Influence of nanometer scale film structure of ZDDP tribofilm on Its mechanical properties: A computational chemistry study

We investigated the influence of a nanometer scale film structure of a tribofilm generated from zinc dialkyldithiophosphate (ZDDP) anti-wear additive on its mechanical properties using a combined molecular dynamics (MD) and finite element (FE) method. The frictional behavior of an interface between a native iron oxide layer on steel surface and zinc metaphosphate - regarded as a model material of ZDDP tribofilm - was firstly studied using the MD method. The results showed that the iron atoms in the oxide layer diffused into the phosphate layer during the friction process. The zinc atoms in the phosphate layer also diffused into the oxide layer. Significant interdiffusion of iron and zinc atoms was observed with increasing simulation time. Thus, metallic phosphate with a gradient composition of iron and zinc atoms was formed on the phosphate/oxide interface. We then constructed an axisymmetric nanoindentation simulation model from the MD-derived structures at a certain simulation time and carried out a FE calculation. As a result, we found that the rubbed ZDDP tribofilm, including the phosphate with the gradient composition of metallic atoms, showed larger contact stiffness and hardness. The combined MD/FE simulation indicates that the tribofilm becomes stiffer and harder due to the interdiffusion of iron and zinc atoms on the tribofilm/oxide interface. We have found that the gradient composition formation in ZDDP tribofilm during friction process influences on its mechanical properties.     

Consistent inlet and outlet boundary conditions for particle methods

In this paper, simple and consistent open boundary conditions are presented for the numerical simulation of viscous incompressible laminar flows. The present approach is based on an arbitrary Lagrangian-Eulerian particle method using upwind interpolation. Three kinds of inlet/outlet boundary conditions are proposed for particle methods, a pressure specified inlet/outlet condition, a velocity profile specified inlet/outlet condition, and a fully developed flow outlet condition. These inlet/outlet conditions are realized by using boundary particles and modification to the physical value such as velocity. Poiseuille flows, flows over a backward-facing step, and flows in a T-shape branch are calculated. The results are compared with those of mesh-based methods such as the finite volume method. The method presented herein exhibits accuracy and numerical stability.     

Modification of macrophage functions by Shosaikoto (kampo medicine) leads to enhancement of immune response

The effects of Shosaikoto, one of the Kampo medicines, on macrophage functions were studied in mice. Oral administration of Shosaikoto (1.2 g/kg of body weight) increased the change of the membrane fluidity of macrophages and diminished prostaglandin E2 production. Moreover, macrophages from mice orally given Shosaikoto phagocytized antigen more efficiently than control macrophages, resulting in presentation of much more antigen to lymphocytes. These results suggest that Shosaikoto enhances the immune response through at least two different routes, that is, through eliminating the inhibition of lymphocyte functions by prostaglandin E2 and through presenting antigen more efficiently.     

Mass distribution of fission fragments in the19F+197Au reaction

Mass distributions of fission fragments have been measured for the reaction of¹⁹F on¹⁹⁷Au as a function of scattering angle. The mean fragment mass is dependent on the scattering angle, the asymmetry increasing with increasing projectile energy.     

Effects of saikosaponin metabolites on the hemolysis of red blood cells and their adsorbability on the cell membrane

The hemolytic properties and the adsorbability on red blood cells of saikosaponin a, saikosaponin d and 13 metabolites formed in the alimentary tract were investigated. Among these compounds, saikosaponin d and its intestinal product, prosaikogenin G, which possess an alpha-hydroxyl function at C16, showed the strongest hemolytic activity at the dose range of 1.0 to 5.0 micrograms/ml. Saikosaponin a and its intestinal product, prosaikogenin F, which possess a beta-hydroxyl function at C16, showed activity above 10 micrograms/ml. In this case, the monoglycoside, prosaikogenin F, showed the stronger activity than the diglycoside, saikosaponin a. Among the gastric products whose ether ring was cleaved to produce a carbinol, the monoglycosides, prosaikogenin A and prosaikogenin H, showed a slight activity above 25 micrograms/ml, and the saikogenins except saikogenin A were inactive. Saikogenin A, however, had hemolytic activity at a dose of 15 micrograms/ml. The adsorbabilities of these compounds on red blood cell membranes closely paralleled their degrees of hemolytic activity.     

Membrane disordering induced by chloroform and carbon tetrachloride

We studied effects of chloroform and carbon tetrachloride on bilayer membranes of dimyristoyl-phosphatidylcholine (DMPC) and egg yolk phosphatidylcholine (Egg-PC) by birefringence, dynamic light scattering and fluorescence methods. It is shown that interference light due to the membrane birefringence considerably decreases by addition of the organohalogen compounds for both lipid membranes, indicating a significant decrease in membrane order. In addition, results of dynamic light scattering and turbidity measurements show a rupture of multilamellar DMPC vesicles induced by addition of chloroform at concentrations above 0.2 v/v%. No rupture of the vesicles is observed within the limit of solubility of carbon tetrachloride in water, but excessive addition of carbon tetrachloride (above 0.2 v/v%) induces the vesicle rupture. Chain orientational order was estimated from the interference light intensity at low concentrations of the organohalogen compounds without the occurrence of the vesicle rupture. The estimation shows a monotonic decrease in the chain order with increasing the concentration. The decreases in DMPC chain order by chloroform and by carbon tetrachloride are about 17% at 0.2 v/v% and 23% at 0.05 v/v%, respectively. The reduction in the chain order is correlated with an increase in the membrane fluidity observed by excimer fluorescence of pyrene incorporated to the membrane. Behavior of membrane disordering of Egg-PC is approximately similar with that of DMPC. This implies the strong interaction between the organohalogen compounds and the lipid chains, whether or not the bilayer has the vacancy resulted from unsaturated double bonds and different chains in length. The results of this work suggest that damages of biological membranes by chloroform and tetrachloride are not only induced by a direct attack on proteins but also by a significant membrane disorder.     

A single-chain magnet formed by a twisted arrangement of ions with easy-plane magnetic anisotropy

A unique "single-chain quantum magnet" was formed by an alternating arrangement of high-spin FeII/low-spin FeIII ions. Although the predominant spin-carrier components (high-spin FeII) possess easy-plane magnetic anisotropy (D > 0), twisted arrangement of easy-planes along the chain axis defines a novel class of one-dimensional Ising system.     

Simultaneous multi-element determination of trace metals in sea water by inductively-coupled plasma atomic emission spectrometry after coprecipitation with gallium

Coprecipitation with gallium hydroxide is studied for the preconcentration of trace metals in sea water before multi-element analysis by inductively-coupled plasma/atomic emission spectrometry. Gallium precipitates at pH 9 only when magnesium is present. Optimum conditions are established for multi-element preconcentration and removal of matrix elements. The method is almost free from contamination because of the use of highly pure gallium meetal and only a small amount of sodium hydroxide for pH adjustment. Spectral interferences from gallium are negligible and a concentratioin factor of more than 200 can be obtained. Detection limits range from a few ng l^?1 to 150 ng l^? for Al, Co, Cr, Fe, La, Mn, Ni, Ti, V, Zn, Y and Pb. Artificial and natural sea-water samples can be analyzed with adequate precision.     

New lignan glycosides from Chinese medicinal plant,Sinopodophillum emodi

Two new podophillotoxin glucosides, L-picropodophillotpxin 7'-O-(beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranoside) (2) and L-picropodophillotpxin 7'-O-beta-D-glucopyranoside (3), were isolated from Chinese medicinal plant, Sinopodophillum emodi, together with 4 known compounds, podophillotoxin (1), podorhizol 4'-O-beta-D-glucopyranoside (4), deoxypodophillotoxin (5), and dehydropodophillotoxin (6). The structures of 2 and 3 were finally determined by the extensive decouping and nuclear Overhauser effect (NOE) experiments in NMR spectra and circular dichroism (CD) spectra. Compound 2 is the second example of podophillotoxin diglucoside, and both the first one and 2 were isolated from S. emodi. X-ray crystal structure analysis of 1, 5, and 6 was carried out. Compounds 1 and 5 showed the different conformations from those reported.