Femtosecond dynamics of electron transfer in a neutral organic mixed-valence compound

In this article we report a femtosecond time-resolved transient absorption study of a neutral organic mixed-valence (MV) compound with the aim to gain insight into its charge-transfer dynamics upon optical excitation. The back-electron transfer was investigated in five different solvents, toluene, dibutyl ether, methyl-tert-butyl ether (MTBE), benzonitrile and n-hexane. In the pump step, the molecule was excited at 760 nm and 850 nm into the intervalence charge-transfer band. The resulting transients can be described by two time constant. We assign one time constant to the rearrangement of solvent molecules in the charge-transfer state and the second time constant to back-electron transfer to the electronic ground state. Back-electron transfer rates range from 1.5 × 10¹² s⁻¹ in benzonitrile through 8.3 × 10¹¹ s⁻¹ in MTBE, around 1.6 × 10¹¹ s⁻¹ in dibutylether and toluene and to 3.8 × 10⁹ s⁻¹ in n-hexane.     

Localized electron traps on extended molecular surfaces

We have previously alluded to the fact that concentrated charge pockets can form on molecular surfaces that can act to stabilize excess electrons. These charge pockets are formed from systems, which posses a network of hydrogen bonded OH groups on one side of the surface and hydrogen atoms on the opposite side of the molecular surface. In this work, we have increased the size of our recently reported molecular surfaces (Jalbout and Adamowicz, Mol Phys, 2006, 19, 3101) while keeping the number of OH groups constant, to investigate localized charge concentration on extended frameworks. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Highly sensitive tITP‐CZE determination of l‐histidine and creatinine in human blood plasma using field‐amplified sample injection with mobility‐boost effect

2D computer simulation revealed that amino acids and weak electrolytes were cationized because of the migration of counter‐ion from a BGE zone to a sample zone, which encouraged electrokinetic injection (EKI) of these analytes (by the mobility‐boost (MB) effect). To investigate the effects of kinds and concentrations of counter‐ions on the MB effect and the analyte amount injected into the capillary, experiments, and 1D computer simulations were performed. When acetate was used as the counter‐ion, the LODs (S/N = 3) of l ‐histidine and creatinine, respectively, reached 0.10 and 0.25 nM because of the concentration effect by transient ITP (tITP). The concentrations of l ‐histidine and creatinine in human blood plasma obtained using the proposed method were agreed with those obtained using the conventional methods. The proposed method can be applied to the analysis of amino acids and weak bases that have similar pI and pK_a to l ‐histidine and creatinine.     

过渡金属羰基化合物Mn(CO)5Br和Re(CO)5Br结构与动力学的超快光谱

利用超快泵浦探测红外光谱、稳态线性红外光谱和计算化学方法,对过渡金属羰基化合物Mn(CO)₅Br和Re(CO)₅Br的振动和结构动力学进行了研究. 借助羰基的两个伸缩振动峰(处于低频的A₁模式和处于高频的简并E模式)进行了观测. 结果表明,在两个配合物中,A₁和E模式振动峰的振动频率位置及频率差都与中心金属原子对羰基的键级和振动力常数的影响相关. 而A₁模式比E模式的线宽宽一些,部分由于振动寿命的影响. 此外,从瞬态光谱中获得了振动模式依赖的对角非谐性常数,发现在两个羰基化合物中E模式的非谐性总是较小.     

聚离子亚基化合物结构影响外源基因转染效率

合成了带正电荷密度不同的聚离子亚基化合物,探讨了聚合物结构对外源基因转染真核细胞的影响规律。从实验结果看,聚离子亚基化合物结构影响外源基因转染效率,但其影响程度与靶细胞的种类相关,对ＨｅＬａ细胞,ＮＩＨ３Ｔ３细胞,聚离子亚基化合物的正电荷密度加大,其促基因转移功能加强;而对ＰＡ３１７包装细胞,结果相反。     

暂留对称扩散过程全占据时的大偏差

本文讨论暂留对称扩散过程的全占据时的大偏差．我们证明在一致椭圆条件下,暂留对称扩散过程的全占据时满足大偏差原理．     

The characterisation and application of a pulsed neodymium YAG laser DGV system to a time-varying high-speed flow

Doppler Global Velocimetry (DGV) is a whole-field measurement technique which has attracted significant interest from the fluid-flow research community since its introduction in 1991. Practical implementations of the methodology have focused on two principal laser light sources: the argon ion laser, applied to steady state or slowly varying flows; and the pulsed neodymium YAG laser for the measurement of instantaneous velocity fields. However, the emphasis in the published literature has been very much on research using the argon laser. This paper reports the application of a Q-switched, injection-seeded neodymium YAG laser to the proven Oxford DGV system, and the use of this combination in a short duration unsteady high-speed flow. The pertinent characteristics of the apparatus are described, and the impact of these on the integrity of the resulting velocity measurements is presented. Adaptations to the commercial laser system that make it suitable for application to the measurement of transient high-speed flows are described. Finally, the application of this system to a short duration unsteady flow is described. This application is based on the flow found in a new type of transdermal drug delivery device, where particles of the drug material are projected at high speed through the skin. Whole-field velocities are recorded, and values as high as 800 m/s are evident.     

Modelling an anomalous stress relaxation in glassy polymers (the Kitagawa effect)

Constitutive relations are derived for the nonlinear viscoelastic response of glassy polymers. The model is based on the concept of adaptive links (a version of the theory of transient networks), where the rates of annihilation of active links are determined by the Eyring formula. Adjustable parameters in the constitutive equations are found by using experimental data for a polyester resin in standard relaxation tests. The stress-strain relations are applied to describe an anomalous stress relaxation in solid polymers observed in tensile test after strain reversal (the Kitagawa effect). Qualitative agreement is demonstrated between results of numerical simulation and observations.     

地下水位上升下黄土斜坡稳定性分析

黄土高原一些地区,由于塬上引水灌溉使得地下水位不断抬升,造成黄土滑坡频繁发生。地下水位变化严重影响着黄土斜坡的稳定性。基于饱和-非饱和渗流理论和延伸的摩尔-库伦破坏准则,结合室内饱和和非饱和试验结果,针对泾阳南塬一典型黄土斜坡,考虑地下水位上升情况下,对其进行了瞬态饱和-非饱和渗流分析;然后将计算得到的瞬态孔隙水压力分布用于斜坡的极限平衡分析。结果表明:地下水位上升对暂态渗流场和斜坡稳定性有明显影响;考虑非饱和渗流和吸力强度的边坡稳定分析方法更加符合实际情况。     

模拟 ps激光驱动的类氖锗19.6 nm X光激光

 瞬态电子碰撞激发产生X光激光的机制可以极大减少X光激光的泵浦能量。模拟了脉宽为1 ps,波长1.053 μm的钕玻璃激光驱动的类氖锗X光激光。模拟表明,在临界面附近可以产生高达60 cm ^-1的增益,还计算了X光激光在等离子体中的传播,计算表明X光激光在等离子体中的折射效应仍然是影响X光激光输出强度及分布的重要因素。