Low-energy ion-assisted control of interfacial structures in metallic multilayers

A molecular dynamics method has been used to simulate the argon ion-assisted deposition of Cu/Co/Cu multilayers and to explore ion beam assistance strategies that can be used during or after the growth of each layer to control interfacial structures. A low-argon ion energy of 5–10 eV was found to minimize a combination of interfacial roughness and interlayer mixing (alloying) during the ion-assisted deposition of multilayers. However, complete flattening with simultaneous ion assistance could not be achieved without some mixing between the layers when a constant ion energy approach was used. It was found that multilayers with lower interfacial roughness and intermixing could be grown either by modulating the ion energy during the growth of each metal layer or by utilizing ion assistance only after the completion of each layers deposition. In these latter approaches, relatively high-energy ions could be used since the interface is buried and less susceptible to intermixing. The interlayer mixing dependence upon the thickness of the over layer has been determined as a function of ion energy.     

A new approach to potential flow around axisymmetric bodies

A new method is introduced to solve potential flow problems around axisymmetric bodies. The approach relies on expressing the infinite series expansion of the Laplace equation solution in terms of a finite sum which preserves the Laplace solution for the potential function under a Neumann-type boundary condition. Then the coefficients of the finite sum are calculated in a least squares approximation sense using the Gram-Schmidt orthonormalization method. Sample benchmark problems are presented and discussed in some detail. The solutions are accurate and converged faster when a rather small number of terms were used. The method is simple and can be easily programmed.     

Least‐squares finite element method on adaptive grid for PDEs with shocks

We apply the least‐squares finite element method with adaptive grid to nonlinear time‐dependent PDEs with shocks. The least‐squares finite element method is also used in applying the deformation method to generate the adaptive moving grids. The effectiveness of this method is demonstrated by solving a Burgers' equation with shocks. Computational results on uniform grids and adaptive grids are compared for the purpose of evaluation. The results show that the adaptive grids can capture the shock more sharply with significantly less computational time. For moving shock, the adaptive grid moves correctly with the shock. © 2005 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2006     

Molecular dynamics studies on octadecylammonium chloride at the air/liquid interface

Molecular dynamics simulations on surfactant octadecylammonium chloride at the air/liquid interface were performed. It was found that the alkyl chains of octadecylammonium would change to order with increasing the concentration of octadecylammonium at the air/liquid interface. Some functions, such as the concentration distributions, the radial distribution function and the mean squared displacement (MSD) were evaluated to investigate the structural properties of interface. We found that the salts can affect octadecylammonium aggregate at the interface: (1) univalent ions, such as chloride and sodium ions, affect slightly the structure of monolayer and (2) bivalent ions, such as sulfate or calcium ions, affect greatly, especially for the bivalent negative ions.     

Chiral separation of 1,1'-bi-2-naphthol and its analogue on molecular imprinting monolithic columns by HPLC

Two molecular imprinting polymer (MIP) monolithic columns with (S)-(-)-1,1'-bi-2-naphthol and (R)-(+)-5,5',6,6',7,7',8,8'-octahydro-1,1'-bi-2-naphthol as the templating molecules, respectively, have been prepared by in situ polymerization using 4-vinylpyridine and ethylene dimethacrylate as functional monomer and cross-linker, respectively. The columns with good flow-through properties were obtained by changing the molar ratio of the functional monomer and the template molecule. The effects of mobile-phase composition on separation of enantiomers were systematically investigated. The results indicate that hydrophobic interaction in aqueous solution and hydrogen-bonding interaction in ACN between the enantiomers and polymers could play important roles in the retention and resolution. The effects of chromatographic conditions, such as flow rate, column temperature, sample loading, on the enantioseparation were also studied. Further, these two MIP columns show a cross-reactivity.     

Molecular potential-energy surfaces for chemical reaction dynamics

This paper reviews the construction of molecular potential-energy surfaces by an interpolation method which has been developed over the last several years. The method uses ab initio quantum chemistry calculations of the molecular electronic energy in an automated procedure to construct global potential- energy surfaces which can be used to simulate chemical reactions with either classical or quantum dynamics. The methodology is explained and several applications are presented to illustrate the approach. Received: 22 February 2002 / Accepted: 2 May 2002 / Published online: 6 November 2002 Correspondence to: M. A. Collins e-mail: collins@rsc.anu.edu.au Acknowledgements. The methods described in this overview are the result of collaborations with former members of my group, in particular with Josef Ischtwan, Meredith Jordon, Keiran Thompson and Ryan Bettens. I am also indebted for inspiration gained from many discussions with my colleagues Leo Radom and Donghui Zhang (National University of Singapore). This work has been supported by the Supercomputer Facility of the Australian National University and the Australian Partnership for Advanced Computing.     

Molecular determinants in the bioactivation of the dopaminergic neurotoxin N-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP)

Summary Nineteen analogs of the dopaminergic neurotoxin N-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP) have been used as probes to study the structural parameters that influence MAO-catalyzed oxidation. In this study, the efficiency of enzyme-catalyzed substrate oxidation was found to be unrelated to parameters such as the ionization potential, dipole moment, net atomic charge at C5 and the dihedral angle between the phenyl ring and the tetrahydropyridine moiety. Conformational analysis revealed that substitution at the C2 position of MPTP yields atropisomers. It is suggested that one of these atropisomers would be either inactive or substantially less active than the other. Therefore, the relative oxidative efficiency and toxicity of these compounds reported earlier may have been significantly underestimated. Based on the conformational analysis and other data, a rudimentary model of the MAO substrate site has been developed which partially explains the substrate specificities of MAO A and MAO B.Each substrate binding site can be divided into two regions, (a) an amine-binding pocket (for the tetrahydropyridine moiety), and (b) a bulky substituent region (for the phenyl group and its substituents). The length of the substrate binding site (measured along the long axis of MPTP) is approximately 8.5 Å, and the width of the amine-binding pocket is approximately 2.5 Å (from C3 to C5). The bulky substituent region contains a central area for binding the phenyl group of MPTP. This central area is flanked by two hydrophobic pockets, P2 and P3. In MAO A, the pocket P2-A is oriented 45–135° relative to the plane of the tetrahydropyridine moiety, with a radius of 3.1 Å from C2 of the phenyl ring. The radius of a similar but smaller pocket, P2-B, in MAO B, is approximately 2.7 Å. In MAO B, the pocket P3-B (radius 2.36 Å from C3) is larger than a similar pocket P3-A (radius 1.70 Å from C3) in MAO A. The foregoing characterization suggests that differences in the size and topography of both of the substituent pockets play an important role in determining the substrate specificities of these two isozymes.     

Adsorption of water molecules in slit pores

We report molecular dynamics (MD) simulations on the adsorption of water in attractive and repulsive slit pores, where the slit and a bulk region are in contact with each other. Water structure, surface force and adsorption behavior are investigated as a function of the overall density in the bulk region. The gas–liquid transition in both types of pores occurs at similar densities of the bulk region.     

Reagentless system for sulphite determination based on polyaniline

A new reagentless system for sulphite (or sulphur dioxide) determination is reported based on the use of an organic conducting polymer, polyaniline, and its absorbance variation at 550 nm, depending on the sulphite concentration. After chemical polymerisation of aniline a very thin film of polyaniline is obtained. Although the response is not fully reversible, each film can be used for at least 10 measurements for low analyte concentrations (up to 0.5 mg l⁻¹) and five measurements for higher sulphite concentrations. Moreover, the reproducibility, ease of preparation and low cost of the films, permit the use of a new disposable system for each measurement. When the change in absorbance at 550 nm was measured for 210 s (stabilisation time), the system showed a linear response, which ranged from 0.025 to 1.50 mg l⁻¹ of sulphite. A theory with regard to the reaction mechanism between the polyaniline films and sulphite is also proposed. The system was applied to sulphite determination in wine samples and the results were in agreement with those obtained by the Official Method of Analysis (iodometric titration).     

一种测定蛋白质的分子吸收光谱分析新体系

使用四溴荧光素(TBFS)作为蛋白质的染色剂,建立了一种测定蛋白质的分子吸收光谱分析新体系———BSA 四溴荧光素,体系十分简单,BSA浓度在0.11～60.0μg·ml-1范围符合比耳定律;测定15.0μg·ml-1BSA溶液10次,求得相对标准偏差为1.26%,桑德尔灵敏度为0 094μg·cm-2。可直接用于血清样品中蛋白质的测定,测得质量控制血清样品中蛋白质质量为35.4±2.4mg,与标准值36.9mg吻合。回收率在97.0%～108.3%之间,结果满意。