Triplet topology of self-assembled zinc porphyrin-pyridylfullerene complex

This work extends a recent EPR study on light-driven electron and energy transfer in a self-assembled zinc porphyrin-pyridylfullerene (ZnP-PyrF) complex. We report on a triplet line shape analysis of the photoexcited PyrF monomer and the ZnP-PyrF complex dissolved in isotropic and anisotropic matrixes of different polarity, namely, toluene, tetrahydrofuran (THF), and the nematic liquid crystals (LCs), E-7 and ZLI-4389. The line shape of the unbound *(3)PyrF obtained in both isotropic matrixes exhibits triplet parameters similar to those obtained for other monoadducts of C(60) under similar experimental conditions. On the other hand, 8(3)PyrF oriented in the LCs shows a complicated line shape, which is attributed to two conformers: (a) an axial dominant (85%) configuration characterized by triplet parameters, similar to those obtained in the isotropic matrixes and (b) a bent configuration associated with spin density localized about the poles accompanied by sign reversal of the ZFS parameter D of the *(3)C(60) moiety. Further, since in both LCs the ZnP-PyrF complex mainly exhibits a conformation with axial symmetry, the differences between the electron and the energy transfer routes in each LC are attributed to their different polarity. This study reflects the strength of LC matrixes to serve as a topological tool, enabling us to determine the conformers' distribution and to differentiate between electron and energy transfer routes.     

Reactions of alkyl-radicals with gold and silver nanoparticles in aqueous solutions

Silver and gold nanoparticles are very efficient catalysts for the dimerization of methyl-radicals in aqueous solutions. The rate constants for the reaction of methyl-radicals with the gold and silver nanoparticles were measured and found to be 3.7 x 10(8) M(-1) s(-1) and 1.4 x 10(9) M(-1) s(-1), respectively. The results thus suggest that alkyl-radicals, also not reducing ones, are scavenged by these nanoparticles. This might explain the role, if such a role exists, of these nanoparticles in medical applications.     

A Mo(VI) alkylidyne complex with polyhedral oligomeric silsesquioxane ligands: homogeneous analogue of a silica-supported alkyne metathesis catalyst

A highly active alkyne metathesis catalyst is realized by replacing the amide ligands of a molybdenum(VI) trisamide alkylidyne complex with silanol groups from incompletely condensed POSS (polyhedral oligomeric silsesquioxane) ligands. This catalyst serves as an effective homogeneous mimic of an amorphous silica-supported catalyst. Reactivities of various catalytic mixtures are reported along with an X-ray structure of the aniline-coordinated amidodisiloxymolybdenum(VI) alkylidyne complex.     

微尺度色谱通道截面形状优化

本文将基于体积平均方法的理论模型与拓扑优化工具结合,以减小弥散系数为优化目标对微尺度色谱通道的截面形状进行了优化。优化结果表明色谱通道截面形状优化可以明显削弱通道内弥散过程。优化得到的截面形状明显不同于常见的矩形截面,具体形状取决于流动阻力系数的数值,流动阻力系数越大,截面的宽高比越大。将优化截面用于微尺度色谱设计可以显著改善分离速度及分离精度。