Combination of LFP‐TRIR spectroscopy and DFT computation as a tool to determine the intermediate during the photooxidation of triarylphosphine

Laser flash photolysis‐time‐resolved infrared spectroscopy (LFP‐TRIR) was performed on an acetonitrile or dichloromethane solution of triarylphosphines, Ar₃P, in air. A transient spectrum consisting of several absorption bands appeared in the region of 1050–1300 cm^?1 on the TRIR on a microsecond timescale, which disappeared on a millisecond timescale. To identify the observed transient intermediate, the IR spectra of possible intermediates of the photoreaction were simulated by theoretical calculations based on density functional theory (DFT). The IR spectrum simulated for the phosphine peroxidic radical cation, Ar₃P⁺OO^?, well predicted the observed IR spectrum, showing that Ar₃P⁺OO^? is formed as a transient intermediate upon the LFP of Ar₃P in air. Copyright © 2014 John Wiley & Sons, Ltd.     

电阻式核磁共振测量的最新进展

电阻式核磁共振(RDNMR)测量是1988年由德国马普所的von Klitzing研究小组针对GaAs二维电子气中少量核自旋的探测而提出的一种具有超高灵敏度的实验技术. 目前, RDNMR已经成为研究单层或双层GaAs二维电子气核自旋和电子自旋特性的重要手段. 由于为实现电阻式核磁共振测量所建立的动态核极化方法强烈依赖于GaAs特有的材料属性, 至今这一技术一直没有扩展应用到其他半导体低维系统中. 最近,本研究小组发展了一种动态核极化新方法,成功实现了对典型窄带半导体锑化铟(InSb) 二维电子气的电阻式核磁共振测量.本文在介绍电阻式核磁共振测量工作原理及已建立的典型动态核极化方法的基础上,着重讨论所提出的动态核极化新方法的机理、 实验结果以及对今后研究的展望.     

Status of prediction methods for critical heat fluxes in mini and microchannels

Saturated critical heat flux (CHF) is an important issue during flow boiling in mini and microchannels. To determine the best prediction method available in the literature, 2996 data points from 19 different laboratories have been collected since 1958. The database includes nine different fluids (R-134a, R-245fa, R-236fa, R-123, R-32, R-113, nitrogen, CO₂ and water) for a wide range of experimental conditions. This database has been compared to 6 different correlations and 1 theoretically based model. For predicting the non-aqueous fluids, the theoretical model by Revellin and Thome [Revellin, R., Thome, J.R., 2008. A theoretical model for the prediction of the critical heat flux in heated microchannels. Int. J. Heat Mass Transfer 51, 1216–1225] is the best method. It predicts 86% of the CHF data for non-aqueous fluids within a 30% error band. The data for water are best predicted by the correlation by Zhang et al. [Zhang, W., Hibiki, T., Mishima, K., Mi, Y., 2006. Correlation of critical heat flux for flow boiling of water in minichannels. Int. J. Heat Mass Transfer 49, 1058–1072]. This method predicts 83% of the CHF data for water within a 30% error band. Some suggestions have also been proposed in this paper for the future studies.     

Orthogonal-polarization compensation method for measuring unsteady vertical force of a bumblebee in a wind tunnel

It is important to measure the unsteady vertical force of an insect in a wind tunnel for studying the flight performance of insects. Optical method can measure it with high accuracy, but it is affected by air turbulence. An orthogonal-polarization compensation (OPC) method is developed for measuring the beating force of a bumblebee in a wind tunnel and compensating the error due to beam fluctuations induced by air turbulence. The applicability of the OPC method was confirmed by using a piezo translator to generate the tilt angle variation. The results show that by using the OPC method, the error in tilt angle measurement due to air turbulence can be decreased by about 80% compared with that using the conventional angle measurement method. The OPC method was then applied to measure the tilt angle variation caused by the beating motion of a bumblebee attached to one end of a sensor block in a wind tunnel for a wind velocity of 1.1 ms⁻¹. The results confirmed the effectiveness of this new method.     

Effects of the dark-exciton state on photoluminescence dynamics in surface-modified CdS quantum dots prepared by a colloidal method

We have investigated exciton dynamics in surface-modified CdS quantum dots (QDs) prepared by a colloidal method. The size- and surface-controlled CdS QDs have been successfully prepared by using a size-selective photoetching and surface modification technique. The decay profiles exhibit an unusual temperature dependence: increase of the decay time with increase in temperature. The temperature dependence of the decay profiles can be explained in terms of a three-level model including the exciton state with a triplet origin, the so-called dark-exciton state.     

Acid-base equilibria in nonpolar media. 4. Extension of the self-consistent basicity scale in THF medium. Gas-phase basicities of phosphazenes

Eleven new phenyl-substituted phosphazenes (P1-, P3-, and P4-bases) have been synthesized by the Staudinger or the Kirsanov reactions. The UV-vis spectrophotometric titration method was used to establish the relative basicity of them, and to extend the ion-pair basicity scale for THF medium. These measurements together with our previous work give a continuous basicity scale in THF ranging from 2.6 (2-MeO-pyridine) to 26.6 (2-Cl-C6H4P4(pyrr) phosphazene) in pKalpha units: that is for 24 orders of magnitude and containing 58 compounds (pyridines, anilines, amines, guanidines, amidines, phosphazenes). Ion-pair formation was taken into account by using the Fuoss equation. DeltapKip values of some phosphazene indicators estimated earlier by the 13C NMR method were revised. For some of the phosphazenes gas-phase basicities were measured.     

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.