电子捕获裂解质谱研究进展

过去的二十年中，以电子捕获裂解为代表的离子反应技术，极大地推动了气相自由基离子化学的研究.该领域的发展是现代质谱的前沿问题，同时也是后基因组时代生物分析的重要技术手段.总结了电子捕获裂解的研究进展，并对其产生、裂解规律以及机理的研究进行了详细的综述.     

质谱参数改变对化合物负离子化学电离质谱行为的影响

负离子化学电离质谱中负离子的相对丰度随着离子源压力、电子能量和离子源温度等质谱参数的改变发生了明显的变化。负离子形成过程中共振电子俘获和裂解电子俘获之间的竞争与质谱参数有关,其中以离子源温度的影响最为显著。热电子的比例随着离子源压力增大而减小,随着电子能量增大而增大。低离子源温度有利于共振俘获形成分子负离子,而高离子源温度则有利于裂解电子俘获形成碎片负离子,特别是热力学稳定的负离子。     

傅立叶变换离子回旋共振质谱进展

综述了傅立叶变换离子回旋共振质谱（ＦＴＩＣＲＭＳ）仪器特点和各种新技术。主要对紫外光解离技术、红外多光子解离技术、表面诱导解离、黑体红外辐射离、电子捕获解离等离子解离新方法进行了介绍。此外,应用多次激发碰撞活化技术、超低能量激发技术、持续偏共振激发、存储波形逆傅立叶变换技术等离子再测量技术能提高源内离子碰撞诱导解离效率,更好的实现ＭＳ＾n的产技术。文章最后阐述了ＦＴＭＳ在生物分析及气相分子离子反应     

铝酸钠溶液中超声诱致自由基的检测

文首次应用自由基捕获方法和电子顺磁共振技术(EPR),检测铝酸钠溶液在超声波空化作用下产生的羟自由基.本实验利用DMPO捕获羟自由基而生成寿命较长的DMPO-OH这一特性,分析了超声输出功率、超声处理时间等对DMPO-OH的自旋共振谱图中对称振动峰强弱的影响.实验结果表明:当超声输出功率达到或超过空化阈值,过饱和中等浓度铝酸钠溶液中水分子可裂解为羟自由基和氢原子自由基;同时自由基的产量与超声输出功率、超声作用时间以及溶液浓度有关.     

脂族酰基过氧化物分解动力学的研究X: 过氧化酰热分解反应的自旋捕获ESR研究

用亚硝基丁烷(TNB)、亚硝基苯和C-苯基-N-叔丁基硝酮作为自旋捕获剂来捕获和检出一些二酰基过氧化物类化合物分解时形成的短命烷基自由基. 报导了烷基自由基对自旋捕获剂加成的氮氧化物自由基的电子自旋共振谱, 并观察到2,4,4-三甲基戊基自由基中α-CH2的氢是非对映和非等价的. 据此, 认为与这一类自由基的加合物产生的电子自旋共振谱与其它类型自由基是不同的.     

气相色谱-选择离子监测质谱法快速检测进口小麦中多残留农药

农药残留的检测有气相色谱火焰光度检测法,电子捕获检测法,氮磷检测法,液相色谱-荧光检测法,气质联用法等.气相色谱或液相色谱由于检测器选择性较强,分析农药品种的范围较窄,质谱作为广谱的检测器1次可同时分析多种类型的残留农药,节省了大量的分析时间.     

甲醛光催化氧化的反应机理

采用程序升温脱附（TPD）, 电子自旋共振（ESR）及自旋捕获 电子自旋共振(ST ESR)等物理方法对甲醛光催化氧化过程中,反应物的吸附状态、自由基中间物种及反应机理 进行了研究.结果表明,在光催化氧化空气中微量甲醛的反应条件下,吸附在催化剂表面的空 气中的氧气被光生电子还原为•O－2,微量水被空穴氧化为•OH.二者为甲醛的深度氧化提供了高活性的氧化剂.甲醛是通过中间产物甲酸而氧化为终点 产物二氧化碳的.     

糖蛋白糖基化位点及糖型的多重质谱分析

以糖蛋白核糖核酸酶B(RNase B)为研究对象,采用基质辅助激光解吸电离-串联飞行时间质谱(MALDI-TOF/TOF-MS)、傅里叶变换离子回旋共振质谱(FT-ICR-MS)的碰撞活化解离(CAD)和电子转移解离(ECD)多种质谱技术对RNase B的糖肽的完整信息进行解析.通过多种质谱相互验证,确定了RNase B的糖肽组分的氨基酸序列为SRNLTK、糖链结构为(HexNAc)2(Hex)5-(HexNAc)2(Hex)9及糖基化位点为第34位氨基酸残基.本方法为糖蛋白结构的全面解析提供了一种快速、有效、全面的研究思路.     

新颖瞬态物种的产生与表征

基于对紫外光电子能谱(PES)仪的不断改进, 成功地生成与表征了系列新颖瞬态物种. 简要综述了PES的基本原理; 系列新颖瞬态物种活性卤素化合物、短寿命自由基、亚稳态拟卤素化合物的PES实验和理论量子化学研究; 以及新建立的紫外光电子能谱与HeI光光电离飞行时间质谱联合谱仪(PES/HeI-TOFMS)在瞬态物种的研究进展. 而PES/HeI-TOFMS联合谱仪的建立使得PES在复杂化学过程以及瞬态物种的捕获与表征研究中发挥更大的作用.     

ECD & CAD裂解方式的FT-ICR-MS研究

傅立叶变换离子回旋共振质谱(Fourier transform ion cyclotron resonance mass spectrometry,FTICR-MS),具有经典质谱及现代质谱技术的多种功能,由于采用离子回旋共振质量检测器,FT-ICR-MS具有超高分辨率、超高灵敏度(fmol),以及较宽的质量范围(m/z＞10 000 u).多级质谱功能与肽库配合越来越广泛地应用到生物大分子的研究中[1-2],已经成为生命科学相关前沿领域如蛋白质组研究不可缺少的工具之一.     

CDW and CDW-EIS investigations in an independent electron approximation for the resonant double electron capture by swift He2+ in helium

The CDW and CDW-EIS approximations are used to study the resonant double electron capture by He²⁺ in helium at intermediate and high impact velocities. Calculations of the total cross sections as a function of the impact energy are performed in an Independent Electron Approximation. A very good agreement with recent experimental data for capture into all states of the projectile is found although neither angular nor dynamical electron correlations are included in the calculations.     

Does double electron capture lead to the formation of biradicals? An ECD-SORI-CID study on lacticin 481

We studied lacticin 481, a small lantibiotic with three lanthionine bridges, by electron capture dissociation (ECD) in a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. Following electron capture, very little fragmentation was observed, but species formed by nondissociative single and multiple electron capture were abundant. Ions formed by double electron capture were subjected to sustained off resonance irradiation collision induced dissociation (SORI-CID) to determine whether stable biradicals were formed. In the SORI-CID spectra of the ions formed by double electron capture, some, but minor, H* radical loss was observed, which was not observed at all for regularly protonated ions. A small part of the ions formed by double electron capture are thus long-lived biradicals. Apart from the observed H* loss, the SORI-CID spectra of ions that captured two electrons was similar to that of regularly protonated ions and quite different from the SORI-CID spectra of radical ions formed by single electron capture. This implies that recombination of the two radical sites is the dominant process in biradical lacticin 481 ions, at least on the time scale of our SORI-CID experiments.     

Theoretical studies on the electron capture properties of the H2SO4...HOO˙ complex and its implications as an alternative source of HOOH

To better understand the potential role of sulfuric acid aerosols in the atmosphere, the electron capture properties of the H(2)SO(4)...HOO˙ complex have been systematically investigated by employing the MP2 and B3LYP methods in combination with the atoms in molecules (AIM) theory, energy decomposition analysis (EDA), and ab initio molecular dynamics. It was found that the electron capture process is a favorable reaction thermodynamically and kinetically. The excess electron can be captured by the HOO˙ fragment initially, and then the proton of the H(2)SO(4) fragment associated with the intermolecular H-bonds is transferred to the HOO˙ fragment without any activation barriers, resulting in the formation of the HOOH species directly. Therefore, the electron capture process of the H(2)SO(4)...HOO˙ complex provides an alternative source of HOOH in the atmosphere. The nature of the coupling interactions in the electron capture products are clarified, and the most stable anionic complex is also determined. Additionally, the influences of the adjacent water molecules on the electron capture properties are investigated, as well as the distinct IR features of the most stable electron capture product.     

Side-chain fragmentation of alkylated cysteine residues in electron capture dissociation mass spectrometry

The recent development of novel fragmentation processes based on either electron capture directly or transfer from an anion show great potential for solving problems in proteomics that are intractable by the more widely employed thermal-based fragmentation processes such as collision induced dissociation. The dominant fragmentation occurring upon electron capture dissociation of peptides is cleavage of N-C alpha bonds in the peptide backbone to form c and z* ions. In the case of disulfide-linked peptides, it has also been shown that electron capture on one of the cystine sulfur atoms is favored, resulting in cleavage of the disulfide bond. In this study, we report that electron capture on the sulfur of alkylated cysteine residues is also a dominant process, causing cysteine side-chain loss from z* ions.     

Correlation between Electron Capture Response and Chemical Structure for Sulfur Compounds

Abstract

The temperature dependence of the electron capture process was investigated for a series of divalent sulfur compounds. The electron affinity and/or the activation energy for the electron capture reaction were calculated for individual compounds by plotting In KT^3/2 vs. 1/T, where K is the electron capture coefficient and T is the absolute temperature in the detector. The correlation between these values and chemical structure was discussed by means of 3d orbital resonance of the sulfur atom.     

Improvement of electron capture efficiency by resonant excitation

A novel pulse sequence improving the efficiency for electron capture dissociation (ECD) of an unmodified Fourier transform ion cyclotron resonance (FTICR) mass spectrometer by more than an order of magnitude is presented. Commercially available FTICR instruments are usually equipped with a filament-based electron source producing an electron beam that has a rather small cross section. An ideal overlap between the rotating ion cloud and the electron beam appears to be a prerequisite for a high ECD efficiency. A reduced interception of the ion cloud and the electron beam is probably due to the contribution of the magnetron motion to the trajectory of the ions, resulting in a precession about the z-axis of the instrument. By increasing the kinetic energy and therefore increasing the cyclotron radii of the precursor ions by resonant excitation, the overlap of the rotating ion cloud with the electron beam is improved. By use of this protocol the efficiency of electron capture is substantially increased and consequently the acquisition time of ECD spectra is reduced significantly. The capability of resonant excitation of the precursor ions during the irradiation with electrons is demonstrated for standard peptides. This approach is particularly valuable for analysis and characterization of O-glycosylated peptides. In addition to amino acid sequence information, the attachment site of the labile glycan moiety is determined, and also radical-site-induced fragmentations of the glycosidic bonds are observed.     

LC-electron capture APCI-MS for the determination of nitroaromatic compounds

The determination of selected nitroaromatic compounds in liquid chromatography-mass spectrometry with electron capture (EC) ionisation using a commercial atmospheric pressure chemical ionisation (APCI) interface in the negative mode is described. The electron capture effect is observed for nitroaromatics which do not easily undergo deprotonation under these conditions. Depending on the structure of the analytes, either dissociative or, for the first time in LC-MS, non-dissociative electron capture is observed. Limits of detection and linear range for the determination of the analytes match those obtained for nitroaromatics which undergo deprotonation. The investigated substances comprise numerous substituted nitrobenzenes and nitrobenzooxadiazoles.     

On the calculation of the electron capture within the strong potential born approximation

A new method to perform the calculation the limits of the electron capture cross-section in the Strong Potential Born Approximation is presented. Within this approach, the high velocity limit is obtained by a simple algebraic procedure as an alternative derivation to the complex variable analysis used previously.     

CaO高温吸附捕集CO2-制备CaO的钙基前驱体材料筛选

价格低廉的CaO材料在高温下能高效吸附捕集CO2气体,被认为是碳减排的有效方法之一．然而,CaO长时间循环碳酸化／煅烧解吸后,其CO2的化学吸附容量下降,稳定性较差,限制了该材料的工业应用．本文采用天然钙源（牡蛎壳和方解石等）和化学试剂（醋酸钙）为钙基前驱材料制备CaO．采用扫描电子显微镜（SEM）,X射线衍射仪（XRD）和氮气吸附仪等手段对制备的CaO材料进行形貌和物理结构的分析表征;在高温和模拟的烟道气氛条件下（10％C02和90％N2）,采用热重分析仪测量CaO吸附CO2的能力和长时间循环碳酸化／煅烧解吸后的稳定性．我们经过与目前所报道的其他钙基吸附材料进行比较,并结合钙基前驱材料的市场价格,发现CaO（醋酸钙）的CO2吸附能力和稳定性较为理想,醋酸钙在高温烟气捕碳方面具有非常好的应用前景．