Photoinduced graft polymerization of 2-methacryloyloxyethyl phosphorylcholine on polyethylene membrane surface for obtaining blood cell adhesion resistance

Phospholipid polymer, poly[2-methacryloyloxyethyl phosphorylcholine (MPC)], was grafted with polyethylene (PE) membrane using photoinduced polymerization technique to make the membrane resistant to cell adhesion. The water contact angle on the PE membrane grafted with poly(MPC) decreased with an increase in the photopolymerization time. This decrease corresponded to the increase in the amount of poly(MPC) grafted on the PE surface. The same graft polymerization procedure was applied using other hydrophilic monomers, such as acrylamide (AAm), N-vinylpyrrolidone (VPy) and methacryloyl poly(ethylene glycol) (MPEG). These monomers were also polymerized to form grafted chains on the PE membrane, and the grafting was confirmed with X-ray photoelectron spectroscopy. Analysis of amount and distribution of plasma proteins at the plasma-contacting surface of the original and the modified PE membranes were analyzed using immunogold assay. The grafting of poly(MPC) and poly(VPy) on PE membrane reduced the plasma protein adsorption significantly compared with that on the original PE membrane. However, the PE membranes grafted with poly(AAm) or poly(MPEG) did not show any effects on protein adsorption. Platelet adhesion on the original and modified PE membranes from platelet-rich plasma was also examined. A large number of platelets adhered and activated on the original PE membrane. Grafting with poly(AAm) did not suppress platelet adhesion, but grafting with poly(MPC) or poly(VPy) on the PE membrane was effective in preventing platelet adhesion. It is concluded that the introduction of the phosphorylcholine group on the surface could decrease the cell adhesion to substrate polymer.     

Orientation-selected 15N-HYSCORE detection of weakly coupled nitrogens around the archaeal rieske [2Fe-2S] center

The weakly coupled 15N atoms around a reduced Rieske [2Fe-2S] cluster of the uniformly 15N-labeled, hyperthermostable archaeal Rieske protein appear to produce readily observable cross-peaks in the HYSCORE spectra, with the well-resolved couplings of 0.3-0.4 MHz for the Nepsilon and 1.1 MHz for the peptide backbone nitrogens, in addition to the contributions from the coordinated Ndelta atoms. These features can be used for structure-mechanism studies of the biological redox protein system involving the weakly coupled nitrogens in coupled electron-proton transfer reactions.     

Radical cyclization by ipso substitution of the methoxy group: considerable effect of HMPA on samarium-mediated cyclization

Alkyl radicals generated by treatment of thiocarbamates of conformationally favorable 3-alkyl-3-arylpropan-1-ols with tris(trimethylsilyl)silane and AIBN efficiently undergo intramolecular ipso substitution of the methoxy group, yielding the corresponding cyclized products. In contrast, either conformationally favorable or flexible 1-arylalkan-3- or 4-ones easily cyclize into five- or six-membered condensed rings by treatment with SmI(2) via ketyl radical intermediates. The addition of HMPA as cosolvent dramatically changes the cyclization mode of the SmI(2)-induced reaction, and the para-cyclization products are exclusively formed. This "HMPA effect" can be rationalized by the strong chelating ability of HMPA with the samarium atom.     

Multicolor photochromism of two- and three-component diarylethene crystals

Novel photochromic single crystals composed of three different kinds of diarylethenes, 1,2-bis(3,5-dimethyl-2-thienyl)perfluorocyclopentene (1a), 1,2-bis(2,5-dimethyl-3-thienyl)perfluorocyclopentene (2a), and 1,2-bis(2-methyl-5-p-methoxyphenyl-3-thienyl)perfluorocyclopentene (3a), have been prepared. The three-component crystals turned yellow, orange, red, purple, blue, green, or black upon irradiation with light of appropriate wavelengths. The colors of the crystals were thermally stable in the dark and completely bleached by irradiation with visible light. Such multicolored photochromic crystals have potential for the application to optoelectronic devices, such as multifrequency three-dimensional optical memory media or full-color displays.     

Double-chelation-assisted Rh-catalyzed intermolecular hydroacylation between salicylaldehydes and 1,4-penta- or 1,5-hexadienes

Intermolecular hydroacylation between salicylaldehydes 1, 26-40 and 1,4-penta- or 1,5-hexadienes 4-13 by Rh-catalyst proceeded under mild reaction conditions to give a mixture of iso- and normal-hydroacylated products 14-25, 41-55, and 57-60. In the hydroacylation reaction, chelation of both salicylaldehyde and diene to the Rh-complex plays a crucial role. The ratio of iso- and normal-hydroacylated products could be regulated by the addition of salicylic acid or amines. The effects of various Rh-complexes, solvents, and additives were examined, and the plausible mechanisms of the catalytic cycle were proposed on the basis of the deuterium-labeling salicylaldehyde experiments.     

可见光照射下丙炔光催化水解反应的研究 Ⅱ．钒离子对二氧化钛催化性能的影响

 研究了几种不同粒径的TiO2在CH3CCH和H2O的光催化反应中的催化活性．结果表明,利用离子注入法可以拓展纳米TiO2催化剂的光吸收区域,使其吸收带向可见光方向偏移,且偏移程度随着TiO2粒径的增大而增大;特别是注入V离子使TiO2催化剂在可见光区域具有光催化活性．V离子注入后,TiO2催化剂在紫外区域的光催化活性没有下降,但在可见光区域的光催化活性有所提高．在五种光催化剂中,具有中等粒径大小的P－25注入V离子后表现出最高的光催化活性．在太阳光直接照射下,这些光催化剂也具有较高的催化活性．     

Starburst dendrimer-supported pseudostationary phases for electrokinetic chromatography

Pseudo-stationary phases for electrokinetic chromatography were prepared by the alkylation of starburst dendrimers (SBDs). The SBD-supported pseudo-stationary phase with dodecyl groups showed higher efficiency than short-akyl derivatives, and maintained the hydrophobic property inthe presence of methanol. The dodecyl-modified SBD provided wide migration time windows ar high methanol content to effect the separation of sixteen aromatic hydrocarbons, the priority pollutants designated by EPA, in 65% methanol. The selectivity of polymer-supported pseudo-stationary phase can be varied simply by changing the length of the alkyl groups. The dodecyl SBD showed relatively similar selectivity as sodium dodecyl culfate micelle, whereas short alkyl derivatives showed preference towards rigid and planar compounds based on the rigid and planar compounds based on the rigid polymer backbones. The selectivity of SBD-supported pseudo-stationary phases was dominated by the chain length of the alkyl groups, with the minor effect of the structure of the core and the generation of SBD where alkyl groups were attached.     

Determination of rare earth elements in geological samples by inductively-coupled plasma atomic emission spectrometry after oxalate coprecipitation and cation-exchange column separation

A method for separation and determination of traces of 14 rare earth elements (REEs) in geological samples is described. Determination by inductively-coupled plasma atomic emission spectrometry follows oxalate coprecipitation of the REEs with calcium as carrier and cation- exchange column separation in nitric acid. The combination of the two separation techniques improved the low recoveries found for Sm, Eu, and Gd when only ion-exchange was used, especially for iron- and aluminum-rich samples. The method was applied to the analysis of geological standard materials NBS SRM 688 (basalt), NBS SRM 278 (obsidian), GSJ JB-1 (basalt), GSJ JA- 2 (andesite), and CCRMP SY-3 (syenite). The results were evaluated on the basis of chondrite- normalized rare earth element distribution patterns.     

Development of a cooled He*(23S) beam source for measurements of state-resolved collision energy dependence of Penning ionization cross sections: Evidence for a stereospecific attractive well around methyl group in CH3CN

A low-temperature discharge nozzle source with a liquid-N(2) circulator for He*(2(3)S) metastable atoms has been developed in order to obtain the state-resolved collision energy dependence of Penning ionization cross sections in a low collision energy range from 20 to 80 meV. By controlling the discharge condition, we have made it possible to measure the collision energy dependence of partial ionization cross sections (CEDPICS) for a well-studied system of CH(3)CN+He*(2(3)S) in a wide energy range from 20 to 350 meV. The anisotropic interaction potential energy surface for the present system was obtained starting from an ab initio model potential via an optimization procedure based on classical trajectory calculations for the observed CEDPICS. A dominant attractive well depth was found to be 423 meV (ca. 10 kcal/mol) at a distance of 3.20 A from the center of mass of CH(3)CN in the N-atom side along the CCN axis. In addition, a weak attractive well (ca. 0.9 kcal/mol) surrounding the methyl group (-CH(3)) has been found and ascribed to the interaction between an unoccupied molecular orbital of CH(3)CN and 2s atomic orbital of He*(2(3)S).     

Structure-activity relationship (SAR) studies on oxazolidinone antibacterial agents. 2. Relationship between lipophilicity and antibacterial activity in 5-thiocarbonyl oxazolidinones

5-Thiourea and 5-dithiocarbamate oxazolidinones were synthesized as a continuation of research on 5-thiocarbonyl oxazolidinone antibacterial agents considering the hydrophobic parameters of the molecule. The structure-activity relationship (SAR) study revealed that the antibacterial activity on 5-thiocarbonyl oxazolidinones was significantly affected by the lipophilicity, especially the calculated log P value and the balance between 5-hydrophilic (or hydrophobic) substituent and hydrophobic (or hydrophilic) substituents on the benzene ring. Some of 5-thiocarbonyl oxazolidinones were found to have good in vitro antibacterial activity against gram-positive bacteria including methicillin-resistant Staphylococcus aureus (MRSA) and vancomycin-resistant enterococci (VRE).