Geometric phase opens new frontiers in nonlinear frequency conversion of light

Narrow-bandgap materials possess the intriguing optical-electric properties and unique structures,which can be widely applied in the field of photonics,energy optoelectronic sensing and biomedicine,etc.Nowadays,the researches on nonlinear optical properties of narrow-bandgap materials have attracted extensive attention worldwide.In this paper,we review the progress of narrow-bandgap materials from many aspects,such as background,nonlinear optical properties,energy band structure,methods of preparation,and applications.These materials have obvious nonlinear optical characteristics and the interaction with the short pulse laser excitation shows the extremely strong nonlinear absorption characteristics,which leads to the optical limiting or saturable absorption related to Pauli blocking and excited state absorption.Especially,some of these novel narrow-bandgap materials have been utilized for the generation of ultrashort pulse that covers the range from the visible to mid-infrared wavelength regions.Hence,the study on these materials paves a new way for the advancement of optoelctronics devices.     

Reduction of ethylene by Ni(I)(cyclam)+ in aqueous solutions

Ni(I)(1,4,8,11-tetraazacyclotetradecane)(+) reduces ethylene quantitatively to ethane plus butane (and hexane traces) in neutral aqueous solutions. A radical mechanism is proposed.     

On the Lifetime of the Transients (NP)?(CH3)n (NP=Ag0, Au0, TiO2 Nanoparticles) Formed in the Reactions Between Methyl Radicals and Nanoparticles Suspended in Aqueous Solutions

Methyl radicals react in fast reactions, with rate constants k>1×10⁸ M ^?1 s^?1, with Au⁰, Ag⁰ and TiO₂ nanoparticles (NPs) dispersed in aqueous solutions to form intermediates, (NP)? (CH₃)_n, in which the methyl groups are covalently bound to the NPs. These intermediates decompose to form ethane. As n≥2 is required for the formation of C₂H₆, the minimal lifetime (τ) of the methyls bound to the NPs, (NP)? CH₃, can be estimated from the rate of production of the CH₃^. radicals and the NPs concentration. The results obtained in this study, using a very low dose rate γ‐source for NP=Ag⁰, Au⁰, and TiO₂ point out that τ of these intermediates is surprisingly long, for example, ≥8 and ≥188 sec for silver and gold, respectively. These data point out that the NP? C bond dissociation energies are ≥70 kJ mol^?1. Under low rates of production of CH₃^., that is, when the rate of formation of ethane is very low, other reactions may occur, consequently the mechanism proposed is “broken”. This is observed in the present study only for TiO₂ NPs. These results have to be considered whenever alkyl radicals are formed near surfaces. Furthermore, the results point out that the rate of reaction of methyl radicals with (NP)? (CH₃)_n depends on n, that is, the number of methyl radicals bound to the NPs affect the properties of the NPs.     

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。     

Preliminary Investigation on the Effect of Production Parameters on the Strength of Large Tablets

A case study of large tablet manufacturing in the chemical industry is presented. Since the tablets are much larger than the usual scale in the pharmaceutical industry, common practice that was developed mainly for pharmaceutical tablets could not be applied directly. Customer complaints concerning damaged tablets were the reason for this comprehensive study, which was aimed first at evaluating a testing method for process control, then to provide some hints for stabilizing the manufacturing process and for producing stronger tablets. Three test methods were evaluated: measuring compression and tension crush strengths and wear tests in a rotating drum. It was shown that the wear test provides sufficient results faster and easier than the other methods. By testing hundreds of tablets, produced in various batches, production parameters such as granule aging, surrounding humidity, tableting pressure and tablet aging were evaluated in order to provide stronger tablets. The strongest tablets were achieved by using fresh granules at very high humidity and compacting pressure and by allowing the tablets to age for at least 2 weeks.