不同基体改进剂对电感耦合等离子体质谱法测量血清中甲胎蛋白的影响

血清中甲胎蛋白(AFP)的准确测量对于癌症的临床诊断和治疗具有重要意义.电感耦合等离子体质谱法(ICP-MS)具有灵敏度高、检出限低、多元素同时检测等优点,但用于血清中低丰度蛋白的检测时,检出限常不及荧光检测法,因此,提高ICP-MS免疫分析测量低丰度蛋白质时的灵敏度具有重要意义.本研究发现,增强液能很大程度增加Eu信号强度,选取醋酸、醇类、EDTA三类有机试剂模拟增强液来探索增强机理.结果表明:酸性体系能增加目标元素在基体中的稳定性,减少其在管壁的吸附;碳原子或分子容易接受电子提高Eu的电离效率;EDTA能与金属离子结合,减少吸附,但同时EDTA与其它金属结合引入更多的干扰,从而使空白信号增大,5％ HAc既能满足酸性要求也能满足含碳量要求,作为基体时铕的灵敏度最高,同时也不影响空白信号.因此选择5％ HAc作为解离液,并应用于人血清中甲胎蛋白含量的测定,线性范围为1～600 μg/L,检出限为0.57 μg/L,采用基体改进ICP-MS测量人血清中AFP的含量与TRFIA测量结果一致,且精密度要优于TRFIA的测量结果.     

Ti/α-PbO2/β-PbO2电极电化学降解2-氯酚

采用电化学沉积法在Ti基底上制备了复合电极Ti/α-PbO2/β-PbO2,扫描电镜结果表明电极呈现由β-PbO2小晶体组成的菜花状微观形貌.所制电极在电化学降解环境污染物2-氯酚时表现出较高的电催化效率、较好的电极稳定性和较长的电极寿命.用正交实验优化了电化学降解2-氯酚的实验条件.在最优的实验条件(2-氯酚初始浓度50 mg/L,电解质0.1 mol/L Na2SO4,温度35oC,阳极电流密度20 mA/cm2)下电化学降解180 min后,2-氯酚的去除率达100%.动力学结果表明, Ti/α-PbO2/β-PbO2电极上2-氯酚的电化学氧化符合准一级动力学过程.     

Theoretical investigation to characterize the inclusion complex of α-lipoic acid and β-cyclodextrin

We simulated the docking of α-lipoic acid (α-LA) in β-cyclodextrin (β-CD) using two models. We considered in this study complexes formed by 1:1 host–guest stoichiometry in vacuo and in aqueous phase, using PM6, DFT and ONIOM2 hybrid calculations. The results obtained with PM6 method clearly indicate that the complexes formed are energetically favored with or without solvent, model 2 (α-LA entering the cavity of β-CD from its wide side by COOH group) is found more favored than model 1 (α-LA entering into the cavity of β-CD from its wide side by cyclic group), the preference being greater in the case of ONIOM2 calculations. In addition, NBO analysis gives that mutual interactions between the donor and acceptor orbitals of α-lipoic acid and β-CD plays an important role to the stabilization of such a complex. Finally, ¹H nuclear magnetic resonance (NMR) chemical shifts of free and complexed α-LA were calculated by the Gauge-Including Atomic Orbital (GIAO) method and compared with available experimental data. The results of GIAO calculations were analyzed and discussed.     

The banded spherulites of iPP induced by pressure vibration injection molding

Isotactic polypropylene(i PP) samples obtained by pressure vibration injection molding(PVIM) and conventional injection molding(CIM) were studied by polarized-light microscopy(PLM), respectively. It was found that the alternating bright and dark banded spherulites were generated in the transitional region of PVIM parts. It is the first time that the banded spherulites of isotactic polypropylene were observed in polymer processing. What's more, the banded spherulites were proved to be constituted of ?-form crystal by hot stage polarized-light microscopy(HT-PLM) and wide angle X-ray diffraction(WAXD). Morphology of the banded spherulites was also studied by scaning electronical microscopy(SEM).     

铜催化α-重氮酮对硼氢键的不对称插入反应

手性有机硼化合物在有机合成、医药、材料等诸多领域中有广泛的应用,发展该类化合物的高效合成方法一直广受关注.此前,我们发展了过渡金属催化卡宾对硼氢键(B—H)的插入反应,并实现了α-重氮酯对B—H键的不对称插入反应.本文以手性螺环双噁唑啉配体和铜的络合物作为催化剂,首次实现了α-重氮酮对膦-硼烷加合物的B—H键不对称插入反应,获得了较高的收率和高达83%ee的对映选择性.该研究成果是为数不多的以α-重氮酮作为卡宾前体的不对称杂原子氢键插入反应,为手性α-硼取代酮化合物这类新的有机硼化合物的合成提供了有效方法.     

氨甲酰基硅烷与酮反应合成α-硅氧基酰胺衍生物

N,N-二甲基氨甲酰基三甲基硅烷与一系列芳基酮、不饱和芳基酮在无水无氧、105℃、甲苯作溶剂的条件下反应,合成了α-三甲基硅氧基酰胺衍生物,收率60%~89%,其结构用元素分析、1H NMR、13C NMR和IR等方法进行了表征.烷基烷基酮、烷基芳基酮、烷基不饱和芳基酮与N,N-二甲基氨甲酰基三甲基硅烷不反应.通过研究反应的影响因素发现,反应底物酮中与羰基相连的芳环上取代基的电子效应是该加成反应的重要影响因素,芳环上取代基的给电子能力越強,反应越慢.     

Environmentally Benign Synthesis of 2-Pyrazolines and Cyclohexenones Incorporating Naphthalene Moiety and Their Antimicrobial Evaluation

We reported the environmental benign synthesis of chalcones,2-pyrazolines and cyclohexanones under microwave irradiation.Chalcones were obtained by the condensation of each of 2-hydroxyacetophenone derivatives with a-naphthaldehyde under microwave irradiation.The condensation reactions of each of synthesized chalcones with phenyl hydrazine under microwave irradiation in the presence of dry acetic acid as a cyclizing agent gave 2-pyrazolines.Also,the new cyclohexenone derivatives,valuable intermediates to synthesize fused heterocycles,have been prepared by the cyclocondensation of each of hydroxychalcones with ethyl acetoacetate.The structures of the synthesized compounds were elucidated by infrared（IR） spectrometry,nuclear magnetic resonance（NMR）,mass spectrometry（MS） and elmental analysis.The results indicate that unlike classical heating,microwave irradiation results in higher yields with shorter and cleaner reactions.The synthesized compounds were screened for antimicrobial activity against Staphylococcus aureus,Escherichia coli,Candida Albicans and Aspergillus niger.We clarified the effects of different substituents in the tested compounds on the obtaind antibacterial activities and antifungal activities.     

Bulk derivatization and cation exchange restricted access media-based trap-and-elute liquid chromatography–mass spectrometry method for determination of trace estrogens in serum

Estrone (E1), estradiols (α/β-E2), and estriol (E3) are four major metabolically active estrogens exerting strong biological activities at very low circulating concentrations. This paper reports a sensitive and efficient method with automated, on-line clean-up and detection to determine trace estrogens in a small volume of serum samples using liquid chromatography–electrospray ionization–tandem mass spectrometry directly, without off-line liquid–liquid or solid-phase extraction pretreatments. Serum aliquots (charcoal stripped fetal bovine serum, 100 μL) were spiked with four estrogen standards and their corresponding isotope-labeled internal standards, then bulk derivatized with 2-fluoro-1-methyl-pyridium p-toluenesulfonate (2-FMP) to establish the calibration curves and perform method validation. Calibration was established in the concentration ranges of 5–1000 pg mL⁻¹, and demonstrated good linearity of R² from 0.9944 to 0.9997 for the four derivatized estrogens. The lower detection limits obtained were 3–7 pg mL⁻¹. Good accuracy and precision in the range of 86–112% and 2.3–11.9%, respectively, were observed for the quality control (QC) samples at low, medium, and high concentration levels. The stability tests showed that the derivatized serum samples were stable 8 h after derivatization at room temperature and at least to 48 h if stored at −20 °C. The method was applied to measure trace estrogens in real human and bovine serum samples, and three of four estrogen compounds studied were observed and quantified.     

Tutorial review on validation of liquid chromatography–mass spectrometry methods: Part I

This is the part I of a tutorial review intending to give an overview of the state of the art of method validation in liquid chromatography mass spectrometry (LC–MS) and discuss specific issues that arise with MS (and MS/MS) detection in LC (as opposed to the “conventional” detectors). The Part I briefly introduces the principles of operation of LC–MS (emphasizing the aspects important from the validation point of view, in particular the ionization process and ionization suppression/enhancement); reviews the main validation guideline documents and discusses in detail the following performance parameters: selectivity/specificity/identity, ruggedness/robustness, limit of detection, limit of quantification, decision limit and detection capability. With every method performance characteristic its essence and terminology are addressed, the current status of treating it is reviewed and recommendations are given, how to determine it, specifically in the case of LC–MS methods.     

基于罗丹明B的激活型α-酮戊二酸荧光探针

α-酮戊二酸(α-KA)是人体三羧酸循环的一个重要代谢中间体,异柠檬酸脱氢酶-1(IDH1)及异柠檬酸脱氢酶-2(IDH2)的突变将导致α-KA转化为2-羟基戊二酸(2HG),该过程与急性骨髓性白血病(AML)密切相关,因此检测人体内α-KA的含量变化具有重要意义。本文以罗丹明B作为荧光基团,通过将罗丹明B与水合肼反应得到能够检测α-KA的荧光增强型探针RBN,并优化了检测温度、pH及响应时间等条件。研究表明,RBN对α-KA表现出很好的选择性,不受人体内常见氨基酸、化学结构类似的羰基化合物及活性氧化物(ROS)的影响,具有潜在的应用价值。