超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法非靶向筛查苹果中苯脲类农药

建立了超高效液相色谱－四极杆/静电场轨道阱高分辨质谱（UPLC-Q/Orbitrap HRMS）非靶向筛查苹果中苯脲类农药的方法。样品采用QuEChERS法提取净化,Acquity BEH C18色谱柱（100 mm × 2.1 mm,1.7 μm）分离,以甲醇和含0.1%甲酸的水溶液为流动相进行梯度洗脱,在电喷雾正离子模式下采用四极杆/静电场轨道阱高分辨质谱进行检测。将13种苯脲类除草剂和9种苯甲酰脲类杀虫剂按化学结构分为4类。首先通过对4类22种典型苯脲类农药标准品的准分子离子和二级质谱碎片进行分析,总结苯脲类农药的质谱裂解规律如下：绿麦隆等9种苯脲类除草剂的主要特征离子碎片为m/z 72.044 59,可通过特征丢失中性分子二甲胺（m/z 45.058 03）产生特征离子碎片;绿谷隆等4种苯脲类除草剂可通过特征丢失中性分子甲醇［CH3OH］或卤化氢［HR1］（R=Cl,Br,F）产生离子碎片;除虫脲等7种含氟苯甲酰脲杀虫剂的主要特征离子碎片为 m/z 158.040 47、141.015 00,也可发生特征中性丢失2,6-氟苯甲酰胺结构［C8H3F2O2NH2］（m/z 183.013 21）;杀铃脲等2种含氯苯甲酰脲类杀虫剂的主要特征离子碎片为m/z 156.020 25、138.993 76、113.015 28。利用该方法对北京12份市售苹果进行非靶向筛查,在1份样品中筛查出绿麦隆。该方法可为快速筛查农产品中相似结构特征的苯脲类化合物提供参考。     

大学基础化学教学中的知其所以然*

针对大学本科一年级基础化学如“化学概论”等课程教学中,学生对于不断出现的专业名词及物理化学含义的理解问题,以“焓”“熵”等外来词汇以及角动量l、能级分裂单位“Dq”等缩写为例,从专业名词来源开始讲解,使学生在学习过程中既知其然又知其所以然,更好地理解化学专业词汇,尤其是外来词汇的内涵与物理化学意义。     

超高效液相色谱-四极杆静电场轨道阱高分辨质谱测定聚丙烯酰胺中丙烯酰胺单体的残留

通过Hypercarb色谱柱分离,建立了四极杆静电场轨道阱高分辨质谱平行反应监测(PRM)模式检测聚丙烯酰胺(PAM)中单体残留量的方法。PAM经水稀释,高速搅拌溶解均匀,过0.22μm水相滤膜后,直接用高分辨质谱Q Exactive采集数据。以Hypercarb色谱柱为分析柱,水和甲醇为流动相,柱温为20℃,采用PRM模式,提取目标化合物及其二级子离子的精确质量数,并对二级特征碎片进行同位素匹配,推测碎裂规律,以强化定性效果。结果表明:在2~50μg/L范围内线性关系良好(相关系数为0.999 8),方法检出限(LOD)可达到1.5μg/kg,满足食品级PAM的检测要求。通过加标验证,回收率为101.3%~107.1%,相对标准偏差为3.1%~4.1%。实际样品验证结果表明,PAM中丙烯酰胺(AM)单体的残留质量分数范围为0~0.43%,存在一定的安全风险。该方法简单、准确、高效,可作为快检和确证检测技术广泛使用。     

超高效液相色谱-四极杆/静电场轨道阱高分辨质谱检测食品中的牛奶过敏原酪蛋白

基于超高效液相色谱-四极杆/静电场轨道阱高分辨质谱系统,建立了食品中牛奶过敏原酪蛋白的快速筛查和定量检测方法。样品经缓冲液提取后,采用5 kD超滤膜去除小分子杂质,得到蛋白质提取液。以数据依赖采集(data-dependent acquisition,DDA)方式获得全扫描质谱图,进行蛋白质定性确证,以平行反应监测(parallel reaction monitoring,PRM)技术对目标特征肽段进行定量分析。针对特征肽段,设计并合成了内标肽和内标物质,以降低基质效应和抵消处理过程中的损失。该方法应用于食品中的α-酪蛋白、β-酪蛋白和κ-酪蛋白的快速筛查和定量检测。结果表明,该方法在5~250μg/L范围内线性关系良好,定量限为0.2~5.5μg/kg,平均回收率在68.8%~104.4%之间,RSD6%。该方法可用于果汁饮料、果酱、面包、早餐谷物中牛奶过敏原酪蛋白的快速筛查和定量分析。     

Response of Bi-disperse Polyelectrolyte Brushes to External Electric Fields——A Numerical Self-consistent Field Theory Study

The self-consistent field theory has been employed to numerically study the response of bi-disperse flexible polyelectrolyte (PE) brushes grafted on an electrode to electric fields generated by opposite surface charges on the PE-grafted electrode and a second parallel electrode. The numerical study reveals that, under a positive external electric field, the shorter and negatively charged PE chains are more responsive than the longer PE chains in terms of the relative changes in their respective brush heights. Whereas under a negative external electric field, the opposite was observed. The total electric force on the grafted PE chains was calculated and it was found that, under a positive external electric field, the magnitude of the total electric force acting on one shorter PE chain is larger than that on one longer PE chain, or vice versa. The underlying mechanism was unraveled through analyzing the total electric field across the two oppositely charged electrodes.     

Optimisation of alignment materials for minimising residual retardation in in-plane switching liquid crystal display

The light leakage in a black state of in-plane switching (IPS) liquid crystal display (LCD) associated with rubbing process has been investigated. The mechanical rubbing process with a cloth caused orientation disorders in the liquid crystal directors and these partial orientation disorders result in residual retardations of the IPS LCD, causing the light leakages at the black state. In this study, we theoretically estimated how the light leakage is associated with the rubbing uniformity using 2 × 2 Jones matrix equation and also experimentally confirmed how it is associated with structural properties of the alignment layer. The light leakage was clearly reduced in the alignment layer with reduced crystallinity and flexibility.     

胜利断块油藏细分注水技术界限研究

老油田进入特高含水期后,剩余油分布更加零散,各种地质因素也因长期注水开发而发生了一定的改变.此时稳油控水难度进一步加大,为了进一步挖掘剩余油,控制含水上升速度、减缓产量递减,必须对注水井采取进一步的细分调整.基于水湿油藏注水井注水层段吸水效果,从注入水受力分析入手,运用达西定律推导出了水驱油藏水驱油全过程中的单位体积注入水沿竖直、地层两个方向运移的渗流速度公式,明晰了水驱油藏注水层段不同开发阶段砂岩吸水机理.研究结果表明,水驱油藏细分注水效果与岩石绝对渗透率、水相相对渗透率、注入水黏度、水动力压力梯度、注水井启动压力梯度、含水饱和度、地层倾角、油水密度差等参数有关.结合胜利油田断块油藏地质特征及细分注水工艺要求,制定了一套适合胜利油田不同断块区的细分注水技术政策界限:层段内渗透率变异系数小于0.3,砂岩条带宽度极比小于2.5,且东辛油区断块油藏层段内砂岩厚度小于6m,小层数小于4个;现河油区断块油藏层段内砂岩厚度小于5m,小层数小于5个;临盘油区断块油藏层段内砂岩厚度小于6m,小层数小于6个.矿场试验证实,该细分注水技术政策界限是合理、实用的,其为胜利断块油藏注上水、注够水、注好水,实现多层断块油藏的高效开发提供了技术保障,对类似油藏细分注水技术界限研究具有一定的借鉴意义.     

Influence of the Oxide Content in the Catalytic Power of Raney Nickel in Hydrogen Generation

The influence of oxides in the hydrogen evolution on Raney nickel electrocatalysts was characterized by electrochemical impedance measurements. In addition, these materials show competitive overpotentials for hydrogen evolution with a modified Watts bath as a binder for the Raney nickel. The optimum result was ?190?mV of overpotential at 100?mA?cm^?2. Oxygen in the Raney Ni catalyst affects its electroactivity toward hydrogen evolution. The source of oxygen is related to the presence of chloride ions in the modified Watts bath. A Watts bath binds Raney Ni particles to the surface of the catalysts and chloride regulates the oxygen content in the nickel binder during electrodeposition. High oxygen content increases the hydrogen evolution overpotential of the electrode. The electroactivity of the synthesized porous coatings was evaluated by polarization curves and impedance plots. In addition, surface characterization by X-ray diffraction, field emission–scanning electron microscopy equipped with energy-dispersive analysis, and X-ray photoelectron spectroscopy is reported.     

Preparation of Ag Nanowire @ Au Nanoparticle Hybrid Nanowires and their Influence on the Fluorescence Properties of P3HT

In this study, the galvanic displacement reaction between silver and AuCl₄⁻ was carried out to synthesize a series of silver nanowire (Ag NW) @ gold nanoparticle (Au NP) hybrid nanowires. The influence of Ag NW @ Au NP hybrid nanowires on the fluorescence properties of the poly (3‐hexylthiophene) (P3HT) was investigated. The particle sizes of Au NPs on the hybrid nanowires could be adjusted by varying the reaction time and the concentration of the HAuCl₄ solution. Furthermore, steady‐state fluorescence measurements showed that the fluorescence intensity of the P3HT films was higher on various Ag NW @ Au NP hybrid nanowires compared to that on a bare silicon substrate. This was due to the increase in the intensity of electromagnetic field by the localized surface plasmon resonances of Au NPs and surface plasmon polaritons of Ag NWs from the hybrid nanowires. The results were further confirmed by the Raman spectra of the P3HT films on different substrates.     

Improved separation and size characterization of gold nanoparticles through a novel capillary zone electrophoresis method using poly(sodium4‐styrenesulfonate) as stabiliser and a stepwise field strength gradient

A novel capillary zone electrophoresis (CZE) method was developed for an improved separation and size characterization of pristine gold nanoparticles (AuNP) using uncoated fused‐silica capillaries with UV‐Vis detection at 520 nm. To avoid colloid aggregation and/or adsorption during runs, poly(sodium 4‐styrenesulfonate) (PSS) was added (1%, w/v) in the running buffer (CAPS 10 mM, pH 11). This polyelectrolyte conferred an enhanced stabilization to AuNP, both steric and electrostatic, exalting at the same time their differences in electrophoretic mobility. Resolution was further and successfully improved through a stepwise field strength gradient by the application of 25 kV for the first 5 min and then 10 kV. Migration times varied linearly with particles diameters showing relative standard deviations better than 1% for daily experiments and 3% for interday experiments. A comparison with the size distribution obtained by transmission electron microscopy (TEM) allowed assessing that the electrophoretic profile can reasonably be considered as representative of the effective size heterogeneity of each colloid. Finally, the practical utility of the proposed method was demonstrated by measuring the core diameter of a gold colloid sample produced by chemical synthesis which was in good agreement with the value obtained by TEM measurements.