傅利叶变换离子回旋共振质谱在团簇化学中的应用（Ⅰ）第一过渡系金属离子与丙烯腈的吸附和反应

利用傅利叶变换离子回旋共振质谱(FT-ICR／MS)研究了气相中第一过渡系金属离子和丙烯腈(AN)的吸附和反应,讨论了过渡金属离子与丙烯腈吸附和反应的规律和机理。     

离子色谱法测定高纯Eu2O3中的微量Cu和Ni

报导了用离子色谱法测定高纯EU_2O_3中Cu和Ni的实验结果。用强酸型阳离子交换树脂预分离柱除去稀土基体;用吡啶-2.6-二羧酸(PDCA)作为淋洗螯合剂,使镧系与过渡金属生成不同电荷的络合物,镧系金属保留在分析柱上端,通过梯度淋洗使稀土元素与过渡金属得到分离。最后利用与4(2-吡啶偶氮)间苯二酚(PAN)的柱后反应,于波长520nm处用光度法同时测定高纯Eu_2O_3中的非稀土杂质Cu和Ni。本法对Cu和Ni的检则范围为50～300ng/mL。分析150ng/mL Cu和Ni的相对标准偏差为±5％.本法亦适用于测定其它高纯稀土中的非稀土杂质。     

傅立叶变换-离子回旋共振质谱法在蛋白质分析中的应用

对傅立叶变换 -离子回旋共振质谱 (FT/ICRMS)的仪器特点及 FT/ICRMS在研究蛋白质结构鉴定、蛋白质翻译后修饰和蛋白组学中的应用等方面进行了综述和讨论。给出参考文献 4 5篇     

气相过渡金属离子化学研究进展

本文从五个方面简要介绍了气相过渡金属离子化学的进展:(1)一般研究方法;(2)反应类型;(3)反应规律(同烃、醇、卤代烃、胺、腈、羰基化合物、多官能团化合物、金属羰基化合物、硝基化合物及亚硝酸酯等的反应);(4)热力学数据的测定;(5)反应机理研究。     

Liranaftate的傅立叶变换-离子回旋共振质谱研究

用傅立叶变换 -离子回旋共振质谱 (FT/ ICRMS)和傅立叶变换 -离子回旋共振串级质谱 (FT/ ICRMSn,n=2 )研究新药 Liranaftate的裂解机理 ,探讨了相应的碎裂方式和机理 ,发现了该化合物的一个七元环重排裂解规律 ,给出了相应的准确分子量测定数据加以证实 ,同时也对比了 EI和 MAL DI两种不同离子化方式所得到的质谱结果 ,进一步证实了该重排是一个通过 Liranaftate吡啶环上氮原子的七元环重排。     

PAN纤维共聚单体作用机理的光电离质谱研究

本工作以丙烯腈/衣康酸(IA)二元共聚原丝以及丙烯腈/IA/丙烯酸甲酯(MA)三元共聚原丝为研究对象,利用热重分析仪(TG)和热解-同步辐射真空紫外光电离质谱(Py-SVUV-PIMS)对其热稳定化过程进行研究。TG结果表明,氮气气氛下,二元共聚原丝(PAN/IA)和三元共聚原丝(PAN/IA/MA)分别呈现三阶段和两阶段的热分解过程,其中PAN/IA的第一和第二阶段均对应PAN线型分子链的断裂,但前者是由自由基环化反应放热引发的,后者则是由正常温度下的热分解所致,而单体MA的加入显著抑制了自由基环化反应,使得PAN原丝的热稳定化能够以单体IA诱导的离子型环化反应为主较平缓地进行,相应的热失重过程也由两阶段转变为了单阶段。Py-SVUV-MS的实验结果表明,两种共聚PAN原丝在程序升温过程中会生成包括含氮小分子、丙烯腈单体及低聚物、成环化合物在内的三类主要热解产物,对比各类产物的生成趋势和产量,推断单体MA通过降低PAN结构的规整度,使其无定形化,从而增加环化反应的引发点,促进PAN原丝向稳定的预氧丝转变,同时由典型热解产物——甲基丙烯腈的生成路径可知,MA本身并不参与PAN大分子的环...     

基于MALDI源红外光解离质谱-光谱技术的金属-氨基酸配合物离子的结构研究

红外光解离(IRPD)质谱-光谱技术是研究气相离子结构的有力工具。本工作结合傅里叶变换离子回旋共振质谱(FT-ICR-MS)和台式光学参量振荡器(OPO)红外激光系统,针对气相中铷-组氨酸和铷-赖氨酸配合物离子进行红外光解离光谱研究。实验中配合物离子通过基质辅助激光解吸电离(MALDI)产生,而非由常用的电喷雾离子源(ESI)产生。光谱结果显示,两种配合物离子[His+Rb]+和[Lys+Rb]+分别在3 500 cm-1和2 935 cm-1处存在最大吸收。通过密度泛函理论(DFT)计算方法对[His+Rb]+的结构进行进一步研究,结果表明,[His+Rb]+离子主要来源于His+Rb-03,而非其最低能量构型His+Rb-01。     

傅里叶变换-离子回旋共振质谱

本文介绍了傅里叶变换-离子回旋共振质谱(FT-ICRMS)的基本原理、发展历史、仪器特点。与其它类型质谱相比较,FT-ICRMS具有超高质谱分辨率、高质量测量准确度、回旋池内现场反应等显著优点,有望在多种学科的研究中得到更广泛的应用。     

由喷射粒子形成的金属表面浸渍—激光浸渍

金属的耐磨性,可以利用激光浸渍的方法改进。即用激光化基体材料表层,并把高抗磨碳化物粒子浸渍到(?)池中。以前的方法主要用10kW激光功率在真空中进行。本文给出了用1.5和2.5kW的激光功率在大气压下进行试验的结果。经激光浸渍的金属表层的耐磨性大大提高,比未处理的铝提高20～40倍,比淬火的碳钢提高了5～20倍。     

ECR结合磁控溅射——制备DLC薄膜的新方法

介绍了新型的结合电子回旋共振(ECR)微波等离子体气相沉积与磁控溅射镀膜特点的ECR-650型镀膜系统,并利用该系统通过溅射石墨靶和金属钛靶在不锈钢基底上制备了具有Ti/TiNx/TiNxCy中间层结构的C薄膜。由于镀膜工艺问题,得到的薄膜主要由石墨构成。研究了制备时不同的气压和氩气分压对薄膜表面形貌、硬度等的影响。     

吸毒现场吸毒工具中的甲基苯丙胺分析

Based on the details in the case, the analysis method of methamphetamine was built up, which is supposed to be used for in vitro material taken from the criminal scene. It is suggested that GC-FID is first used for methamphetamine concentration scanning. Thus, according to the results, the sample could be concentrated or diluted for the next GC/MS analysis. Using this procedure, the satisfying result was achieved.     

新型直接采样电离方法研究及其毒品快速质谱分析应用

在新型毒品层出不穷的背景下,对毒品进行现场快速检测的需求日益增加.直接采样电离技术与小型质谱系统的结合是对多类型毒品进行现场快速检测的重要途径.针对目前直接电离采样方法对部分毒品分子电离效率低的问题,本工作开发了一种基于快速采样萃取的新型直接毛细管喷雾方法(DCS)及相应的一体化试剂盒.分析流程包括表面采样、溶剂洗涤、...     

表面解吸常压化学电离质谱法快速测定冰毒

A method for rapid determination of narcotics by surface desorption atmospheric pressure chemical ionization mass spectrometry (DAPCI-MS) was established. The operation parameters including spray voltage, capillary temperature ect. on analysis performance were systematically investigated. Under the optimized experimental conditions, trace amounts of methamphetamine and caffeine in ice drug were detected rapidly without any sample preparation and pretreatment. Since DAPCI-MS allows rapid analyzing trace amounts of narcotics without sample pretreatment, it was also proposed to couple DAPCI source to a miniature mass spectrometer for fast in-situ analysis of narcotics．     

影像测量法辅助电喷雾萃取电离源喷头的研制

电喷雾萃取电离（EESI）源具有无需样品复杂预处理、易于集成和小型化、适于现场分析等特点,是近年来研究的热点。喷头孔是影响EESI源性能的关键部件。然而,因喷头孔几何参数非常小,使用常规方法无法对其进行精确地检测与评估,一直无法满足EESI源的要求。本工作开发了一种基于影像测量的检测与评估方法,通过提取喷头孔的几何轮廓坐标参数,对比分析两种工艺制造的喷头孔的直径与圆度误差。在优化仪器参数的条件下,采用新工艺制造的EESI源对甲基苯丙胺进行检测,检出限从0.101 μg/L降至0.041 7 μg/L,RSD从0.9%～5.8%降至0.6%～4.2%,实验结果与采用影像测量法的评估结果一致。采用新工艺制造的EESI源对尿液中的可待因、海洛因、氯胺酮、苯丙胺、咖啡因、麻黄碱、甲基苯丙胺、地西泮、戊巴比妥和舒乐安定进行连续5日检测,各样品的最大RSD均小于5.2%。结果表明,该影像测量法可缩短EESI源研制周期、降低成本,EESI源的稳定性与灵敏度可得到较大提高。     

GC/MS法在海洛因毒品稀释剂分析中的应用研究

目的：开展气相色谱/质谱联用（GC/MS）法在海洛因毒品稀释剂分析中的应用研究。方法：用GC/MS方法对北京地区2007-2008年收缴的海洛因毒品中的稀释剂进行分析。结果：在223例海洛因毒品中检出的有机稀释剂有烟酰胺180例（80.7%）、咖啡因111例（49.8%）、扑热息痛49例（22.0%）、氨基比林41例（18.4%）、茶碱20例（8.97%）、脑复康25例（11.2%）、非那西丁35例（15.7%）、安眠镇静药34例（15.2%）、氯氮平13例（5.83%）、甲基苯丙胺16例（7.17%）、氯胺酮2例（0.90%）、曲马多1例（0.45%）;未检出有机稀释剂的有32例占14.3%。结论：应GC/MS法可准确、快速的分析海洛因毒品中的有机稀释剂。     

Programmed neuronal cell death induced by HIV-1 tat and methamphetamine

Apoptosis and autophagy are the two major types of programmed cell death (PCD) in neurons. Homeostatic autophagy often precedes apoptosis, and when apoptosis is blocked, the failure to keep homeostasis will lead to necrosis instead. It has been reported that human immunodeficiency virus (HIV) infected methamphetamine (Meth) abusers represent greater neuropathological abnormalities than Meth abusers or HIV-positive non-Meth users. Recent publications suggest that Tat and Meth when administered together result in greater neuronal damage than when administered separately. However, the cellular events of the combined Tat-Meth effect have not yet been fully characterized. Therefore, we investigated the effects of Tat and/or Meth on apoptosis and autophagy to elucidate whether PCD was involved in Tat and/or Meth-induced neuronal damage. Annexin-V-FITC/PI staining assay was used to detect cellular apoptosis using a neuroblastoma cell line SH-SY5Y. Cellular ultrastructural changes were observed under transmission electron microscopy (TEM). Flow-cytometric data showed apoptosis following Meth treatment, and more extensive apoptosis with Tat + Meth treatment. The most important finding was that the autophagosome and/or multilamellar bodies (MLBs) were most pronounced with Tat + Meth treatment, were less so with Meth treatment, and infrequent with Tat treatment. This suggests the involvement of autophagy and apoptosis in Tat with Meth-elicited cell damage. However, the relation between apoptosis and autophagy remains unknown in this experiment. Further research is needed to analyze the relation among related molecules. A thorough understanding of this multifaceted relationship will be critical for the assessment of therapeutic modalities for patients with HIV with drug abuse.     

城市生活污水中阿片类、苯丙胺类以及苯二氮卓类滥用物质的高分辨质谱筛选及确证

本研究采用固相萃取对城市生活污水样品进行前处理,超高效液相色谱-串联高分辨质谱法筛选及确证污水中阿片类、苯丙胺类和苯二氮卓类等36种滥用物质,并将其应用于实际污水样品。结果表明,该方法的专属性强,36种滥用物质的检出限范围为5~20 ng/L。在12个污水样品中共检出吗啡、可待因、哌替啶、曲马多4种阿片类滥用物质,甲基苯丙胺1种苯丙胺类滥用物质以及地西泮、去甲西泮、艾司唑仑、阿普唑仑4种苯二氮卓类滥用物质。城市生活污水中存在多种滥用物质,区域流行性不同,利用本方法可进行快速、准确地筛选与确认。     

Gas discharge ion source. I. Duoplasmatron

The effects of the plasma expansion cup on the operation of a duoplasmatron ion source have been investigated by measuring the total ion current and the distributions of the ion energy, mass, and current density. A copper expansion cup did not affect the magnetic field near the anode of the ion source and consequently the ion current density distribution was sharply peaked near the center of the cup. Ion energy distributions were approximately symmetrical about anode potential. The dominant ionic species were D(+) (3) and D(+) at low and high arc currents, respectively. Changes in the electrical potential of the copper cup with respect to the anode produced negligible changes in the above data. A mild steel plasma expansion cup caused the magnetic field to diverge and intercept the cup walls, resulting in ion current density distributions that were flatter and more amenable to focusing than the ones with the copper cup. With the steel cup at anode potential, the ion mass distribution was similar to that from the copper cup; however, the ion energy distribution was asymmetrical about the anode potential with a peak about 10-20 V above anode potential. The total ion current from this mode of operation was about one-third the value from the copper cup. If the steel cup assumed floating potential, about 50 V below anode potential, the total current increased to the level observed from the copper cup and the ion energy distribution was similar to that observed with the copper cup but the current density distribution was much flatter than that of the copper cup. The ion mass distribution was 60%-70% atomic ions over the entire arc current range investigated. Based on these data, a modified plasma expansion cup was designed with tapered steel walls lined with a boron nitride insert. The overall performance of the duoplasmatron ion source with this cup was superior to any of the previous three modes of operation. The improved design uses a molybdenum anode insert which is far superior to copper in regard to erosion over extended operating times. A total beam current of 200 mA was produced at an arc current of 24 A.     

内燃机进气道的计算机辅助设计与制造

这里主要探讨了内燃机进气道的CAD/CAM,采用正向设计方法和逆向设计方法设计了进气道,并利用快速成型和数控机加工制作出气道的相关模型,通过应用发动机气道的CAD/CAM技术,缩短了气道的开发时间,减少了开发成本。     

高效液相色谱-高分辨质谱法鉴定拉萨大黄化学成分

建立了高效液相色谱-高分辨质谱法分析鉴定拉萨大黄化学成分。选用Agilent Zorbax SB-C18柱（150 mm×4.6 mm×5 μm）,以乙腈和水为流动相进行梯度洗脱,流速0.5 mL/min;采用电喷雾离子源,在正、负离子模式下对拉萨大黄提取物进行一级和多级全扫描质谱分析。综合分析化合物的色谱和质谱行为,并结合对照品、文献和数据库等相关数据鉴定化合物。在负离子模式下,鉴定出63种化合物;正离子模式下,鉴定出54种化合物。所检测到的化合物包括22种鞣质类、28种茋类、6种黄酮类、3种苯丙酸类、2种苯丁酮类和2种有机酸类,其中有53种化合物为在该药材中首次发现,且未发现蒽醌类成分。该方法快速、灵敏,不仅提高了拉萨大黄复杂基质中微量化合物的鉴定效率,同时实现了对拉萨大黄提取物中不同类型化合物的分析鉴别,为进一步阐明拉萨大黄的药效物质基础及质控标准提供了科学依据。