A rapid UPLC‐MS/MS method for the determination of oleanolic acid in rat plasma and liver tissue: application to plasma and liver pharmacokinetics

A reliable high‐throughput ultra‐high performance liquid chromatography–tandem mass spectrometry (UPLC‐MS/MS) method was developed and validated for oleanolic acid (OA) determination in rat plasma and liver tissue using glycyrrhetic acid as the internal standard (IS). Plasma and liver homogenate samples were prepared using solid‐phase extraction. Chromatographic separation was achieved on a C₁₈ column using an isocratic mobile phase system. The detection was performed by multiple reaction monitoring mode via positive electrospray ionization interface. The calibration curves showed good linearity (R² > 0.9997) within the tested concentration ranges. The lower limit of quantification for plasma and liver tissue was ≤0.75 ng/mL. The intra‐ and inter‐day precision and accuracy deviations were within ±15% in plasma and liver tissue. The mean extraction recoveries ranged from 80.8 to 87.0%. In addition, the carryover, matrix effect, stability and robustness involved in the method were also validated. The method was successfully applied to the plasma and hepatic pharmacokinetics of OA after oral administration to rats. Copyright © 2015 John Wiley & Sons, Ltd.     

亲水性相互作用色谱-串联质谱联用法检验鱼塘水中的草甘膦

建立了亲水性相互作用色谱-串联质谱联用法检验鱼塘水中草甘膦的方法。样品经去离子水提取,C18固相萃取柱和滤膜净化后,以0.5%异丙胺-乙腈为流动相,亲水性相互作用色谱柱分离,负离子扫描和多反应监测模式质谱监测,基质匹配标准溶液外标法定量。草甘膦质量浓度在10～1000 ng/mL范围内线性良好(r≥0.9973),日内、日间精密度RSD≤10%(n=5),鱼塘水中草甘膦的回收率在90%以上。该方法不需衍生化,净化步骤简便快捷,定量准确,可满足侦查和诉讼中草甘膦的检测要求。     

合成气一步法制二甲醚的动力学研究

采用固定床积分反应器，研究了用浸渍法制备的CuO-ZnO/Y-zeolite双功能催化剂上CO加氢直接合成二甲醚的反应动力学，按一氧化碳加氢先合成甲醇，再由甲醇脱水生成二甲醚两步串联的反应机理，分别建立了动力学模型，并对该催化剂对甲醇合成及甲醇脱水的机理作了探讨。模型的计算值和实验值能较好吻合，两步反应的表观活化能分别为27．98kJ/mol和30.62kJ/mol。     

Divergent Syntheses of Fused β‐Naphthol and Indene Scaffolds by Rhodium‐Catalyzed Direct and Decarbonylative Alkyne–Benzocyclobutenone Couplings

A tunable rhodium‐catalyzed intramolecular alkyne insertion reaction proceeding through the C? C cleavage of benzocyclobutenones is described. Selective formation of either the direct or decarbonylative insertion product can be controlled by using different catalytic systems. A variety of fused β‐naphthol and indene scaffolds were obtained in good yields with high functional group tolerance. This work illustrates a divergent approach to synthesize fused‐ring systems by C? C activation/functionalization.     

Investigation on Photophysical Properties of D–π–A–π–D‐Type Fluorenone‐Based Linear Conjugated Oligomers by Using Femtosecond Transient Absorption Spectroscopy

The effects of π‐spacer and electron donor groups on the photophysical behaviors of fluorenone‐based linear conjugated oligomers have been systemically investigated. Solvent‐dependent steady‐state measurements exhibit that the fluorene vinylene (FV) spacer and the electron‐donating ability of donor group are able to modulate the spectral features of oligomers and the fluorescence quantum yield could decrease with the increasing of the solvent polarity. Meanwhile, quantum chemical calculation simulates their absorption spectra, and analyzes their electron transition components simultaneously. The transient absorption measurements focus on the photoexcitation dynamics of these oligomers in the toluene solution, which show that an intramolecular charge transfer state exists in the relaxation process of excited states, and its generation process could accelerate with the introduction of FV spacer and the enhancement of donor strength.     

反应烧结碳化硅复合材料的磨损机理研究

采用销－盘摩擦磨损试验机考察了反应烧结碳化硅及含Ｎｉ碳化硅复合材料在不同温度下的干摩擦磨损性能。结果表明,Ｎｉ有利于改善反应烧结碳化硅复合材料的摩擦磨损性能。ＳＥＭ磨损表面和亚表面分析表明,复合材料在常温下的磨损机理为削和犁沟;６００℃下反应烧结碳化硅的磨损机理为表面裂纹形成及断裂;而含Ｎｉ碳化硅复合材料的磨损机理为亚表面裂纹扩展导致表面局部剥落。     

TiN涂层的径向微动行为

对ＧＣｒ１５／４５＃钢和ＧＣｒ１５／离子镀ＴｉＮ涂层的４５钢摩擦副进行了径向微动试验,试验的最大载荷从２００Ｎ到８００Ｎ,循环次数为１０＾５。摩擦磨损试验结果表明,ＴｉＮ涂层的抗塑性变形能力和抗么向微动损伤能力比基体好,ＳＥＭ分析表明,ＴｉＮ涂层的磨屑呈现剥层特征钢试样表现出粘着现象。     

新型径向微动装置

通过对高精度平移式微动试验台夹具和控制程度进行改造,研制了径向微动试验装置,该装置可以分别在控制荷载和控制变形量２种模式下进行试验,可以通过改变变形速率（频率）来控制接触偶件之间的相对运动速度,因此能较好地模拟真实的径微动动运动,且试验结果有很好的可比性和重现性。     

MILO中场不稳定性的非线性发展及混沌行为

 以磁绝缘传输线振荡器中电子运动和辐射场演化方程为基础，分析了场与电子相互作用过程中的不稳定性。这种不稳定性的发展导致场出现极限环振荡和混沌。在软非线性区域，辐射场表现为不连续的极限环振荡；在硬非线性区域，辐射场表现为连续的混沌行为。控制失谐量可加速或抑制这些不稳定态的出现。优化和调节参数可控制器件的运行状态, 获得较高的输出功率。     

磁绝缘传输线振荡器中辐射场的非线性行为

 导出了磁绝缘传输线振荡器(MILO)中辐射场的非线性演化方程，并讨论了在临界值点附近可能出现非线性不稳定解的条件。结论是：(1)非线性增长速率与线性增长速率的比值g<1.2，且远离g+γ=1(γ为非线性相位增长率与线性相位增长率的比值)点时，出现非稳定解的失谐量临界值很小，而线性增长速率临界值临界值很大，容易出现非稳定解；(2)当g≥1.2时，任意小的失谐量都可以使场出现非稳定解；(3)线性增长速率越大，越不容易出现非稳定解。