Mass spectrometry of rhenium complexes: a comparative study by using LDI-MS, MALDI-MS, PESI-MS and ESI-MS

A group of rhenium (I) complexes including in their structure ligands such as CF(3)SO(3)-, CH(3)CO(2)-, CO, 2,2'-bipyridine, dipyridil[3,2-a:2'3'-c]phenazine, naphthalene-2-carboxylate, anthracene-9-carboxylate, pyrene-1-carboxylate and 1,10-phenanthroline have been studied for the first time by mass spectrometry. The probe electrospray ionization (PESI) is a technique based on electrospray ionization (ESI) that generates electrospray from the tip of a solid metal needle. In this work, mass spectra for organometallic complexes obtained by PESI were compared with those obtained by classical ESI and high flow rate electrospray ionization assisted by corona discharge (HF-ESI-CD), an ideal method to avoid decomposition of the complexes and to induce their oxidation to yield intact molecular cation radicals in gas state [M](+·) and to produce their reduction yielding the gas species [M](-·). It was found that both techniques showed in general the intact molecular ions of the organometallics studied and provided additional structure characteristic diagnostic fragments. As the rhenium complexes studied in the present work showed strong absorption in the UV-visible region, particularly at 355?nm, laser desorption ionization (LDI) mass spectrometry experiments could be conducted. Although intact molecular ions could be detected in a few cases, LDI mass spectra showed diagnostic fragments for characterization of the complexes structure. Furthermore, matrix-assisted laser desorption ionization (MALDI) mass spectra were obtained. Nor-harmane, a compound with basic character, was used as matrix, and the intact molecular ions were detected in two examples, in negative ion mode as the [M](-·) species. Results obtained with 2-[(2E)-3-(4-tert-buthylphenyl)-2-methylprop-2-enylidene] malononitrile (DCTB) as matrix are also described. LDI experiments provided more information about the rhenium complex structures than did the MALDI ones.     

Mass Spectrometry,Review of the Basics: Ionization

Abstract: Mass spectrometry (MS) has become an integral tool in life sciences. The first step in MS analysis is ion formation (ionization). Many ionization methods currently exist; electrospray ionization (ESI) and matrix-assisted laser desorption ionization (MALDI) are the most commonly used. ESI relies on the formation of charged droplets releasing ions from the surface (ion evaporation model) or via complete solvent evaporation (charge residual model). MALDI ionization, however, is facilitated via laser energy and the use of a matrix. Despite wide use, ESI cannot efficiently ionize nonpolar compounds. Atmospheric pressure chemical ionization (APCI) and atmospheric pressure photo ionization (APPI) are better suited for such tasks. APPI requires photon energy and a dopant, whereas APCI is similar to chemical ionization. In 2004, ambient MS was introduced in which ionization occurs at the sample in its native form. Desorption electrospray ionization (DESI) and direct analysis in real time (DART) are the most widely used methods. In this mini-review, we provide an overview of the main ionization methods and the mechanisms of ion formation. This article is educational and intended for students/researchers who are not very familiar with MS and would like to learn the basics; it is not for MS experts.     

The analysis of alkyl-capped alcohol ethoxylates and alcohol ethoxycarboxylates from alcohol ethoxylates by atmospheric pressure chemical ionization mass spectrometry

Alcohol ethoxylates (AEs) are nonionic surfactants. They are industrially important compounds that have historically been difficult to analyze, with the best results to date achieved through derivatization (e.g., silylation) followed by analysis by gas chromatography/mass spectrometry (GC/MS). Recently, mass spectrometric techniques such as field desorption (FD), time-of-flight secondary ion mass spectrometry (TOF-SIMS), fast atom bombardment (FAB), electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) have been employed to analyze surfynol(R) 4xx. In an effort to produce low-cost alkyl-capped AEs and anionic detergents from AEs, a fast and reliable measure of the product yields and conversions from AEs is required in research. We found that the product yields and conversions from reactions of AEs, obtained by the employment of atmospheric pressure chemical ionization (APCI), were in good agreement with those obtained from proton nuclear magnetic resonance spectroscopy ((1)H-NMR). Therefore, APCI can be used as a validated tool for studying AE reactions. Mixtures that contain either silylated or unsilylated ethoxylates and/or carboxylates yield the same APCI mass spectra. Copyright -Copyright 1999 John Wiley & Sons, Ltd.     

Electrospray ionization multiple-stage tandem mass spectrometric analysis of diglycosyldiacylglycerol glycolipids from the bacteria Bacillus pumilus

Electrospray ionization (ESI) combined with multiple-stage tandem mass spectrometry (MS(n)) was used to directly analyze the glycolipid mixture from bacteria Bacillus pumilus without preliminary separation. Full scan ESI-MS revealed the composition of picomole quantities of glycerolglycolipid species containing C(14)-C(19) fatty acids, some of which were monounsaturated. Two main components were identified from their molecular masses and fragmentation pathways. The fragmentation pathway of the known compound compared with the investigated compound verified the proposed structure as 1(3)-acyl-2-pentadecanoyl-3(1)-O-[beta-D-glucopyranosyl-(1-->6)-O-beta-D-glucopyranosyl]-sn-glycerols. A comparison of the multiple tandem mass spectra of the different alkali-metal cation adducts indicates that the intensity of fragments and the dissociation pathways are dependent on the alkali-metal type. The basic structures of glycerolglycolipids were reflected clearly from the fragmentation patterns of the sodium cations. The intense fragments of the sugar residue from the precursor ions were obtained from the lithiated adduct ions. ESI-MS(n) spectra of [M + K](+) ions did not provide as much fragmentation as [M + Na](+) and [M + Li](+) adducts, but their spectra allow the position of glycerol acylation to be determined. On the basis of MS(2) spectra of [M + K](+) ions, it was established that all components have a C(15:0) fatty acid at the sn-2 position of the glycerol backbone and C(14)-C(19) acids at the sn-1 position of the glycerol backbone. Copyright 1999 John Wiley & Sons, Ltd.     

Nebulizing conditions of pneumatic electrospray ionization significantly influence electrolyte effects on compound measurement

Composition of mobile phase can greatly influence the success of electrospray ionization (ESI)-interfaced liquid chromatography-mass spectrometry analysis. To investigate the relationship between formic-acid-based modification of mobile phase and ESI nebulizing conditions, an API 4000 ESI source and a TSQ Quantum one were compared under the same chromatographic conditions. Ginkgo terpene lactones and flavonols were measured in plasma, which involved using ascorbic acid to circumvent cross-interference between the analytes. ESI responses to using formic acid included changes in signal intensity, matrix effect, and upper limit of quantification. Significant disparities in the responses were observed between the two ESI sources, suggesting that the use of electrolyte modifier in liquid chromatography mobile phase and the pneumatic nebulization for ESI should be properly balanced to accomplish optimal ESI-based analysis. The distribution of unpaired ions toward the surface of the initial droplet was assumed to be an important step in the pneumatic ESI process. When using the electrolyte in mobile phase, a too fast droplet reduction by rapid-heating-assisted pneumatic nebulization could negatively decrease the time available for the unpaired ions to migrate from droplet interior to its surface. Ascorbic acid was identified as a major interfering substance for the bioanalytical assay; the interference mechanism might be associated with hindering the unpaired analyte ions from distributing toward the droplet surface rather than outcompeting the analyte ions for the limited excess charge on droplets surface. The current work extends the knowledge base of pneumatic ESI, which has implication for optimal use of the ESI-interfaced liquid chromatography-mass spectrometry technique.     

Structures and reactions of hydrated biomolecular cluster ions

Photo-induced reactions and metastable decompositions of cluster ions containing glycine, tryptophan, tryptophanylglicine and [Fe(III)-protoporphyrin]⁺ (hemin⁺) ions solvated with water molecules are studied with electrospray ionization (ESI). The ESI ion source is improved to produce hydrated biomolecular cluster ions. Metastable decompositions of the hydrated clusters following primary mass selection are measured to determine the incremental solvent binding energies for the clusters by using evaporative ensemble model. From these experimental findings, stability of the cluster ions is discussed in terms of delocalization of ionic charges. We also measure the photodissociation yields of mass-selected water clusters containing hemin⁺ ions at 355 and 532 nm. The mass spectra of photofragments show the β-cleavage of carboxymethyl groups in addition to the evaporation of solvent molecules.     

高气压强电场电离过程中的离子浓度分布规律

研究了高气压强电场电离区域的离子浓度分布的连续性方程, 对电离区域的电离物的产生、消失和输运进行了研究。通过采用电离放电增加了输入能量密度、G 值、电离占空比等, 从而提高了离子产生率。通过外加电场和离子“雪崩”头部的本征电场的叠加作用, 离子被束缚在放电通道中。对离子施加垂直电场方向的作用力, 就能把电场中的等离子体成束输送出去。已经能够做到有效体积仅为1cm³的等离子体源, 输运等离子体率达到 10¹² cm^{- 3}•s^{- 1}。     

非链式化学HF（DF）激光器工作气体中电子分离的非稳定性和气体放电等离子体的自组织现象

报道了放电引发的非链式HF（DF）激光器中的激活介质由电子碰撞负离子分离引起的电离非稳定性。这种非稳性出现在电极空间分离、脉冲CO2激光加热的基于sF6的混合气体的大体积放电中。实验研究了自引发体放电过程中由激光加热引起的放电等离子体的自组织现象以及由此在放电间隙的大部分区域形成的准周期等离子体结构。重点分析了等离子体结构随气体温度和注入能量的变化,讨论了等离子体自组织对电子碰撞分离不稳定性所产生的影响,解释了混合气体中由于电子碰撞使负离子消失导致的单等离子体通道移动的产生机理。     

Properties of surface dielectric barrier discharge plasma generator for fabrication of nanomaterials

This paper presents surface dielectric barrier discharge plasma generators as an efficient source of low-energy ions. Either positive or negative ions can be extracted from a plasma cloud with an external DC field created by the third electrode. Three different cross-section geometries of DBD generators were analyzed, simulated and fabricated. Currents of ions extracted from the plasma cloud were measured and the results were discussed. It was demonstrated that if the third electrode consists of liquid–gas interface, the presented arrangement can be used as a versatile reactor for nanomaterial synthesis (on the example of the synthesis of silver nanoparticles).     

辉光放电等离子体镁电离的研究

以铝镁合金作阴极,采用吸收光谱测定了辉光放电放电等离子体中镁离子和原子的相对密度。提出了在近似条件下,由镁离子和原子吸光度比法求算镁电离度的方法。探讨了电离对常规分析的干扰与校正,以及影响镁电离的因素。     

闪电放电通道等离子体成分及相关特性的研究

以无狭缝摄谱仪获得了青海和西藏地区的云对地闪电回击过程的光谱,依据谱线波长和相对强度等信息,结合等离子体相关理论,得到了放电通道温度和电子密度;在此基础上,根据Saha方程、电荷守恒方程和粒子数守恒方程计算了闪电通道主要元素各级电离的离子数密度,进而得到通道质量密度、压强及平均电离度, 并分析了不同强度闪电放电通道的电离度、粒子数密度及其分布特征。结果表明：回击通道接近于完全电离,一次电离离子占主要地位,且NⅡ离子数密度最高;不同强度的闪电放电通道中,NⅡ和OⅡ离子的相对浓度值变化不大;计算过程中考虑带电离子间库仑相互作用以后,原子电离能的计算值降低,中性原子以及一次电离离子数密度的计算值变小,高次电离离子数密度的计算值变大。     

高功率脉冲磁控溅射的阶段性放电特征

本文从放电靶电流出发,采用一种新的研究方法,即将靶电流分解为多个代表具体放电特性的特征参数,全面而系统的研究了不同的工作气压条件下,靶电流各特征参数随靶电压的增加而进行的演化.结果发现高功率脉冲磁控溅射技术(HPPMS)放电靶电流在靶电压由低向高增加的过程中,出现靶电流峰值和平台值的交替变化,体现出明显的阶段性放电特征,且不同的放电阶段在不同气压下出现一定的移动,会在测量范围内出现某些放电阶段的缺失.本文还通过等离子体发射光谱对HPPMS放电靶前等离子体测量发现五个不同的放电阶段分别主要对应氩原子、铬原子、氩离子、铬离子和氩、铬高价离子的放电,但不同的放电条件下相邻的阶段会出现一定程度的交叠.     

High-order harmonic generation from ions in a capillary discharge

We demonstrate a significant extension of the high-order harmonic cutoff by using a fully-ionized capillary discharge plasma as the generation medium. The preionized plasma dramatically reduces ionization-induced defocusing and energy loss of the driving laser due to ionization. This allows for significantly higher photon energies, up to 150 eV, to be generated from xenon ions, compared with the 70 eV observed previously. We also demonstrate enhancement of the harmonic flux of nearly 2 orders of magnitude at photon energies around 90 eV when the capillary discharge is used to ionize xenon, compared with harmonic generation in a hollow waveguide. The use of a plasma as a medium for high-order harmonic generation shows great promise for extending efficient harmonic generation to much shorter wavelengths using ions.     

Dynamics of an RF Discharge in a Magnetic Field under Strong Initial Preionization

We demonstrate experimentally the possibility to create and sustain a strongly ionized plasma at low gas pressures by the electromagnetic radiation of the intensity which is below the conventional breakdown level. The conditions of ignition and sustaining the plasma are found, and the plasma parameters are measured. The necessary condition for the discharge formation is strong preliminary ionization of an initial gas. Significant electron heating in the RF field, which ensures the effective gas ionization takes place due to Coulomb collisions with protoplasma ions. Such collisions are much more frequent than the electron-neutral collisions. We propose a qualitative analytical model of the discharge evolution, which describes the effects observed.     

环丙烷衍生物在D2O离子体系中的H/D交换反应

在Ｄ２Ｏ化学反应气条件下环丙烷衍生物的Ｈ／Ｄ交换反应特性,发现了三种新的产物离子（Ｍ＋１）＾＋、（Ｍ＋２）＾＋和（Ｍ＋３）＾＋。应用碰撞诱导碎裂（ＣＩＤ）技术研究了这些离子的碎裂反应特性。实验结果表明三种新的产物离子是由反应物与试剂离子间发生Ｈ／Ｄ交换反应生成的。并获得了环丙烷衍生物结构中活泼氢位置及其数量的信息。     

Seed oil triglyceride profiling of thirty-two hybrid grape varieties

Triglyceride profile of seed oil samples from 32 hybrid grape varieties not studied before was investigated. A new method for the analysis of triacylglycerols (TAGs) has been developed based on the direct infusion in the electrospray ionization (ESI) source and employing tetrahydrofuran/methanol/water (85:10:5 v|v|v) as solvent; the formation of [M?+?Na](+) ions in high yield has been observed. TAGs were identified by ESI-tandem mass spectrometry analysis, and the matrix-assisted-laser-desorption-ionization and time-of-flight profile of samples was determined. Six were the principal TAGs identified in seed oil: trilinolein (LLL) was the most abundant (43%), followed by dilinoleoyl-oleoylglycerol (LOL, 23%), and dilinoleoyl-palmitoylglycerol (LPL, 15%). Compounds present in lower concentration were LSL and LOO (11%), LOP (6%), and LSP (2%). Compared with seed oils produced from V. Vinifera grapes, some significant differences in the relative abundances of TAGs were found, in particular hybrid grape seed oils showed higher LOL and lower LPL content, respectively. Among the samples studied, a particularly high content of LLL (rich in unsaturated fatty acids) was found in seed oils from two red varieties. Copyright ? 2012 John Wiley & Sons, Ltd.     

Mass Spectrometry,Review of the Basics: Electrospray,MALDI, and Commonly Used Mass Analyzers

Abstract

Mass spectrometry (MS) has progressed to become a powerful analytical tool for both quantitative and qualitative applications. The first mass spectrometer was constructed in 1912 and since then it has developed from only analyzing small inorganic molecules to biological macromolecules, practically with no mass limitations. Proteomics research, in particular, increasingly depends on MS technologies. The ability of mass spectrometry analyzing proteins and other biological extracts is due to the advances gained through the development of soft ionization techniques such as electrospray ionization (ESI) and matrix-assisted laser desorption ionization (MALDI) that can transform biomolecules into ions. ESI can efficiently be interfaced with separation techniques enhancing its role in the life and health sciences. MALDI, however, has the advantage of producing singly charges ions of peptides and proteins, minimizing spectral complexity. Regardless of the ionization source, the sensitivity of a mass spectrometer is related to the mass analyzer where ion separation occurs. Both quadrupole and time of flight (ToF) mass analyzers are commonly used and they can be configured together as QToF tandem mass spectrometric instruments. Tandem mass spectrometry (MS/MS), as the name indicates, is the result of performing two or more sequential separations of ions usually coupling two or more mass analyzers. Coupling a quadrupole and time of flight resulted in the production of high-resolution mass spectrometers (i.e., Q-ToF). This article will historically introduce mass spectrometry and summarizes the advantages and disadvantages of ESI and MALDI along with quadrupole and ToF mass analyzers, including the technical marriage between the two analyzers. This article is educational in nature and intended for graduate students and senior biochemistry students as well as chemists and biochemists who are not familiar with mass spectrometry and would like to learn the basics; it is not intended for mass spectrometry experts.     

电子与多电荷离子的碰撞电离(英文)

主要揭示了不同电离机制对高电荷态离子单电离和多重电离的贡献 ,包括直接电离 (一步过程 )、激发 自电离 (两步过程 )以及内壳Auger过程 ,研究了高电荷态镨离子的电子碰撞电离. Electron-impact ionization of ions is one of the most fundamental processes in every kind of plasma. Especially in high-temperature plasmas-whether in laboratory (nuclear fusion) or in astrophysics (atmosphere of stars)-atoms become ionized into multiply-charged ions by electron impact. The main purpose of our investigations is to unravel the contributions from different ionization mechanisms-like direct ionization (one-step process), excitation-autoionization (two-step process) and...     

不同电极结构下介质阻挡放电电离特征的试验研究

由于具有工作气压高、放电均匀等特点,大气压介质阻挡放电成为近年来非平衡等离子体领域研究的主要技术。电极结构是电离特性的主要影响因素之一,因此,通过电极结构优化来改善电离特性,对等离子体放电设备的应用领域拓展及性能优化至关重要。为改善大气压介质阻挡放电的电离特性,产生高活性、高均匀性的低温等离子体,基于自主设计的同轴介质阻挡放电装置进行了不同电极结构的电离试验及参数诊断;在一个标准大气压、放电频率11.4 kHz、放电峰值电压5.4～13.4 kV条件下进行了氩气电离试验;采用原子发射光谱法（AES）对氩等离子体谱线的激发、分光进行了检测分析;研究了螺纹电极、齿状电极、圆柱电极放电的特征光谱参数及外施电压对介质阻挡放电特征参数的影响。结果表明,齿状电极放电所形成等离子体的放电强度更大且放电效果显著,电子平均能量利用率低,电子激励温度弱于圆柱电极;圆柱电极放电强度较弱,但易形成大面积均匀性等离子体;大气压环境下电子激励温度不因外源电压的升高而单调递加,这表明通道内微放电的主要特征并不依赖于外施电压的供给,而是取决于电极结构、气体组份、气体压强;增大外施电压仅能增加单位时间内微放电的数量,经整合电子激励温度可达3 500 K,符合典型的低温等离子体特征。     

酮类有机物放电离子淌度谱研究

离子淌度谱是一种快速检测痕量挥发性有机物的高灵敏方法。在放电离子源离子淌度谱装置上,研究了八种酮类有机物的离子淌度谱。实验测量了各种离子的约化迁移率,其中丙酮、正丁酮、1-甲基-2-吡咯烷酮、环己酮、苯乙酮的实验结果与前人63Ni放射源离子淌度谱相一致,而甲基异丙基酮、4-甲基-2-戊酮、环戊酮单体和二聚体离子的约化迁移率则是首次报道。实验测量的约化迁移率与离子质量线性相关,获得的对酮类有机物检测灵敏度在ng·L-1量级。