Biogenic aldehyde determination by reactive paper spray ionization mass spectrometry

Ionization of aliphatic and aromatic aldehydes is improved by performing simultaneous chemical derivatization using 4-aminophenol to produce charged iminium ions during paper spray ionization. Accelerated reactions occur in the microdroplets generated during the paper spray ionization event for the tested aldehydes (formaldehyde, n-pentanaldehyde, n-nonanaldehyde, n-decanaldehyde, n-dodecanaldehyde, benzaldehyde, m-anisaldehyde, and p-hydroxybenzaldehyde). Tandem mass spectrometric analysis of the iminium ions using collision-induced dissociation demonstrated that straight chain aldehydes give a characteristic fragment at m/z 122 (shown to correspond to protonated 4-(methyleneamino)phenol), while the aromatic aldehyde iminium ions fragment to give a characteristic product ion at m/z 120. These features allow straightforward identification of linear and aromatic aldehydes. Quantitative analysis of n-nonaldehyde using a benchtop mass spectrometer demonstrated a linear response over 3 orders of magnitude from 2.5 ng to 5 μg of aldehyde loaded on the filter paper emitter. The limit of detection was determined to be 2.2 ng for this aldehyde. The method had a precision of 22%, relative standard deviation. The experiment was also implemented using a portable ion trap mass spectrometer.     

Detection of histamine in beer by nano extractive electrospray ionization mass spectrometry

In this study, rapid quantitative detection of histamine in beer was achieved by using nano extractive electrospray ionization mass spectrometry (nano EESI‐MS) coupling with standard addition method. Based on the MS² experiment, histamine concentrations in three beer samples were determined to be 1.10 ± 0.12 µg/ml, 0.81 ± 0.09 µg/ml and 0.79 ± 0.09 µg/ml. The limit of detection for this method was calculated to be 0.02 µg/ml. These results show that this novel method can be used for direct, rapid and sensitive detection of histamine in beer without any tedious sample pretreatment. Copyright © 2014 John Wiley & Sons, Ltd.     

介质阻挡放电离子源质谱分析

敞开式离子化质谱可对表面样品进行直接快速分析而受到关注,成为质谱分析的热点研究方向.介质阻挡放电离子源是一种基于等离子体放电机理的敞开式离子源,近年来得到了较快的发展.本文着重介绍该离子源的基本原理、性能特征以及应用进展,并对其发展趋势进行了展望.     

Recent advances of ambient ionization mass spectrometry imaging in clinical research

The structural information and spatial distribution of molecules in biological tissues are closely related to the potential molecular mechanisms of disease origin, transfer, and classification. Ambient ionization mass spectrometry imaging is an effective tool that provides molecular images while describing in situ information of biomolecules in complex samples, in which ionization occurs at atmospheric pressure with the samples being analyzed in the native state. Ambient ionization mass spectrometry imaging can directly analyze tissue samples at a fairly high resolution to obtain molecules in situ information on the tissue surface to identify pathological features associated with a disease, resulting in the wide applications in pharmacy, food science, botanical research, and especially clinical research. Herein, novel ambient ionization techniques, such as techniques based on spray and solid‐liquid extraction, techniques based on plasma desorption, techniques based on laser desorption ablation, and techniques based on acoustic desorption were introduced, and the data processing of ambient ionization mass spectrometry imaging was briefly reviewed. Besides, we also highlight recent applications of this imaging technology in clinical researches and discuss the challenges in this imaging technology and the perspectives on the future of the clinical research.     

Real-time traceability of sorghum origin by soldering iron-based rapid evaporative ionization mass spectrometry and chemometrics

Sorghum is an important grain with a high economic value for liquor production. Tracing the geographical origin of sorghum is vital to guarantee the liquor flavor. Soldering iron-based rapid evaporative ionization mass spectrometry (REIMS) combined with chemometrics was developed for the real-time discrimination of the sorghum's geographical origin. The working conditions of soldering iron-based ionization were optimized, and then the obtained MS profiling data were processed using chemometrics analysis methods, including principal component analysis–linear discriminant analysis and orthogonal projection to latent structures discriminant analysis (OPLS-DA). A recognition model was established, and discriminations of sorghum samples from 10 provinces in China were achieved with a correct rate higher than 90%. On the basis of OPLS-DA, the specific ions of m/z 279.2327, 281.2479, and 283.2639 had relatively strong discrimination power for the geographical origins of sorghum. The developed method was successfully applied in the discrimination of sorghum origins. The results indicated that the soldering iron-based REIMS technique combined with chemometrics is a useful tool for direct, fast, and real-time ionization of poor conductivity samples and acquisition of metabolic profiling data.     

等离子体常压解吸离子源质谱

近年来,常压开源质谱解吸/离子化(ambient desorption/ionization mass spectrometry)技术的开发促进了质谱分析的蓬勃发展.作为常压开源质谱技术的一大重要分支,基于等离子体的常压质谱解吸/离子化技术因无需样品预处理、无溶剂化过程、高灵敏度、高通量、能实时在线检测样品等优点,受到了学术界及仪器制造、化学和生物分析等相关产业界的广泛关注.本文从离子源的种类、原理及应用等角度对目前我国在开源质谱领域中自主研发的基于等离子体的常压离子源的研究进展进行了总结,并对此类等离子体常压离子源的发展进行了展望,重点涉及微波等离子体源、常压微辉光放电等离子体源和解吸电晕束离子源.     

On‐surface Fenton and Fenton‐like reactions appraised by paper spray ionization mass spectrometry

On‐surface degradation of sildenafil (an adequate substrate as it contains assorted functional groups in its structure) promoted by the Fenton (Fe²⁺/H₂O₂) and Fenton‐like (Mⁿ⁺/H₂O₂; Mⁿ⁺ = Fe³⁺, Co²⁺, Cu²⁺, Mn²⁺) systems was investigated by using paper spray ionization mass spectrometry (PS‐MS). The performance of each system was compared by measuring the ratio between the relative intensities of the ions of m/z 475 (protonated sildenafil) and m/z 235 (protonated lidocaine, used as a convenient internal standard and added to the paper just before the PS‐MS analyzes). The results indicated the following order in the rates of such reactions: Fe²⁺/H₂O₂ ≫ H₂O₂ ≫ Cu²⁺/H₂O₂ > Mⁿ⁺/H₂O₂ (Mⁿ⁺ = Fe³⁺, Co²⁺, Mn²⁺) ~ Mⁿ⁺ (Mⁿ⁺ = Fe²⁺, Fe³⁺, Co²⁺, Cu²⁺, Mn²). The superior capability of Fe²⁺/H₂O₂ in causing the degradation of sildenafil indicates that Fe²⁺ efficiently decomposes H₂O₂ to yield hydroxyl radicals, quite reactive species that cause the substrate oxidation. The results also indicate that H₂O₂ can spontaneously decompose likely to yield hydroxyl radicals, although in a much smaller extension than the Fenton system. This effect, however, is strongly inhibited by the presence of the other cations, ie, Fe³⁺, Co²⁺, Cu²⁺, and Mn²⁺. A unique oxidation by‐product was detected in the reaction between Fe²⁺/H₂O₂ with sildenafil, and a possible structure for it was proposed based on the MS/MS data. The on‐surface reaction of other substrates (trimethoprim and tamoxifen) with the Fenton system was also investigated. In conclusion, PS‐MS shows to be a convenient platform to promptly monitor on‐surface oxidation reactions.     

Determination of trace cobalt in fruit samples by resonance ionization mass spectrometry

1-color 2-photon resonance ionization mass spectrometry (RIMS) with a new electro-thermal atomizer equipped with six filaments has been applied for quantitative analysis of trace cobalt in fruit samples. The efficient transition lines for sensitive detection were investigated in the wavelength range of 283-302 nm and a transition at 298.71 nm was chosen as an excited state for the determination of Co. A proper calibration curve for cobalt up to 1 ppb has been constructed with satisfactory results. The minimum detectible amount of cobalt in this RIMS system was identified as less than 5 pg. The content of Co in three different fruits, pear, apple and Korean mandarin orange, have been determined by adopting standard addition to the fruit sample juice. The content of the Co in 5 μl of apple, pear and Korean mandarin juice was identified as 150, 45 and 100 pg, respectively.     

Comparative study on ambient ionization methods for direct analysis of navel orange tissues by mass spectrometry

It is of sustainable interest to improve the sensitivity and selectivity of the ionization process, especially for direct analysis of complex samples without matrix separation. Herein, four ambient ionization methods including desorption atmospheric pressure chemical ionization (DAPCI), heat‐assisted desorption atmospheric pressure chemical ionization (heat‐assisted DAPCI), microwave plasma torch (MPT) and internal extractive electrospray ionization (iEESI) were employed for comparative analysis of the navel orange tissue samples by mass spectrometry. The volatile organic compounds (e.g. ethanol, vanillin, leaf alcohol and jasmine lactone) were successfully detected by non‐heat‐assisted DAPCI‐MS, while semi‐volatile organic compounds (e.g. 1‐nonanol and ethyl nonanoate) together with low abundance of non‐volatile organic compounds (e.g. sinensetin and nobiletin) were obtained by heat‐assisted DAPCI‐MS. Typical nonvolatile organic compounds [e.g. 5‐(hydroxymethyl)furfural and glucosan] were sensitively detected with MPT‐MS. Compounds of high polarity (e.g. amino acids, alkaloids and sugars) were easily profiled with iEESI‐MS. Our data showed that more analytes could be detected when more energy was delivered for the desorption ionization purpose; however, heat‐sensitive analytes would not be detected once the energy input exceeded the dissociation barriers of the analytes. For the later cases, soft ionization methods such as iEESI were recommended to sensitively profile the bioanalytes of high polarity. Copyright © 2017 John Wiley & Sons, Ltd.     

Salicylaldehyde azine cluster formation observed by cold‐spray ionization mass spectrometry

We installed a cold‐spray ionization (CSI) source on a mass spectrometer to investigate the self‐assembly behavior of an aggregation‐induced emission enhancement system. Using a CSI source and the three‐dimensional platform, a self‐assembly system of a salicylaldehyde azine (SAA) was studied in mixture solution. This method permitted the determination of the structural information of the solution state, which cannot be detected by conventional mass spectrometry. In addition to the [M+H]⁺ ion (M is the SAA molecule), many major ion clusters such as [2M+Na]⁺ at m/z 503, [3M+Na]⁺ at m/z 743, [4M+Na]⁺ at m/z 983 and higher order aggregates were observed in the CSI mass spectra. However, many fragment ions, with the exception of cluster ions, appeared with high abundance when the ESI ion source was used due to the desolvation chamber temperature, suggesting that some aggregation can be detected at low temperatures. To investigate the effect of solvent on the aggregation, the CSI‐mass spectrometry (MS) experiments of SAA in absolute ethanol solution and ethanol/water (good/poor solvent) mixture solution were conducted. The most abundant ion peak was protonated SAA (m/z 241) in absolute ethanol, but many cluster ions and some multiple charged ion peaks were observed after adding a small amount of water into the ethanol solution. The results showed good agreement with that inferred by the combinational analysis of scanning electron microscope and fluorescence microscopy, indicating that CSI‐MS is capable of providing self‐assembly information of labile molecules in the solution state. Copyright © 2013 John Wiley & Sons, Ltd.     

原位电离质谱技术在食品质量安全检测中的应用

原位电离质谱技术能够在常压环境下直接分析各种食品样品,无需或仅需极少的食品制备,大大提高了分析效率,已经成为一种重要的食品快速分析方法。本文对原位电离质谱的离子化技术和工作流程进行了介绍,从食品污染物检测、非法添加物筛查、食品真伪鉴别和品质评价等方面出发,综述了该技术在食品质量安全检测中的应用。讨论了其应用于食品分析领域时面临的挑战和未来发展趋势。     

Critical assessment of ionization patterns and applications of ambient desorption/ionization mass spectrometry using FAPA–MS

Ambient desorption/ionization mass spectrometry (MS) has gained growing interest during the last decade due to its high analytical performance and yet simplicity. Here, one of the recently developed ambient desorption/ionization MS sources, the flowing atmospheric‐pressure afterglow (FAPA) source, was investigated in detail regarding background ions and typical ionization patterns in the positive as well as the negative ion mode for a variety of compound classes, comprising alkanes, alcohols, aldehydes, ketones, carboxylic acids, organic peroxides and alkaloids. A broad range of signals for adducts and losses was found, besides the usually emphasized detection of quasimolecular ions, i.e. [M + H]⁺ and [M ? H]^? in the positive and the negative mode, respectively. It was found that FAPA–MS is best suited for polar analytes containing nitrogen and/or oxygen functionalities, e.g. carboxylic acids, with low molecular weights and relatively high vapor pressures. In addition, the source was used in proof‐of‐principle studies, illustrating the capabilities and limitations of the technique: Firstly, traces of cocaine were detected and unambiguously identified on euro banknotes using FAPA ionization in combination with tandem MS, suggesting a correlation between cocaine abundance and age of the banknote. Secondly, FAPA–MS was used for the identification of acidic marker compounds in organic aerosol samples, indicating yet‐undiscovered matrix and sample surface effects of ionization pathways in the afterglow region. Copyright © 2016 John Wiley & Sons, Ltd.     

Ambient imaging mass spectrometry by electrospray ionization using solid needle as sampling probe

Although being an atmospheric pressure ion source, electrospray ionization (ESI) has rarely been used directly for ambient imaging mass spectrometry because the sample has to be introduced as liquid solution through the capillary. Instead of capillary, probe electrospray ionization (PESI), which has been developed recently, uses a solid needle as the sampling probe, as well as the electrospray emitter, and has been applied not only for liquid solutions but also for the direct sampling on wet samples. Biological tissues are composed of cells that contain 70–90% water, and when the surface is probed by the needle tip, the biological fluid adhering to the needle can be electrosprayed directly or assisted by additional solvent added onto the needle surface. Here, we demonstrate ambient imaging mass spectrometry of mouse brain section using PESI, incorporated with an auxiliary heated capillary sprayer. The solvent vapor generated from the sprayer condensed on the needle tip, re‐dissolving the adhered sample, and at the same time, providing an indirect means for needle cleaning. The histological sections were prepared by fixation using paraformaldehyde, and the spatial analysis was automated by maintaining an equal sampling depth into the sample in addition to raster scan. Phospholipids and galactosylceramides were readily detected from the mouse brain section in the positive ion mode, and were mapped with 60 µm lateral resolution to form mass spectrometric images. Copyright © 2009 John Wiley & Sons, Ltd.     

Document authentication at molecular levels using desorption atmospheric pressure chemical ionization mass spectrometry imaging

Molecular images of documents were obtained by sequentially scanning the surface of the document using desorption atmospheric pressure chemical ionization mass spectrometry (DAPCI‐MS), which was operated in either a gasless, solvent‐free or methanol vapor‐assisted mode. The decay process of the ink used for handwriting was monitored by following the signal intensities recorded by DAPCI‐MS. Handwritings made using four types of inks on four kinds of paper surfaces were tested. By studying the dynamic decay of the inks, DAPCI‐MS imaging differentiated a 10‐min old from two 4 h old samples. Non‐destructive forensic analysis of forged signatures either handwritten or computer‐assisted was achieved according to the difference of the contour in DAPCI images, which was attributed to the strength personalized by different writers. Distinction of the order of writing/stamping on documents and detection of illegal printings were accomplished with a spatial resolution of about 140 µm. A Matlab® written program was developed to facilitate the visualization of the similarity between signature images obtained by DAPCI‐MS. The experimental results show that DAPCI‐MS imaging provides rich information at the molecular level and thus can be used for the reliable document analysis in forensic applications. © 2013 The Authors. Journal of Mass Spectrometry published by John Wiley & Sons, Ltd.     

Real time monitoring of accelerated chemical reactions by ultrasonication‐assisted spray ionization mass spectrometry

Ultrasonication has been used to accelerate chemical reactions. It would be ideal if ultrasonication‐assisted chemical reactions could be monitored by suitable detection tools such as mass spectrometry in real time. It would be helpful to clarify reaction intermediates/products and to have a better understanding of reaction mechanism. In this work, we developed a system for ultrasonication‐assisted spray ionization mass spectrometry (UASI–MS) with an ~1.7 MHz ultrasonic transducer to monitor chemical reactions in real time. We demonstrated that simply depositing a sample solution on the MHz‐based ultrasonic transducer, which was placed in front of the orifice of a mass spectrometer, the analyte signals can be readily detected by the mass spectrometer. Singly and multiply charged ions from small and large molecules, respectively, can be observed in the UASI mass spectra. Furthermore, the ultrasonic transducer used in the UASI setup accelerates the chemical reactions while being monitored via UASI–MS. The feasibility of using this approach for real‐time acceleration/monitoring of chemical reactions was demonstrated. The reactions of Girard T reagent and hydroxylamine with steroids were used as the model reactions. Upon the deposition of reactant solutions on the ultrasonic transducer, the intermediate/product ions are readily generated and instantaneously monitored using MS within 1 s. Additionally, we also showed the possibility of using this reactive UASI–MS approach to assist the confirmation of trace steroids from complex urine samples by monitoring the generation of the product ions. Copyright © 2014 John Wiley & Sons, Ltd.     

Direct monitoring of drug degradation by easy ambient sonic-spray ionization mass spectrometry: the case of enalapril

Using enalapril maleate as a test case, the ability of ambient mass spectrometry, namely, via easy ambient sonic‐spray ionization mass spectrometry (EASI‐MS), to perform direct monitoring of drug degradation has been tested. Two manufacturing processes were investigated (direct compression and wet granulation), and the formation of degradation products was measured via both EASI‐MS and high‐performance liquid chromatography with ultraviolet detection for a total period of 18 months. Both techniques provide comparable results, which indicate that direct analysis by ambient mass spectrometric techniques presents a viable alternative for drug degradation monitoring with superior simplicity, throughput, and reliability (no sample manipulation), and comparable quantitative results. In terms of qualitative monitoring, the full mass spectra with intact species provided by EASI‐MS allow for comprehensive monitoring of known and unknown (or unexpected) degradation products. Copyright © 2011 John Wiley & Sons, Ltd.     

Open channel-based microchip electrophoresis interfaced with mass spectrometry via electrostatic spray ionization

The coupling between open channel-based microchip electrophoresis and mass spectrometry via electrostatic spray ionization is proposed for in situ detection of fractionated analytes. Electrophoretic separation is performed in an open channel fabricated in a plastic substrate. The solvent of background electrolyte is evaporated from the open channel because of Joule heating during electrophoresis, leaving the dried electrophoretic bands to be directly analyzed by mass spectrometry via scanning electrostatic spray ionization. Proof-of-concept results are obtained with fluorescent dyes and antibiotics as the test samples, demonstrating an efficient on-chip detection platform based on the electrophoresis and electrostatic spray ionization mass spectrometry.     

Fundamental properties of a touchable high‐power pulsed microplasma jet and its application as a desorption/ionization source for ambient mass spectrometry

Plasma‐based ambient desorption/ionization mass spectrometry (ADI–MS) has attracted considerable attention in many fields because of its capacity for direct sample analyses. In this study, a high‐power pulsed microplasma jet (HPPMJ) was developed and investigated as a new plasma desorption/ionization source. In an HPPMJ, a microhollow cathode discharge is generated in a small hole (500 µm in diameter) using a pulsed high‐power supply. This system can realize a maximum power density of 5 × 10⁸ W/cm³. The measured electron number density, excitation temperature and afterglow gas temperature of the HPPMJ were 3.7 × 10¹⁵ cm^‐3, 7000 K at maximum and less than 60 °C, respectively, which demonstrate that the HPPMJ is a high‐energy, high‐density plasma source that is comparable with an argon inductively coupled plasma while maintaining a low gas temperature. The HPPMJ causes no observable damage to the target because of its low gas temperature and electrode configuration; thus, we can apply it directly to human skin. To demonstrate the analytical capacity of ADI–MS using an HPPMJ, the plasma was applied to direct solid sample analysis of the active ingredients in pharmaceutical tablets. Caffeine, acetaminophen, ethenzamide, isopropylantipyrine and ibuprofen were successfully detected. Application to living tissue was also demonstrated, and isopropylantipyrine on a finger was successfully analyzed without damaging the skin. The limits of detection (LODs) for caffeine, isopropylantipyrine and ethenzamide were calculated, and LODs at the picogram level were achieved. These results indicate the applicability of the HPPMJ for high‐sensitivity analysis of materials on a heat‐sensitive surface. Copyright © 2014 John Wiley & Sons, Ltd.