhesion zone.     

夫兰克─赫兹实验中温度的选择

本文讨论了气体击穿、空间电行与温度的关系，给出了测定原子第一激发电位和电离电位曲线时选择温度应遵循的规律．