Quantitative determination of tiopronin in human plasma by LC-MS/MS without derivatization

Tiopronin (TP) is a synthetic thiol compound without chromophore. By optimizing the chromatographic conditions and sample preparation processes, an improved LC‐MS/MS analytical method without derivatization has been developed and validated to determine TP concentrations in human plasma. After reduction with 1,4‐dithiothreitol, plasma samples were deproteinized with 10% perchloric acid. The post‐treatment samples were analyzed on a C₈ column interfaced with a triple quadrupole tandem mass spectrometer in negative electrospray ionization mode. Methanol–5 mmol/L ammonium acetate (20:80, v/v) was used as the isocratic mobile phase. The assay was linear over the concentration range of 40.0–5000 ng/mL. The intra‐ and inter‐day precisions were within 12.9% in terms of relative standard deviation and the accuracy within 5.6% in terms of relative error. This simple and sensitive LC‐MS/MS method with short analytical time (3.5 min each sample) was successfully applied to the pharmacokinetic study of TP in healthy Chinese male volunteers after an oral dose of 300 mg TP. Copyright © 2011 John Wiley & Sons, Ltd.     

对乙酰基偶氮胂吸光光度法测定微量铜

在pH5.0的(CH2)6N4-HCl缓冲介质中,Cu(Ⅱ)与对乙酰基偶氮胂(ASApA)形成1比2络合物,λmax＝598nm,εmax=1.30×104L·mol-l·cm-1,铜浓度在0～2.0mg·L-1范围内遵从比耳定律。方法用于粮食、食品、水、树叶及人发等试样中铜的测定,结果满意。     

Exploring antibiotic resistant mechanism by microcalorimetry II

In an effort to understand the reaction of antibiotic hydrolysis with B2 metallo-??-lactamases (M??Ls), the thermodynamic parameters of imipenem hydrolysis catalyzed by metallo-??-lactamase ImiS from Aeromonas veronii bv. sobria were determined by microcalorimetric method. The values of activation free energy $ \Updelta G_{ \ne }^{\theta } $ are 86.400?±?0.043, 87.543?±?0.034, 88.772?±?0.024, and 89.845?±?0.035?kJ?mol^?1 at 293.15, 298.15, 303.15, and 308.15?K, respectively, activation enthalpy $ \Updelta H_{ \ne }^{\theta } $ is 18.586?±?0.009?kJ?mol^?1, activation entropy $ \Updelta S_{ \ne }^{\theta } $ is ?231.34?±?0.12?J?mol^?1?K^?1, apparent activation energy E is 21.084?kJ?mol^?1, and the reaction order is 1.5. The thermodynamic parameters reveal that the imipenem hydrolysis catalyzed by metallo-??-lactammase ImiS is an exothermic and spontaneous reaction.     

光纤生物传感器用于核酸的特异性检测

为了利用光纤传感器实现对细菌核酸分子的特异性和相对快速检测，我们使用直径1mm的石英光纤和635nm激光二极管，利用倏逝波原理制作了光纤生物传感器。光纤经过处理后产生醛基化基团，然后与核酸分子进行共价结合。通过3个实验来验证传感器的特异性和灵敏度。蒌光素溶液直接检测，使用互补模式寡核苷酸分子（25mer)进行核酸杂交模式实验和设计嗜肺军团菌一段特异性探针一 光标记嗜肺军团菌染色体DNA杂交。结果表明：光纤检测荧光素的灵敏度可达0.01mmol/L，而生物芯片扫描仪最低可检测到1nmol/L的荧光素；模式寡 核苷酸杂交表明：光纤传感器可以特异地检出目的核酸分子，灵敏度可达纳克级水平；染色体杂交结果显示在正常检测浓度下，光纤检测军团菌之信噪比达到了6：1，同时具有较好的特异性。检测时间约需要3－4h。我们构建的光纤生物传感器可以用于核酸分子的特异性检测，并且具有较好的灵敏度，对光纤表面修饰、样品处理和杂交过程的优化可望使之应用于实际标本的检测。     

一种新型阻燃抗熔滴共聚酯的合成及表征

双酚A与碳酸乙烯酯反应得到改性单体双(羟乙基)双酚A(BHEEB),BHEEB与对苯二甲酸、乙二醇及阻燃剂[(6-氧代-6H-二苯并[c,e][1,2]氧磷杂己环-6-基)甲基]丁二酸(DDP)通过无规共聚合成了一种新型阻燃共聚酯PBPET.用1H-NMR、ICP-AES对共聚酯的结构进行了表征,用热重分析(TGA)、氧指数(LOI)测定、垂直燃烧测试等对共聚酯的热稳定性、阻燃性和熔滴行为进行了研究.结果表明,BHEEB可以提高共聚酯的热稳定性,含5 mol%BHEEB与4.8 mol%DDP的共聚酯P4.8B5PET,其TGA测试中600℃下氮气氛残炭(wt6R00)可达18.0%.燃烧测试表明,P4.8B5PET的LOI值可达37.0,垂直燃烧达V-0级,并且改性单体BHEEB的引入还能有效地改善聚酯燃烧时的熔滴行为.     

Crucial factors affecting the physicochemical properties of sol–gel produced Fe3O4@SiO2–NH2 core–shell nanomaterials

Multifunctional nanomaterials with task-specific physicochemical properties, especially core?Cshell nanostructures with Fe₃O₄ core and NH₂-functional shells (Fe₃O₄@SiO₂?CNH₂), have been extensively investigated as high-performance adsorbents, catalysts and catalyst supports; and in most cases the controllable sol?Cgel technique is the choice for fabrication of this kind of widely applied materials. Herein, we demonstrated that mono-dispersed and spherical Fe₃O₄@SiO₂?CNH₂ nanomaterials with magnetic response core, NH₂-functional shell structure can be facilely prepared by co-condensation of TEOS with APTMS using a versatile sol?Cgel process. It was shown that the proper usage of APTMS and appropriate pre-hydrolysis time of TEOS were crucial and key steps for formation of highly uniform and desirable amino loading Fe₃O₄@SiO₂?CNH₂ materials. The TEOS pre-hydrolysis and the critical time (around 90?min) before the addition of APTMS prove to be vital for uniform structure evolution, while the appropriate concentration of APTMS (~2.28?mmol?L^?1 in our system) leads to well-dispersed materials with relatively high loading of amino functionality. The as-prepared Fe₃O₄@SiO₂?CNH₂ magnetic nanoparticles prepared under optimum conditions possessing superparamagnetic behavior, uniform core?Cshell structure (~200?nm in diameter), relatively large BET surface area (~138?m²/g) and high incorporation of amino-functionality (~2.90?wt?%).     

中国近代化学教育家——张贻侗

张贻侗是中国近代著名的化学教育家。他对北京师范大学、北平大学、西北师范大学及西北大学的化学教育作出了积极贡献,同时他也积极投身科学普及工作。本文介绍了张贻侗的生平简历、科学成就及其思想,以纪念这位对中国化学高等教育做出杰出贡献的化学家。     

中国化学会的创始人之一——叶峤

叶峤是20世纪上半叶中国化学界的一位著名化学家、教育家,在理论有机化学、天然有机化学、中草药化学等领域都有很深的造诣。他对中国化学会、武汉大学化学系的建设和发展做出了积极的贡献,促进了我国近代化学事业的发展、进步和延续。本文介绍了叶峤的生平简历、科学成就及其贡献,借此向大家展示一个较为全面、真实的叶峤。关于叶峤的系统研究对中国近现代化学史具有一定的意义。     

Helical Folding of Conjugated Oligo(phenyleneethynylene): Chain‐Length Dependence,Solvent Effects,and Intermolecular Assembly

As a representative folding system that features a conjugated backbone, a series of monodispersed (o‐phenyleneethynylene)‐alt‐(p‐phenyleneethynylene) (PE) oligomers of varied chain length and different side chains were studied. Molecules with the same backbone but different side‐chain structures were shown to exhibit similar helical conformations in respectively suitable solvents. Specifically, oligomers with dodecyloxy side chains folded into the helical structure in apolar aliphatic solvents, whereas an analogous oligomer with tri(ethylene glycol) (Tg) side chains adopted the same conformation in polar solvents. The fact that the oligomers with the same backbone manifested a similar folded conformation independent of side chains and the nature of the solvent confirmed the concept that the driving force for folding was the intramolecular aromatic stacking and solvophobic interactions. Although all were capable of inducing folding, different solvents were shown to bestow slightly varied folding stability. The chain‐length dependence study revealed a nonlinear correlation between the folding stability with backbone chain length. A critical size of approximately 10 PE units was identified for the system, beyond which folding occurred. This observation corroborated the helical nature of the folded structure. Remarkably, based on the absorption and emission spectra, the effective conjugation length of the system extended more effectively under the folded state than under random conformations. Moreover, as evidenced by the optical spectra and dynamic light‐scattering studies, intermolecular association took place among the helical oligomers with Tg side chains in aqueous solution. The demonstrated ability of such a conjugated foldamer in self‐assembling into hierarchical supramolecular structures promises application potential for the system.     

The Vital Role of Buffer Anions in the Antioxidant Activity of CeO2 Nanoparticles

Cerium oxide (CeO₂) nanoparticles display excellent antioxidant properties by scavenging free radicals. However, some studies have indicated that they can cause an adverse response by generating reactive oxygen species (ROS). Hence, it is important to clarify the factors that affect the oxidant/antioxidant activities of CeO₂ nanoparticles. In this work, we report the effects of different buffer anions on the antioxidant activity of CeO₂ nanoparticles. Considering the main anions present in the body, Tris‐HCl, sulfate, and phosphate buffer solutions have been used to evaluate the antioxidant activity of CeO₂ nanoparticles by studying their DNA protective effect. The results show that CeO₂ nanoparticles can protect DNA from damage in Tris‐HCl and sulfate systems, but not in phosphate buffer solution (PBS) systems. The mechanism of action has been explored: cerium phosphate is formed on the surface of the nanoparticles, which interferes with the redox cycling between Ce³⁺ and Ce⁴⁺. As a result, the antioxidant activity of CeO₂ nanoparticles is greatly affected by the external environment, especially the anions. These results may provide guidance for the further practical application of CeO₂ nanoparticles.