从聚酰亚胺单分子链电荷陷阱特性的改变探讨体材料的沿面放电现象

沿面放电是破坏绝缘系统性能的原因之一.聚酰亚胺常用于高频电力设备的气-固绝缘中,为此利用密度泛函理论,从原子分子层面探讨了在外电场下聚酰亚胺及其受极性基团OH~–影响后的单分子链结构、能级与态密度、静电势、激发态等微观参数对陷阱形成以及沿面放电的影响.结果表明,外电场下,聚酰亚胺分子结构卷曲,偶极矩增加,易于积聚电荷形成空间电荷中心,尤属引入极性基团OH~–后变化较明显;聚酰亚胺分子中,苯环区域形成空穴陷阱,酰亚胺环区域形成电子陷阱,且电子陷阱能级的数量较多,其中空间电荷陷阱深度随外电场的增加逐渐变深;聚酰亚胺分子在引入极性基团OH~–后激发能降低,使得分子内部的电子变得容易被激发;电子与空穴的空间分离度随电场增加而降低,利于空穴与电子的复合而发出光子.     

虚时路径积分的广义四阶拆分方法及其谐振子分析

虚时路径积分方法是计算实际体系量子热力学性质的有效工具. 本文重点分析讨论了基于二阶和四阶拆分的虚时路径积分的有效性,给出谐振子体系配分函数统一的解析形式,进而得到其热力学性质和主要误差的表达式. 通过去除谐振子配分函数的主要误差,广义对称四阶拆分中的自由参数得以固定,以此计算实际体系的热力学量可以达到期望的三阶精度.     

Vitamin C-silver: an environmentally benign choice for DNA visualization on polyacrylamide gels

A practical, sensitive and environment-benign protocol for the detection of DNA on polyacrylamide gels was described. In this method, the most commonly used formaldehyde-based developer in DNA silver stain, which poses potential hazards to the health of operators, is firstly replaced by vitamin C (Vc) in sodium thiosulfate solution. This allows user-friendly and efficient visualization of DNA that takes about 20 min to complete all the procedures, and provides comparable sensitivity (8 pg of single band) to the most sensitive formaldehyde-based silver staining method developed before.     

毛细管电泳-电致化学发光法测定兔血浆中的羟考酮

基于稀土Eu(Ⅲ)掺杂的类普鲁士蓝膜修饰的铂电极为工作电极,建立了测定羟考酮的毛细管电泳-电致化学发光分析方法。考察了检测电位、运行缓冲溶液的酸度及浓度、分离电压、进样条件等对电泳分离效果及检测灵敏度的影响。在最佳的实验条件下,羟考酮可在4 min内得到分离,其ECL强度值与羟考酮的质量浓度在7.0×10-2～7.0μg/mL和7.0～70.0μg/mL范围内呈良好的线性关系,检出限为4.2×10-2μg/mL(3σ),峰高和迁移时间的相对偏差分别为3.6%和0.48%(n=6)。方法用于兔血浆中羟考酮含量的检测,加标回收率在99.7%～101.0%之间。     

KIO4-四硼酸钠系统阻抑亮绿褪色动力学光度法测定痕量Ir（Ⅳ）

基于H2SO4介质及四硼酸钠缓冲溶液中,80℃水浴中,Ir(Ⅳ)对KIO4氧化亮绿褪色反应具有阻抑作用,据此建立了阻抑动力学光度法测定痕量Ir(Ⅳ)的新方法。阻抑反应(吸光度A)与非阻抑反应(吸光度A0)吸光度差值△A与Ir(Ⅳ)的质量浓度ρ在0.0002～0.08μg/mL范围内呈良好的线性关系,检出限为2.969×10-10g/mL。对1μg/25 mL Ir(Ⅳ)标准溶液测定的相对标准偏差为1.7%(n=11)。测定了动力学参数,反应对Ir(Ⅳ)为一级反应,试验条件下,总反应为准一级反应,表观速率系数为2.883×10-4/s,表观活化能为52.2 kJ/mol。方法用于分子筛和活性炭样品中痕量Ir(Ⅳ)测定,加标回收率在98.1%～104.9%范围,符合痕量分析要求。     

Cross double Mannich reaction catalyzed by I2: Synthesis of highly substituted 4-piperidones

Cross double Mannich reaction and tandem cyclization were achieved under iodine catalyzed conditions,yielding a series of highly substituted 4-piperidones.Among the possible diastereomers,only one diastereomer was isolated,which could be ascribed to the chair-like transition state in six-membered ring,in which all of the hindered groups are located in the pseudoequatorial orientation.     

A novel dimeric procyanidin glucoside from Polygonum aviculare

A novel dimeric procyanidin glucoside,catechin 3-O-acetate-(4 α→8)-catechin 3-O-acetate-3’-O- β-D-glucopyranoside(1), along with five flavonoids and one lignan were isolated from the aerial parts of Polygonum aviculare.Their structures were elucidated by spectroscopic analyses including 1D,2D NMR,MS and CD methods.     

支撑磷脂双层膜的研究进展

支撑磷脂双层膜(supported phospholipid bilayers,SPBs)是细胞膜研究中普及的模型,是固定生物活性物质的理想材料,不仅可以保持生物分子的活性,还能有效抑制其他生物分子的非特异性吸附,在跨膜蛋白、仿生膜、水处理、生物医学和生物传感器等研究领域具有广泛的应用前景。本文介绍了支撑磷脂双层膜的表征方法和制备方法,包括Langmuir Blodgett(LB)膜提拉法、囊泡融合法和LB膜提拉法与囊泡融合联合法;详细阐述了囊泡融合法制备SPBs的机理;综述了囊泡融合法制备SPBs的影响因素,包括囊泡浓度、缓冲溶液、温度、囊泡和基底表面电荷等因素;列举了支撑磷脂膜的应用,并展望了支撑磷脂双层膜的研究趋势。     

Crystallization Elution Fractionation and Thermal Gradient Interaction Chromatography. Techniques Comparison

Summary: The chemical composition distribution has been shown to be the most critical and discriminating parameter in understanding the performance of industrial polyolefins with non homogeneous comonomer incorporation. The chemical composition distribution is being analyzed by well known techniques such as temperature rising elution fractionation, TREF, crystallization analysis fractionation, CRYSTAF and crystallization elution fractionation, CEF. These techniques separate according to crystallizability and provide a powerful and predictable separation of components based on the presence of branches, irregularities or tacticity differences, independently of the molar mass. TREF, CRYSTAF and CEF can not be used, however, for the separation of more amorphous resins, and may not always provide the best solution for complex multi-component resins due to the existence of some co-crystallization. The application of high temperature interactive HPLC to polyolefins opened a new route to characterize these types of polymers. The use of solvent gradient HPLC for separation of polyethylene and polypropylene and the developments in HPLC on carbon based columns extended further the application of high temperature HPLC in polyolefins. A new approach has been developed recently using the carbon based column but replacing solvent gradient by a thermal gradient which facilitates the analysis of polyethylene copolymers and provides a powerful tool for the analysis of elastomers. Thermal gradient interaction chromatography (TGIC) is being compared with TREF and CEF with the analysis of model samples. The advantages/disadvantages of each technique are being investigated and discussed. The combination of TGIC and TREF/CEF provides an extended range of separation of polyolefins.     

Simultaneous analysis and retention behavior of major isoflavonoids in Radix Puerariae lobatae and Radix Puerariae thomsonii by high performance liquid chromatography with cyclodextrins as a mobile phase modifier

In order to differentiate two species of Radix Puerariae (Radix Puerariae lobatae and Radix Puerariae thomsonii) and to determine major isoflavonoids (puerarin, daidzin, daidzein and genistein) in the samples, a simple high performance liquid chromatography (HPLC) method with isocratic elution employing cyclodextrins (CDs) as mobile phase additives was developed. Various factors affecting the retention of isoflavonoids in the C₁₈ reversed-phase column, such as the nature of CDs, the concentration of hydroxypropyl-β-cyclodextrin (HP-β-CD) and the methanol percentage in the mobile phase, were studied. Experimental results confirmed that HP-β-CD, as a very effective mobile phase additive, could markedly reduce the retention of isoflavonoids, especially daidzein and genistein. The elution of four isoflavonoids could be achieved on a Kromasil^® C₁₈ column within 56 min by using the methanol–water contained 5 mM HP-β-CD (25/75, v/v) mixture as the mobile phase. The formation of the inclusion complexes between isoflavonoids and HP-β-CD explained the modification of the retention of analytes. The apparent formation constants determined by HPLC confirmed that the stoichiometry of HP-β-CD-isoflavonoid complexes was 1:1, and the stability of the complexes depended on the size and property of isoflavonoids. The optimized method was successfully applied for the simultaneous determination of major isoflavonoids in P. lobatae and P. thomsonii samples. This work provides a useful method for the analysis of traditional Chinese herbs.