Conjugate spacer effect on molecular structures and absorption spectra of triphenylamine dyes for sensitized solar cells: density functional theory calculations

The molecular structures and absorption spectra of triphenylamine dyes containing variable thiophene units as the spacers (TPA1-TPA3) were investigated by density functional theory (DFT) and time-dependent DFT. The calculated results indicate that the strong conjugation is formed in the dyes and the length of conjugate bridge increases gradually with the increased thiophene spacers. The interfacial charge transfer between the TiO2 electrode and TPA1-TPA3 are electron injection processes from the excited dyes to the semiconductor conduction band. The simulated absorption bands are assigned to π→π* transitions, which exhibit appreciable red-shift with respect to the experimental bands due to the lack of direct solute-solvent interaction and the inherent approximations in TD-DFT. The effect of thiophene spacers on the molecular structures, absorption spectra and photovoltaic performance were comparatively discussed and points out that the choice of appropriate conjugate bridge is very important for the design of new dyes with improved performance.     

Structure and properties of composites compression‐molded from silk fibroin powder and waterborne polyurethane

The degummed silk filament was pulverized with a home‐made machine to obtain the silk fibroin (SF) powder with the diameter of around 3 µm. The resulting SF powder was blended with waterborne polyurethane (WPU) aqueous dispersion, and then was dried and compression‐molded to prepare novel blended materials with improved miscibility and mechanical properties. WPU acted as a plasticizer and one of the components for the blends during the compression‐molded process. The structure, morphology, and properties of the blended films were investigated. The results indicated that β‐sheet of SF existed in the blended films. The SEM images showed that the cross‐section of the blended films exhibited an overall homogeneous morphology. Furthermore, the transmission electron microscope observation exhibited that some sphere‐like SF particles were well dispersed in the WPU matrix. The hydrogen bond interaction between SF and WPU in the blended films led to an increase of the glass transition temperature for the soft segment of WPU in the blended films. The blended films showed an improved Young's modulus and tensile strength from 1.2 to 288.9 MPa and 0.3 to 16.5 MPa, respectively, with the increasing of SF up to a content of 70 wt%. The hydrogen‐bonding interactions existing in SF and WPU and compression molding method played the important role in improving the miscibility and mechanical properties of the blended films. Copyright © 2011 John Wiley & Sons, Ltd.     

硅胶负载的亚胺环钯催化剂的制备、表征及催化性能

利用SiO2表面硅羟基与有机硅烷作用制得氨基化SiO2,再与邻甲氧基苯甲醛反应,可得到键合在SiO2微粒表面的席夫碱配体,该配体与Li2PdCl4甲醇溶液反应得到SiO2负载的亚胺环钯催化剂.采用傅里叶变换红外光谱、X射线固体粉末衍射和X射线光电子能谱等手段对催化剂进行了表征,并用于催化碘代苯(PhI)与丙烯酰胺(AM)反应生成反式-肉桂酰胺的反应中,考察了溶剂、温度、原料比、缚酸剂及其用量、催化剂用量和反应时间对催化性能的影响,从而得到适宜的反应条件,并探讨了反应机理.     

NUMERICAL INVESTIGATION ON FLOW-INDUCED VIBRATION OF TWO CYLINDERS IN TANDEM ARRANGEMENTS AND ITS COUPLING MECHANISMS

对雷诺数Re= 100 条件下串列双圆柱的流致振动进行了数值模拟. 圆柱的质量比m^*均为2.0,间距比L/D 为2.0 5.0. 考虑两种工况:(a) 上游圆柱固定,下游圆柱可沿横流向自由振动;(b) 上、下游圆柱均可沿横流向自由振动. 结果表明:无论上游圆柱静止或者振动,下游圆柱横向振幅明显大于单圆柱的. 工况(b) 的下游圆柱最大振幅要大于工况(a) 的,这是由于两圆柱均振动时,两圆柱之间耦合作用增强,上游圆柱的尾流和下游圆柱的振动之间“相互调节” 作用显著. 对工况(b) 的下游圆柱振动和间隙流之间的作用机制进行了详细的研究,发现当上游圆柱脱落的自由剪切层重新附着于下游圆柱上并且完全从间隙之间通过时,下游圆柱的振幅最大.     

Probing redox photocatalysis of trapped electrons and holes on single Sb-doped titania nanorod surfaces

We used a fluorogenic reaction to study in conjunction the photocatalytic properties for both active sites (trapped photogenerated electrons and holes) on individual Sb-doped TiO(2) nanorods with single-molecule fluorescence microscopy. It was found that active sites around trapped holes show higher activity, stronger binding ability, and a different dissociation mechanism for the same substrate and product molecules in comparison with the active sites around trapped electrons. These differences could be elucidated by a model involving the charged microenvironments around the active sites.     

Development of a UHPLC-MS/MS method for the measurement of chlortetracycline degradation in swine manure

An ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was developed capable of simultaneously measuring chlortetracycline (CTC), epi-chlortetracycline, and isochlortetracycline (ICTC), as well as other structurally related tetracyclines in swine manure. A simple sample preparation was used consisting of extraction, dilution, centrifugation, and ultrafiltration. The concentrations of analyte were calculated using d₆-tetracycline as an internal standard in the matrix-matched standard curve. A solvent gradient resolved the compounds in 3.5 min with an additional 1.5 min of re-equilibration allowing the analyses of a large number of samples in a short period of time. MS/MS was used as the detection method giving analyte confirmation in addition to a large dynamic range and low detection limit. The UHPLC-MS/MS method successfully resolved multiple degradation products of CTC from the complex manure matrix. The method detection limits ranged from 1.9 pg/μL for CTC to 7.3 pg/μL for ICTC, and the calibration curve was linear from 1 to 10,000 pg/μL. The method was tested by measuring CTC and its degradation products as a function of time in incurred swine manure that had been incubated at three different temperatures (22 °C, 38 °C, and 55 °C). CTC concentration at 22 °C decreased 44% after 25 days; greater percentage decreases were observed when the manure was stored at elevated temperatures (96% and 98% for 38 °C and 55 °C, respectively). The concentration of the microbiologically inactivate isomer, ICTC, increased over the incubation period. At 22 °C, ICTC continued to increase through 25 days of incubation; at 38 °C, ICTC concentration plateaued on day 14 while at 55 °C ICTC concentration plateaued on day 7, with concentration increases of 198%, 374%, and 282% for 22 °C, 38 °C, and 55 °C, respectively.     

基于色氨酸本征荧光测量的生物气溶胶检测技术研究

生物气溶胶与环境质量和人类健康密切相关。基于光学测量的气溶胶检测技术具有快速、无损和灵敏的优点,是目前的研究主流。而对检测系统的标定技术及其评价方法尚无国家标准可依。基于本征荧光测量技术,研制完成了一套针对包括病毒气溶胶在内的生物气溶胶检测装置。并在此基础上,以色氨酸气溶胶作为被检物,提出了一种生物气溶胶检测与标定方法。实验结果表明,研制的检测装置对色氨酸气溶胶具良好的线性响应特性,线性相关系数R2≥0.99,灵敏度达到4000L-1。证明了通过测量气溶胶中色氨酸含量检测生物气溶胶技术的可行性与可靠性。还探讨了利用多通道本征荧光检测技术实现对生物粒子种类进行预判别的可行性。     

新型WO3/HMS催化剂的制备及其对环戊烯选择氧化反应的催化性能

 采用草酸络合方法将WO3固载到六方介孔全硅分子筛HMS上,制得新型WO3/HMS非均相催化剂. 利用SEM,TEM,N2吸附,XRD及激光拉曼光谱等手段对催化剂进行了表征,研究了催化剂在环戊烯选择性氧化合成戊二醛反应中的催化性能. 结果表明,在WO3/HMS催化下环戊烯和H2O2的转化率均可达100%,戊二醛的选择性可达72%. WO3以高分散状态存在于催化剂表面. 单次反应后钨的溶脱量(5.5 μg/ml)很小,对反应几乎没有影响. 催化剂具有较高的稳定性,可以重复套用6次. 失活后的催化剂可通过简单焙烧的方式再生.     

热声驱动脉管制冷机系统的效率评价

采用热声压缩机驱动脉管制冷机将完全消除系统的机械运动部件 ,大大提高了运行的可靠性。随着热声驱动脉管制冷机研究的不断深入 ,人们迫切需要能真实反映系统效率的评价标准 ,文中给出三种评价方法 :(1 )系统的总效率 ;(2 )系统的相对卡诺效率 ;(3)系统的火用效率。建议采用火用效率对系统效率进行综合评价 ,这对系统的性能改善以及实用化研究具有一定的参考价值