大气压基体辅助激光解析离子源发展及其应用

介绍了国际上新出现的一种离子源——大气压基体辅助激光解析离子源(atmospheric pressure matrix-assisted laser desorption/ionization,AP-MALDI)。该离子源是在真空MALDI的基础上研究发展起来的,广泛应用于生物大分子及其相关领域的研究。该离子源较真空MALDI电离更加柔和,产生的碎片离子更少,又由于其工作在大气压下,可作为外接离子源方便地与各类质谱分析器联用,大大扩展了基体辅助激光解析离子源的应用范围。文章详细介绍了AP-MALDI的基本原理、结构及技术进展。此外,还对该离子源在生物高聚物分析方面的最新应用进行了介绍。     

Desorption/ionization of acrylamide in aqueous solutions in atmospheric pressure air using a microdischarge with vortex focusing of ions

A method of desorption/ionization in a microdischarge with ion vortex focusing (vortex focusing microdischarge, VFM) is suggested. A glow microdischarge is initiated in an air flow, and resulting ions act on the surface of interest. As a model compound, an aqueous solution of acrylamide is taken. Desorption/ionization taking place under atmospheric pressure is followed by the mass-spectrometric identification of the ions. The operating parameters of the VFM system are studied and optimized. Upon optimization of the system, the detection limit of acrylamide trace amounts in aqueous solutions is determined using the suggested method of desorption/ionization and analyte ion focusing with a vortex (swirling) jet. The acrylamide detection limit is found to be 2 × 10^?3 g/L.     

Analysis of lipids with desorption atmospheric pressure photoionization-mass spectrometry (DAPPI-MS) and desorption electrospray ionization-mass spectrometry (DESI-MS)

In this article, the effect of spray solvent on the analysis of selected lipids including fatty acids, fat-soluble vitamins, triacylglycerols, steroids, phospholipids, and sphingolipids has been studied by two different ambient mass spectrometry (MS) methods, desorption electrospray ionization-MS (DESI-MS) and desorption atmospheric pressure photoionization-MS (DAPPI-MS). The ionization of the lipids with DESI and DAPPI was strongly dependent on the spray solvent. In most cases, the lipids were detected as protonated or deprotonated molecules; however, other ions were also formed, such as adduct ions (in DESI), [M-H](+) ions (in DESI and DAPPI), radical ions (in DAPPI), and abundant oxidation products (in DESI and DAPPI). DAPPI provided efficient desorption and ionization for neutral and less polar as well as for ionic lipids but caused extensive fragmentation for larger and more labile compounds because of a thermal desorption process. DESI was more suitable for the analysis of the large and labile lipids, but the ionization efficiency for less polar lipids was poor. Both methods were successfully applied to the direct analysis of lipids from pharmaceutical and food products. Although DESI and DAPPI provide efficient analysis of lipids, the multiple and largely unpredictable ionization reactions may set challenges for routine lipid analysis with these methods.     

Collison nebulizer as a new soft ionization source for mass spectrometry

We have proposed that a Collison-type nebulizer be used as an ionization source for mass spectrometry with ionization under atmospheric pressure. This source does not require the use of electric voltage, radioactive sources, heaters, or liquid pumps. It has been shown that the number of ions produced by the ⁶³Ni radioactive source is three to four times larger than the number of ions produced by acoustic ionization sources. We have considered the possibility of using a Collison-type nebulizer in combination with a vortex focusing system as an ion source for extractive ionization of compounds under atmospheric pressure. The ionization of volatile substances in crossflows of a charged aerosol and an analyte (for model compounds of the amine class, viz., diethylaniline, triamylamine, and cocaine) has been investigated. It has been shown that the limit of detecting cocaine vapor by this method is on the level of 4.6 × 10^–14 g/cm³.     

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.     

Secondary processes in atmospheric pressure chemical ionization-ion trap mass spectrometry: a case study of orotic acid

Atmospheric pressure chemical ionization is known for producing unusual artifacts of the ionization process in some cases. In this work, processes occuring in atmospheric pressure chemical ionization/MS of orotic acid that afforded ions accompanying protonated and deprotonated orotic acid molecules in the spectra were studied. Two processes ran in parallel in the ion source: decarboxylation of neutral orotic acid and collision-induced dissociation of its protonated or deprotonated form. A procedure discerning pre-ionization decomposition and post-ionization dissociation by manipulating ion source parameters was proposed. Experiments with isotopically labeled solvents confirmed ion-molecule reactions of the product of collision-induced dissociation of protonated orotic acid with solvent molecules in the ion source and even under vacuum in the ion trap.     

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.     

Mass spectrometric study of the mechanism of the ionization of nitrogen-containing organic compounds on the surface of a molybdenum microalloyed alloy

Experimental studies of the mechanism of surface ionization of amines on the surface of a microalloyed molybdenum alloy in the air at atmospheric pressure were performed. The products of surface ionization of triethanolamine, Dimedrol, and papaverine were studied using a high-resolution mass spectrometer. The physicochemical parameters of surface ionization of some organic nitrogen compounds were measured. It was shown experimentally that the ionization of organic compounds of this type on the surface of the heated molybdenum alloy in air at atmospheric pressure occurs by a mechanism involving Brønsted sites (Brønsted).     

Interaction between explosive and analyte layers in explosive matrix-assisted plasma desorption mass spectrometry

An HMX/insulin two-layer system was chosen as a model for further investigation of the matrix properties of explosive materials for protein analytes in plasma desorption mass spectrometry. The dependencies of the molecular ion yield and average charge state as a function of the analyte thickness were studied. An increase in the charge state of multiply protonated molecular species was confirmed as the major matrix effect, with the average charge state z at the smallest thickness studied being higher than in matrix-assisted laser desorption/ionization and closer to the value obtained in electrospray ionization under standard acidic conditions. Observed charge state distributions are significantly narrower than the corresponding Poisson distributions, which suggests that the protonation of insulin is limited in plasma desorption by the number of basic sites in the molecule, similar to electrospray ionization. Both the curve displaying total molecular ion yield and the one showing the total charge (proton) yield as a function of the insulin thickness have maxima at a thickness different from an insulin monolayer. These observations diminish the significance of a matrix/analyte interface mechanism for the explosive matrix assistance. Instead, a mechanism related to the chemical energy release during conversion of the explosive after the ion impact is proposed. As additional mechanisms, enhanced protonation of the analyte through collisions with products of the explosive decay is considered, as well as electron scavenging by other products, which leads to a higher survival probability of positively charged protein molecular ions. Copyright 1999 John Wiley & Sons, Ltd.     

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.     

Molecular imaging by Mid-IR laser ablation mass spectrometry

Mid-IR laser ablation at atmospheric pressure (AP) produces a mixture of ions, neutrals, clusters, and particles with a size distribution extending into the nanoparticle range. Using external electric fields the ions can be extracted and sampled by a mass spectrometer. In AP infrared (IR) matrix-assisted laser desorption ionization (MALDI) experiments, the plume was shown to contain an appreciable proportion of ionic components that reflected the composition of the ablated target and enabled mass spectrometric analysis. The detected ion intensities rapidly declined with increasing distance of sampling from the ablated surface to ∼4 mm. This was rationalized in terms of ion recombination and the stopping of the plume expansion by the background gas. In laser ablation electrospray ionization (LAESI) experiments, the ablation plume was intercepted by an electrospray. The neutral particles in the plume were ionized by the charged droplets in the spray and enabled the detection of large molecules (up to 66 kDa). Maximum ion production in LAESI was observed at large (∼15 mm) spray axis to ablated surface distance indicating a radically different ion formation mechanism compared to AP IR-MALDI. The feasibility of molecular imaging by both AP IR-MALDI and LAESI was demonstrated on targets with mock patterns. Presented at the 9-th International Conference on Laser Ablation, 2007 Tenerife, Canary Islands, Spain     

Analysis of dammar resin with MALDI-FT-ICR-MS and APCI-FT-ICR-MS

Comprehensive analysis of high-resolution mass spectra of aged natural dammar resin obtained with Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR-MS) using matrix-assisted laser desorption/ionization (MALDI) and atmospheric pressure chemical ionization (APCI) is presented. Dammar resin is one of the most important components of painting varnishes. Dammar resin is a terpenoid resin (dominated by triterpenoids) with intrinsically very complex composition. This complexity further increases with aging. Ten different solvents and two-component solvent mixtures were tested for sample preparation. The most suitable solvent mixtures for the MALDI-FT-ICR-MS analysis were dichloromethane-acetone and dichloromethane-ethanol. The obtained MALDI-FTMS mass spectrum contains nine clusters of peaks in the m/z range of 420-2200, and the obtained APCI-FTMS mass spectrum contains three clusters of peaks in the m/z range of 380-910. The peaks in the clusters correspond to the oxygenated derivatives of terpenoids differing by the number of C(15)H(24) units. The clusters, in turn, are composed of subclusters differing by the number of oxygen atoms in the molecules. Thorough analysis and identification of the components (or groups of components) by their accurate m/z ratios was carried out, and molecular formulas (elemental compositions) of all major peaks in the MALDI-FTMS and APCI-FTMS spectra were identified (and groups of possible isomeric compounds were proposed). In the MALDI-FTMS and APCI-FTMS mass spectrum, besides the oxidized C(30), triterpenoids also peaks corresponding to C(29) and C(31) derivatives of triterpenoids (demethylated and methylated, correspondingly) were detected. MALDI and APCI are complementary ionization sources for the analysis of natural dammar resin. In the MALDI source, preferably polar (extensively oxidized) components of the resin are ionized (mostly as Na(+) adducts), whereas in the APCI source, preferably nonpolar (hydrocarbon and slightly oxidized) compounds are ionized (by protonation). Either of the two ionization methods, when used alone, gives an incomplete picture of the dammar resin composition.     

Confined direct analysis in real time ion source and its applications in analysis of volatile organic compounds of Citrus limon (lemon) and Allium cepa (onion)

The DART (direct analysis in real time) ion source is a novel atmospheric pressure ionization technique that enables efficient ionization of gases, liquids and solids with high throughput. A major limit to its wider application in the analysis of gases is its poor detection sensitivity caused by open-air sampling. In this study, a confined interface between the DART ion source outlet and mass spectrometer sampling orifice was developed, where the plasma generated by the atmospheric pressure glow discharge collides and ionizes gas-phase molecules in a Tee-shaped flow tube instead of in open air. It leads to significant increase of collision reaction probability between high energy metastable molecules and analytes. The experimental results show that the ionization efficiency was increased at least by two orders of magnitude. This technique was then applied in the real time analysis of volatile organic compounds (VOCs) of Citrus Limon (lemon) and wounded Allium Cepa (onion). The confined DART ion source was proved to be a powerful tool for the studies of plant metabolomics.     

Mechanism of ionization of organic compounds on tip emitters

The current-voltage characteristics of organic compounds at a tip platinum emitter have been studied in 0.2-1.0 V/Å fields. It is shown that the parameter (V-?) does not affect the formation of the desorption ion barrier in the field ionization of atoms and molecules under a high potential gradient providing electron tunneling to the Fermi level of the emitter material and, therefore, the probability of the ion desorption cannot explicitly depend on this parameter.     

Electron-induced desorption of O+ ions from W,Mo and Cr

We have studied the electron-induced desorption (EID) of O⁺ ions from oxygen-covered polycrystalline W, Mo and Cr surfaces. As the incident electron energy is increased, desorption begins at about 25 eV, and increases dramatically at the binding energy major low-lying substrate core levels. In the range of electron energy studied, below about 200 eV, there are also other variations in ion yield not associated with known core levels. The peak ion kinetic energy is 7.8, 5.3 and 3.4 eV for W, Mo and Cr respectively, and is independent of incident electron energy. These measurements imply that the desorption is initiated by a core level ionization event, although the subsequent electronic transitions leading to desorption apparently differ from those occurring on metallic oxide surfaces.     

大气压下电晕电离层离子运动规律的实验研究

对大气压下电晕电离层的离子运动规律进行了实验研究。实验结果表明: 在电晕放电的流光或辉光放电区域, 电离电场强度、注入功率密度、电离能密度等参量对等离子体输运项的影响程度仅在1 个数量级内; 在电离能密度达到0. 4mJ•cm^{- 3} , 气体速度从1. 5m•s^{- 1} 提高到25m•s^{- 1} 时, 离子输运率相应从5. 4× 10⁸ cm^{- 3}•s^{- 1} 增加到8×10¹⁰ cm^{- 3}•s^{- 1} , 提高了近2 个数量级。带电粒子的动量对离子浓度及输运的影响远大于电离电场强度、注入功率密度等的影响。     

Charge transfer activation energy for alkali atoms on Re and Ta

Ion and atom desorption energies for five alkali metals on Re and Ta were determined using the ion thermal emission noise method. The activation energies for the charge transfer process in the adsorbed state were calculated using a special energetic balance equation, which describes the surface ionization and thermal desorption effect. Energies for desorption of Li, Na, K, Rb and Cs from Re and Ta surfaces were determined by measuring the time autocorrelation function of the ion thermoemission current fluctuations.     

Study of a positive corona discharge in argon at different pressures

The corona discharge in argon at atmospheric pressure has been studied by means of a 2D model. The reduced characteristic derived from the experimental data has been described by linear regressions for the different pressures and the two studied inter-electrode distances thus confirming the validity of Townsend's approximation also in case of point to plane configuration and argon as process gas. The model validated this hypothesis which has been attributed to the minor influence of space charge in the ionization zone. Its effect is, on the other hand, more significant in the drift zone where the electric field is greatly enhanced, leading, for higher currents, to the formation of a spark gap. Electron and ion distributions allow the influence of structural (electrode configurations and distance) and operative (pressure and discharge current) parameters to be evaluated including the current loss due to diffusion through different confining boundaries.     

Yttrium ionization scheme development for Ti:Sa laser based RILIS

Resonant ionization laser ion sources (RILIS) are popular ion sources if intense, radioactive ion beams (RIBs) with minimal isobaric contamination are required. The intensity of the ion beam depends strongly on the applied resonant laser ionization scheme. Based on the all solid state laser system TRIUMF’s RILIS (TRILIS) is using, the off-line development towards an efficient ionization scheme for yttrium is presented. Several continuous wavelength scans have been performed to compare different nonresonant ionization schemes and to identify suitable Rydberg or autoionizing states for resonant ionization schemes.     

Isomeric Cl(2)O(2)(+) and Cl(2)O(2)(-) ions

Charged species structurally related to several isomers of Cl(2)O(2), of considerable importance in atmospheric chemistry, were obtained by chemical ionization (CI) and characterized by collisionally activated dissociation (CAD) mass spectrometry. The ClOClO(+) and [Cl(2)-O(2)](+) species were prepared by positive ion Cl(2)/CI of ClO(2) and O(2), respectively, whereas the ClClO(2)(+) isomer proved an elusive species of considerably lower stability. The ClClO(2)(-) anion was obtained from the negative ion Cl(2)/CI of ClO(2). The formation process, structure and stability of the ions are discussed in connection with available theoretical results and related to the recent preparation of (Cl(2)O(2))(+)SbF(6)(-) and (Cl(2)O(2))(+)Sb(2)F(11)(-) salts in the solid phase. Copyright 1999 John Wiley & Sons, Ltd.