Green synthesis of Pd truncated octahedrons using of firmiana simplex leaf extract and their catalytic study for electro‐oxidation of methanol and reduction of p‐nitrophenol

A facile and eco‐friendly biosynthetic route for preparing Pd truncated octahedrons (PdTOs) using firmiana simplex leaf extract was reported without any chemical reducing agents. The information of reducing components, reduction process and time were obtained by ATR‐FTIR imaging, FTIR and UV–Vis spectroscopy, respectively. TEM image revealed that more than 75% of PdNPs were composed of PdTOs with an average diameter of 9.2 nm. HR‐TEM analysis demonstrated that a single PdTO consisted of the mix of {100} and {111} crystal planes. SAED and XRD pattern confirmed the well crystalline nature of fcc structured PdTOs. The model reactions of electro‐oxidation of methanol and reduction of p‐nitrophenol (p‐NP) were adopted to explore the effects of structure and size of PdNPs on the catalytic properties. In the electro‐oxidation of methanol, the forward‐scan peak current density (If) of PdTOs was 10.05 mA cm‐2, 6.3 times and 1.9 times of PdNPs‐0 and PdNPs‐4:1, illustrating its superior electro‐catalytic property to that of spherical PdNPs. In the p‐NP reduction reaction, the apparent rate constant (Ka) over PdTOs was 0.358 min‐1, higher than spherical PdNPs‐0 (0.08 min‐1) with the similar particle size and lower than the same spherical PdNPs‐4:1 (0.562 min‐1) and commercial Pd/C (0.415 min‐1), which all about half the size of PdTOs. It has been demonstrated that electro‐chemical oxidation of methanol was a structure‐sensitive reaction, while the reduction of p‐NP was mainly dependent on the particle size of PdNPs.     

含水合物粉质黏土压裂成缝特征实验研究

水力压裂技术是一种重要的油气井增产、增注措施,已经广泛应用于页岩油气等非常规资源的商业开采中.目前对于粉质黏土水合物沉积物的水力压裂成缝能力尚不清楚.本文采用南海水合物沉积层的粉质黏土制备沉积物试样,并与实验室配制的粉细砂土沉积物对比,分析粉质黏土沉积物的水力成缝能力及主控因素.实验结果表明含水合物和冰的沉积物破裂压力较高,这与粉质黏土沉积物特殊的应力-应变特征和渗透性有关.当沉积物应变高于6%时, 试样强度迅速上升, 呈现应变强化的特征,对水力拉伸裂缝的扩展具有一定的阻碍作用. 粉质黏土沉积物粒径细小, 渗透性差,难以通过渗透作用传递压力, 提高了沉积层的破裂压力. 此外,粉质黏土水合物沉积层裂缝扩展存在明显延迟效应,说明裂缝扩展受到流体压力和热应力的共同影响. 适当延长注入时间,保持流体与沉积层充分接触, 会起到分解水合物、降低破裂压力的作用.该研究成果有利于深入理解水力裂缝在水合物沉积层中的扩展规律,对探索压裂技术在水合物沉积层开发中的应用具有重要意义.      

Agostic Interactions in Early Transition-Metal Complexes: Roles of Hyperconjugation,Dispersion, and Steric Effect

The agostic interaction is a ubiquitous phenomenon in catalytic processes and transition-metal complexes, and hyperconjugation has been well recognized as its origin. Yet, recent studies showed that either short-range London dispersion or structural constraints could be the driving force, although proper evaluation of the role of hyperconjugation therein is needed. Herein, a simple variant of valence bond theory was employed to study a few exemplary Ti complexes with α- or β-agostic interactions and interpret the agostic effect in terms of the steric effect, hyperconjugation, and dispersion. For the complexes [MeTiCl₃(dmpe)] and [MeTiCl₃(dhpe)] with α-agostic interactions, hyperconjugation plays the dominant role with comparable magnitudes in both systems, but dispersion is solely responsible for the stronger agostic interaction in the former compared with the latter. For the complexes [EtTiCl₃(dmpe)] and [EtTiCl₃(dhpe)] with β-agostic interactions, however, hyperconjugation and dispersion play comparable roles, and the weaker steric repulsion leads to a stronger agostic effect in the former than in the latter. Thus, the present study clarifies the variable and sensitive roles of steric, hyperconjugative, and dispersion interactions in the agostic interaction.     

光纤探头烧结电路设计

为了满足烧结光纤探头的需要,设计了一种基于脉宽调制芯片CA1524的高压放电装置.首先通过推挽功率放大电路,将直流电逆变为高压交流电；然后经倍压整流得到2000多伏的直流电,最后连接电极棒进行高压放电.使用芯片LPC1768控制CA1524输出波形的占空比来改变放电强度,以及放电时间.     

Preparation and properties of oxadiazole‐containing polyacetylenes as electron transport materials

A series of functional polyacetylenes (PAs) bearing diphenyl oxadiazole pendant groups ( P1 – P4 ) were prepared, and the resultant polymers are completely soluble in common organic solvents. Their structures and properties were characterized and evaluated by DSC, TGA, UV, PL, CV, and EL analyses. The results show that all the resulting polymers possesses low LUMO energy level and high thermal stability, and the resultant functional polyacetylenes without spacer group between the polyacetylene conjugated main chain and oxadiazole pendant groups ( P1 – P3 ) show lower LUMO energy level (～?3.87 eV) and higher thermal properties (T_g) than that ( P4 ) with a flexible spacer. The resultant polymer ( P2 ) was applied as an ETM in bilayer electroluminescent devices and effectively enhances external quantum efficiency and the brightness of device, and decreases turn‐on voltages of devices. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1406–1414, 2010     

Microsecond timescale MD simulations at the transition state of PmHMGR predict remote allosteric residues

Understanding the mechanisms of enzymatic catalysis requires a detailed understanding of the complex interplay of structure and dynamics of large systems that is a challenge for both experimental and computational approaches. More importantly, the computational demands of QM/MM simulations mean that the dynamics of the reaction can only be considered on a timescale of nanoseconds even though the conformational changes needed to reach the catalytically active state happen on a much slower timescale. Here we demonstrate an alternative approach that uses transition state force fields (TSFFs) derived by the quantum-guided molecular mechanics (Q2MM) method that provides a consistent treatment of the entire system at the classical molecular mechanics level and allows simulations at the microsecond timescale. Application of this approach to the second hydride transfer transition state of HMG-CoA reductase from Pseudomonas mevalonii (PmHMGR) identified three remote residues, R396, E399 and L407, (15–27 Å away from the active site) that have a remote dynamic effect on enzyme activity. The predictions were subsequently validated experimentally via site-directed mutagenesis. These results show that microsecond timescale MD simulations of transition states are possible and can predict rather than just rationalize remote allosteric residues.

Transition state force fields enable MD simulations at the transition state of HMGCoA reductase that sample the transition state ensemble on the μs timescale to identify remote residues that affect the reaction rate.     

基于光信号偏振度的偏振模色散补偿系统的研究

偏振模色散已成为当前发展高速长距离光纤传输系统的主要限制因素。理论上分析了光纤一阶偏振膜色散效应对高速伪随机非归零码／归零码光信号偏振度的影响，并利用数值模拟的方法分析了信号不同输入偏振态以及高阶偏振膜色散效应对非归零码光信号偏振度的影响。最后对利用信号偏振度作为反馈控制信号的自适应偏振膜色散补偿系统的补偿性能进行了分析，大量统计分析结果表明对于10Gbit／s的非归零码光纤传输系统，当传输线路的平均偏振膜色散值小于43ps时，利用极大化输出信号偏振度的偏振膜色散补偿系统对信号眼图的补偿概率可以达到99．99％．     

An Extremely Narrow‐Band‐Gap Conjugated Polymer with Heterocyclic Backbone and its Use in Optoelectronic Devices

Summary: A novel narrow‐band‐gap conjugated polymer with heterocyclic backbone, poly[4,7‐bis(4‐decanyl‐2‐thienyl)‐2′,1′,3^′‐benzothiadiazole‐thiophene‐2,5‐] (PDDBT, E_g = 1.38 eV) was synthesized by a Stille coupling reaction. Prototype bulk heterojunction photovoltaic cells from PDDBT and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) with a ITO/PEDOT:PSS/PDDBT:PCBM(1:3)/Ba/Al device architecture showed power conversion efficiencies up to 0.13% under AM1.5 solar simulator (100 mW · cm⁻²) with an open‐circuit voltage V_oc of 0.65 V, a short‐circuit current density J_sc of 0.6 mA · cm⁻², and a photocurrent response up to 880 nm. The electroluminescent device from PDDBT showed a near‐infrared light emission peak at around 830 nm with maximal external quantum efficiency of 0.08% and a turn‐on voltage at 3.5 V.

Normalized PL and EL spectra of PDDBT and photosensitivity of PVCs based on PDDBT/PCBM (1:3) blend. The scheme shows the chemical structure of PDDBT.     

平面剪切来流作用下串列布置三圆柱流致运动特性研究

基于四步半隐式特征线分裂算子有限元方法,对Re=100时,剪切来流作用下串列三圆柱体双自由度流致振动问题进行了数值计算. 首先,与现有文献结果进行对比验证该方法的正确性. 然后,着重分析剪切率、固有频率比和折减速度三个关键参数对串列三圆柱体结构流致动力响应及流场特性的影响. 数值计算结果表明:剪切率、固有频率比与折减速度对结构振幅和运动轨迹的影响较大. 随剪切率的增大,上游圆柱最大振幅的变化与单圆柱工况类似. 中下游圆柱最大振幅会增大且会出现双向共振现象,同时,发生共振响应区域会扩大. 随固有频率比的增大,上游圆柱顺流向锁定区间范围会减小,而中下游圆柱双向锁定区间会扩大. 另一方面,均匀来流作用下,结构运动轨迹以"8"字形和不规则形状为主. 随剪切率的增大,锁定区间内运动轨迹会由"8"字形转变为"雨滴"形. 在大剪切率与高固有频率比工况下,中游圆柱体结构运动轨迹会出现"双雨滴"形状. 最后,通过对流场特性的分析,揭示了剪切来流作用下串列三圆柱结构流致运动响应的内在机理.