Desorption Electrospray Ionization Source Research Articles

Abstract 16838: Relation of Clinical Status in Heart Failure to Cardiac Lysophosphatidylethanolamine Accumulation in Hypertrophic Cardiomyopathy

Background: Patients with hypertrophic cardiomyopathy (HCM) represents diverse symptoms, morphology, and cardiovascular events. Although myocardium metabolism in patients with HCM has been studied, it is not well elucidated. In this study, we assessed the association between biomarkers, heart failure-related findings, genetic mutations, and myocardium lipid metabolism in HCM patients using imaging mass spectrometry. Method: We prospectively enrolled patients with HCM in Hamamatsu University hospital from July 2020 to October 2022. All patients underwent endomyocardial biopsy and genetic analysis. Obtained myocardial specimens were analyzed using a desorption electrospray ionization source attached to a mass spectrometer. Differences among groups were statistically evaluated with the Fisher’s exact test and Mann-Whitney U test. Correlations between the two values were analyzed using Spearman’s correlation coefficient values. Results: A total of 31 Japanese patients were enrolled in this study. These patients included 18 (58.0%) women, and the mean age was 67.6 ± 10.6 years. Genetic analysis revealed that six (19.4%) patients had pathogenic or likely pathogenic variant. (Frequency of causal genes was as follows: MYBPC3 2 [6.5%], TNNI3 2 [6.5%], MYH7 1 [3.2%], and MYOZ2 1 [3.2%].) We divided the patients into two groups according to their median intensity of candidate molecule to reveal between group differences. The group of high lysophosphatidylethanolamine (LPE) showed lower N-terminal pro-brain natriuretic peptide (NT-proBNP) levels (330.0 [147.0-614.0] pg/mL vs. 933.0 [699.5-2576.5] pg/mL, P = 0.001). A correlation was observed between the intensity of LPE and the NT-proBNP levels (r = -0.455, P = 0.012). There was no association between the presence of genetic mutations and New York Heart Association class and LPE intensity. Conclusion: HCM patients with the high intensity of LPE in myocardial tissue had relatively low NT-proBNP levels.

Quasi-continuous infrared matrix-assisted laser desorption electrospray ionization source coupled to a quadrupole time-of-flight mass spectrometer for direct analysis from well plates.

High-throughput screening (HTS) is a technique mostly used by pharmaceutical companies to rapidly screen multiple libraries of compounds to find drug hits with biological or pharmaceutical activity. Mass spectrometry (MS) has become a popular option for HTS given that it can simultaneously resolve hundreds to thousands of compounds without additional chemical derivatization. For this application, it is convenient to do direct analysis from well plates. Herein, we present the development of an infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) source coupled directly to an Agilent 6545 for direct analysis from well plates. The source is coupled to a quadrupole time-of-flight (Q-TOF) mass spectrometer to take advantage of the high acquisition rates without sacrificing resolving power as required with Orbitrap or Fourier-transform ion cyclotron resonance (FTICR) instruments. The laser used for this source operates at 100 Hz, firing 1 pulse-per-burst, and delivers around 0.7 mJ per pulse. Continuously firing this laser for an extended duration makes it a quasi-continuous ionization source. Additionally, a metal capillary was constructed to extend the inlet of the mass spectrometer, increase desolvation of electrospray charged droplets, improve ion transmission, and increase sensitivity. Its efficiency was compared with the conventional dielectric glass capillary by measured signal and demonstrated that the metal capillary increased ionization efficiency due to its more uniformly distributed temperature gradient. Finally, we present the functionality of the source by analyzing tune mix directly from well plates. This source is a proof of concept for HTS applications using IR-MALDESI coupled to a different MS platform.

Next-Generation Infrared Matrix-Assisted Laser Desorption Electrospray Ionization Source for Mass Spectrometry Imaging and High-Throughput Screening.

Infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) is a hybrid, ambient ionization source that combines the advantages of electrospray ionization and matrix-assisted laser desorption/ionization, making it a versatile tool for both high-throughput screening (HTS) and mass spectrometry imaging (MSI) studies. To expand the capabilities of the IR-MALDESI source, an entirely new architecture was designed to overcome the key limitations of the previous source. This next-generation (NextGen) IR-MALDESI source features a vertically mounted IR-laser, a planar translation stage with computerized sample height control, an aluminum enclosure, and a novel mass spectrometer interface plate. The NextGen IR-MALDESI source has improved user-friendliness, improved overall versatility, and can be coupled to numerous Orbitrap mass spectrometers to accommodate more research laboratories. In this work, we highlight the benefits of the NextGen IR-MALDESI source as an improved platform for MSI and direct analysis. We also optimize the NextGen MALDESI source component geometries to increase target ion abundances over a wide m/z range. Finally, documentation is provided for each NextGen IR-MALDESI part so that it can be replicated and incorporated into any lab space.

Desorption electrospray ionization (DESI) source coupling ion mobility mass spectrometry for imaging fluoropezil (DC20) distribution in rat brain.

Fluoropezil (DC20) is a new selective acetylcholinesterase inhibitor, and it was developed for the treatment of Alzheimer's disease patients. In this study, a desorption electrospray ionization source coupling ion mobility mass spectrometry imaging (DESI/IMS-MSI) method was developed to explore the distribution of DC20 in brain tissue following oral administration. Rat brain coronal slices obtained 1 h and 3 h following drug dosing were used in the study. D6-DC20 was used as internal standard and sprayed by matrix sprayer on the brain slices to calibrate the matrix effect. Ion mobility separation was used to reduce the interference from background noise and the biological matrix. By optimizing DESI-MSI parameters for improved sensitivity, the limit of quantitation of the method was 1.45 pg/mm2 with a linear range from 1.45 to 72.7 pg/mm2. DESI-MSI data showed that DC20 could quickly enter and diffuse across whole brain and tended to be much more enriched in striatum than cerebral cortex and hippocampus, which was consistent with quantitative analysis using high-performance liquid chromatography-electrospray tandem mass spectrometry to measure DC20 concentration in each homogenized brain sub-region. The workflow of tissue imaging method optimization and strategy were established, and for the first time, the DESI-MSI technique and optimized method were used to explore the distribution characteristics of DC20 in rat brain, which could help elucidate pharmacological effect mechanisms and improve clinical outcomes.

Inter-platform assessment of performance of high-throughput desorption electrospray ionization mass spectrometry

High throughput analysis is increasingly relevant in both industry and academia, with applications reaching from enzymology and drug discovery to organic reaction optimization and diagnostics. Currently, chromatography-free mass spectrometry (MS) techniques have acquired an important role in this field due to their inherent speed, versatility, and chemical specificity. Desorption electrospray ionization (DESI) MS is one of these approaches, which allows for direct analysis of complex samples in the ambient environment, with throughputs better than 1 sample per second and no need for sample treatment. Here we assess the evolution of the high throughput DESI-MS analytical performance from the early DESI source developed by Prosolia Inc. to the recently commercialized version of Waters Corporation. The evaluation was carried out through both quantitative and qualitative analysis of biologically relevant compounds including metabolites, peptides, lipids and pharmaceuticals. Our results indicate that both platforms are successful at the direct analysis of these species even from complex matrices such as bioassay buffers. However, the newest iteration of the DESI stage, when combined with a quadrupole time-of-flight (Q-ToF) instrument, provides higher sensitivity (1-3 orders of magnitude lower limits of detection) and reproducibility (ca. 10% average reduction in coefficients of variation for quantitation using an internal standard). The cases explored in this study also showcase the broad applicability of high throughput DESI-MS for bioanalysis and quality control.

Streamlined Multimodal DESI and MALDI Mass Spectrometry Imaging on a Singular Dual-Source FT-ICR Mass Spectrometer.

The study of biological specimens by mass spectrometry imaging (MSI) has had a profound influence in the various forms of spatial-omics over the past two decades including applications for the identification of clinical biomarker analysis; the metabolic fingerprinting of disease states; treatment with therapeutics; and the profiling of lipids, peptides and proteins. No singular approach is able to globally map all biomolecular classes simultaneously. This led to the development of many complementary multimodal imaging approaches to solve analytical problems: fusing multiple ionization techniques, imaging microscopy or spectroscopy, or local extractions into robust multimodal imaging methods. However, each fusion typically requires the melding of analytical information from multiple commercial platforms, and the tandem utilization of multiple commercial or third-party software platforms—even in some cases requiring computer coding. Herein, we report the use of matrix-assisted laser desorption/ionization (MALDI) in tandem with desorption electrospray ionization (DESI) imaging in the positive ion mode on a singular commercial orthogonal dual-source Fourier transform ion cyclotron resonance (FT-ICR) instrument for the complementary detection of multiple analyte classes by MSI from tissue. The DESI source was 3D printed and the commercial Bruker Daltonics software suite was used to generate mass spectrometry images in tandem with the commercial MALDI source. This approach allows for the generation of multiple modes of mass spectrometry images without the need for third-party software and a customizable platform for ambient ionization imaging. Highlighted is the streamlined workflow needed to obtain phospholipid profiles, as well as increased depth of coverage of both annotated phospholipid, cardiolipin, and ganglioside species from rat brain with both high spatial and mass resolution.

Integration of 3D-printing for a desorption electrospray ionization source for mass spectrometry.

The field of ambient ionization mass spectrometry has witnessed the development of many novel and capable methods for the analysis and imaging of surfaces, with desorption electrospray ionization being a prominent technique that has been commercialized. The adaptation of this technique to existing mass spectrometry platforms requires a laboratory-built solution manufactured with the capability of fine, stable adjustments of the electrospray emitter for liquid or solid sampling purposes. The development, fabrication, and machining require tens of hours of labor for many custom solutions. Herein described is a highly modifiable alternative approach for the fabrication of a desorption electrospray ionization source, using computer-aided design and fused deposition modeling to three-dimensionally print a source platform that utilizes standard accessories of a commercial Bruker Daltonics mass spectrometer. Three-dimensional printing allows for the inexpensive, rapid development of highly modifiable plastic parts, with the total printing time of the apparatus requiring a singular day and only a few dollars of material using a consumer grade printer. To demonstrate the utility of this printed desorption electrospray ionization source, it was fitted on an unmodified Fourier transform ion cyclotron resonance mass spectrometer for a lipid fingerprint analysis in serial sections of rat brain tissue, with the acquisition of line scans of dye-coated slides for the demonstration of serial acquisition.

Autarkic desorption electrospray ionization source for on-site analysis of consumer goods.

A general-purpose desorption electrospray ionization (DESI) source is presented which is not bound to the laboratory site. It allows autarkic operation for a few hours and can be connected to different types of (autarkic or non-autarkic) mass spectrometers via an atmospheric-pressure interface. Technical characteristics are described as well as results from direct surface analysis of consumer goods such as plastics, fruit peels or pills, or from living objects such as human skin, demonstrating the detection of various target compounds such as plasticizers, pesticides, drugs or sun blockers. Quantitative analysis is demonstrated for phthalates in plastics. The geometry of the sample, the sample table and the sprayer were modified and characterized for optimization of the method. The autarkic ion source has a total size of 48.4 × 27.0 × 18.0 cm (l×w×h) and a total mass of 7 kg. The source delivers 5.5 bar pressurized air and an adjustable solvent flow rate down to 1.5 μl min-1 for the DESI sprayer. A rechargeable 25.6 V battery allows autarkic runtimes of more than 3.5 hours. Source optimization and characterization was done on an orbital trapping mass spectrometer. Connected to a portable mass spectrometer, the developed device makes DESI suitable for on-site analyses in e.g. consumer protection, border control or homeland security.

Rapid screening of basic colorants in processed vegetables through mass spectrometry using an interchangeable thermal desorption electrospray ionization source

Thermal desorption electrospray ionization/mass spectrometry (TD–ESI–MS) employing a quickly interchangeable ionization source is a relatively new ambient ionization mass spectrometric technique that has had, to date, only a limited number of applications related to food safety control. With reallocation of resources, this direct-analysis technique has had wider use in food analysis when operated in dual-working mode (pretreatment-free qualitative screening and conventional quantitative confirmation) after switching to an ambient ionization source from a traditional atmospheric pressure ionization source. Herein, we describe the benefits and challenges associated with the use of a TD–ESI source to detect adulterants in processed vegetables (PVs), as a proof-of-concept for the detection of basic colorants. While TD–ESI can offer direct qualitative screening analyses for PVs with detection capabilities lower than those provided with liquid chromatography/UV detection within 30 s, the use of TD–ESI for semi-quantification is applicable only for homogeneous food matrices.

Rapid detection of illegal colorants on traditional Chinese pastries through mass spectrometry with an interchangeable thermal desorption electrospray ionization source

Ambient mass spectrometry using an interchangeable thermal desorption/electrospray ionization source (TD–ESI) is a relatively new technique that has had only a limited number of applications to date. Nevertheless, this direct-analysis technique has potential for wider use in analytical chemistry (e.g., in the rapid direct detection of contaminants, residues, and adulterants on and in food) when operated in dual-working mode (pretreatment-free qualitative screening and conventional quantitative confirmation) after switching to a TD–ESI source from a conventional ESI source. Herein, we describe the benefits and challenges associated with the use of a TD–ESI source to detect adulterants on traditional Chinese pastries (TCPs), as a proof-of-concept for the detection of illegal colorants. While TD–ESI can offer direct (i.e., without any sample preparation) qualitative screening analyses for TCPs with adequate sensitivity within 30 s, the use of TD–ESI for semi-quantification is applicable only for homogeneous matrices (e.g., tang yuan).

Characterization and application of a self-aspirating electrospray source with pneumatic-assisted ionization.

A single gas-assisted electrospray ion source developed for ambient mass spectrometry is introduced in this paper. Simultaneous self-aspiration and electrospray could be achieved by using a constant sheath gas flow supplied from a mini air pump. A gas dynamic study of the spray module is carried out for structural optimization. The entire device exhibits a simplified design and has been systematically characterized through both simulated and experimental investigations. According to the results, the ion source exhibited satisfactory stability and the ability for quantitative operation in routine electrospray ionization mass spectrometry. Furthermore, the ion source can be operated as a desorption electrospray ionization source to perform direct desorption/ionization of the solid samples. The versatile source described here appears to provide a practical approach to perform ambient mass spectrometry analysis with unrestricted sampling operation, and the extensive gas dynamic studies together with the experimental characterization are believed to be helpful in building self-aspirating spray devices. Copyright © 2017 John Wiley & Sons, Ltd.

A pneumatically assisted nanospray desorption electrospray ionization source for increased solvent versatility and enhanced metabolite detection from tissue.

Nanospray desorption electrospray ionization (nano-DESI) has been established as a powerful technique for mass spectrometry imaging (MSI) of biomolecules from tissue samples. The direct liquid extraction of analytes from a surface at ambient pressure negates the need for significant sample preparation or matrix application. Although many recent studies have applied nano-DESI to new and exciting applications, there has not been much work in the development and improvement of the nano-DESI source. Here, we incorporate a nebulizer to replace the self-aspirating secondary capillary in the conventional nano-DESI setup, and characterize the device by use of rat kidney tissue sections. We find that the pneumatically assisted nano-DESI device offers improved sensitivity for metabolite species by 1-3 orders of magnitude through more complete desolvation and reduced ionization suppression. Further, the pneumatically assisted nano-DESI device reduces the dependence on probe-to-surface distance and enables sampling and imaging using pure water as the nano-DESI solvent. This provides exclusive detection and imaging of many highly polar endogenous species. Overall, the developed pneumatically assisted nano-DESI device provides more versatile solvent selection and an increased sensitivity for metabolites, which generates ion images of higher contrast - allowing for more intricate studies of metabolite distribution.

3D-printed polylactic acid supports for enhanced ionization efficiency in desorption electrospray mass spectrometry analysis of liquid and gel samples

The potential of 3D printing technology was here exploited to prepare tailored polylactic acid (PLA) supports for desorption electrospray ionization (DESI) experiments. PLA rough solid supports presenting wells of different shape (i.e. cylindrical, cubic and hemispherical cavities) were designed to accommodate samples of different physical state.The potentials of such supports in terms of sample loading capacity, sensitivity, signal stability were tested by analysing a peptide (i.e. insulin) and an aminoglycoside antibiotic (i.e. gentamicin sulphate) from solution and a chitosan-based gel. The results obtained were compared with those obtained by using a traditional polytetrafluoroethylene (PTFE) support and discussed.By using PLA support on the flat side, signal intensity improved almost twice with respect to PTFE support, whereas with spherical wells a five times improved signal sensitivity and good stability (RSD<6%) were obtained for the analysis of two model molecules. Limits of detection were in the 3–10nM range and linearity was demonstrated for both analytes in the 0.05–0.5μM range for semi-quantitative or quantitative purposes.The use of a well and the set-up of optimal source parameters allowed the analysis of samples in a gel state with good precision (RSD<10%) and accuracy (86±6–102±9%), otherwise difficult to analyse on a flat smooth surface.These findings are of great interest and stimulus to exploit the advantages of 3D printing technology for the development of devices for a DESI source, presenting different shapes or configuration as a function of the sample types.

Rapid point-of-care identification of oral medications in gastric lavage content by ambient mass spectrometry in the emergency room.

Acute poisoning should be handled with high efficiency in order to minimize morbidity and mortality in the emergency room. Unfortunately, history-taking and physical examination are not always reliable. Mis-swallowing of oral medications is common in the pediatric group. This study aimed at developing a rapid point-of-care ambient mass spectrometric method for the early identification of ingested oral medications in gastric lavage content. Four different types of oral medications that are most commonly mis-swallowed by children were diluted to different concentrations. Each of these chemical solutions was mixed with human gastric lavage content. A direct metallic sampling probe was dipped into the solution. It was then inserted promptly into the thermal desorption electrospray ionization source to carry out ionization and subsequent mass spectrometric analysis of the medications. The corresponding compounds were identified through matching of the obtained mass spectrometric data with those provided by well-established databases. Since no pretreatment of the specimen was required, the sampling step, and the subsequent thermal desorption electrospray ionization and mass spectrometric detection of the medications were completed within 30s. Mass spectra were obtained for four different kinds of oral medication. The limit-of-detection of the four tested oral medications in gastric lavage content is at sub-ppm level, which is sensitive enough for emergency medicine applications since the quantities of medications ingested by pediatric patients are usually much higher. Thermal desorption electrospray ionization mass spectrometry, with informational support provided by an online mass spectral database, allows for early point-of-care identification of mis-swallowed oral medications in the evacuated gastric lavage contents obtained from gastric lavage of patients in the emergency room, and it is promising in providing important toxicological information to ensure the appropriateness of the subsequent medical management. Copyright © 2016 John Wiley & Sons, Ltd.

Direct detection of chlorpropham on potato skin using desorption electrospray ionization

Most pesticides, herbicides and other plant treatment agents are applied to the crop surface. Direct mass spectrometric methods, such as desorption electrospray ionization (DESI), offer new ways to analyze plant samples directly and rapidly. A strategy for the development and optimization of a DESI method for the direct determination of chemicals on complex surfaces is described. Chlorpropham (CP) was applied to potato surfaces as an example for a crop protection agent and analyzed using a self-made DESI source. Aspects such as instrument selectivity, sensitivity and reproducibility were investigated. The MS(4) fragmentation pattern of CP was analyzed to achieve the necessary detection selectivity, and is discussed in detail. Similar fragmentation was found in the ESI and DESI mass spectra, indicating that the mechanisms of ESI and DESI are closely related. A DESI method for semi-quantification of CP on potatoes was developed. Detection limits of 6.5 µg/kg were found using MS/MS. The reproducibility, in the range of 12% (signal variation), appears to be sufficient for semi-quantitative measurements.

Critical parameters for the analysis of anionic oligosaccharides by desorption electrospray ionization mass spectrometry

Sulfated oligosaccharides derived from glycosaminoglycans (GAGs) are fragile compounds, highly polar and anionic. We report here on the rare but successful application of desorption electrospray ionization (DESI) - LTQ-Orbitrap mass spectrometry (MS) to the high-resolution analysis of anionic and sulfated oligosaccharides derived from the GAGs hyaluronic acid and heparin. For that purpose, key parameters affecting DESI performance, comprising the geometric parameters of the DESI source, the probed surface and the spraying conditions, applied spray voltage, flow rates and solvent composition were investigated. Under suitable conditions, the DESI technique allows the preservation of the structural integrity of such fragile compounds. DESI enabled the sensitive detection of anionic hyaluronic acid and heparin oligosaccharides with a limit of detection (LOD) down to 5 fmol (≈10 pg) for the hyaluronic acid decasaccharide. Detection of hyaluronic acid oligosaccharides in urine sample was also successfully achieved with LOD values inferior to the ng range. Multistage tandem mass spectrometry (MS(n) ) through the combination of the DESI source with a hybrid linear ion trap-orbitrap mass spectrometer allowed the discrimination of isomeric sulfated oligosaccharides and the sequence determination of a hyaluronic acid decasaccharide. These results open promising ways in glycomic and glycobiology fields where structure-activity relationships of bioactive carbohydrates are currently questioned.

Imaging of Human Lens Lipids by Desorption Electrospray Ionization Mass Spectrometry

The lipid composition of the human lens is distinct from most other tissues in that it is high in dihydrosphingomyelin and the most abundant glycerophospholipids in the lens are unusual 1-O-alkyl-ether linked phosphatidylethanolamines and phosphatidylserines. In this study, desorption electrospray ionization (DESI) mass spectrometry-imaging was used to determine the distribution of these lipids in the human lens along with other lipids including, ceramides, ceramide-1-phosphates, and lyso 1-O-alkyl ethers. To achieve this, 25 μm lens slices were mounted onto glass slides and analyzed using a linear ion-trap mass spectrometer equipped with a custom-built, 2-D automated DESI source. In contrast to other tissues that have been previously analyzed by DESI, the presence of a strong acid in the spray solvent was required to desorb lipids directly from lens tissue. Distinctive distributions were observed for [M + H](+) ions arising from each lipid class. Of particular interest were ionized 1-O-alkyl phosphatidylethanolamines and phosphatidylserines, PE (18:1e/18:1), and PS (18:1e/18:1), which were found in a thin ring in the outermost region of the lens. This distribution was confirmed by quantitative analysis of lenses that were sectioned into four distinct regions (outer, barrier, inner, and core), extracted and analyzed by electrospray ionization tandem mass spectrometry. DESI-imaging also revealed a complementary distribution for the structurally-related lyso 1-O-alkyl phosphatidylethanolamine, LPE (18:1e), which was localized closer to the centre of the lens. The data obtained in this study indicate that DESI-imaging is a powerful tool for determining the spatial distribution of human lens lipids.

Desorption electrospray ionization tissue imaging using heated nebulizing gas and high-resolution accurate mass spectra

A new method for tissue imaging using desorption electrospray ionization (DESI) mass spectrometry is described. The technique utilizes a DESI source with a heated nebulizing gas and high-resolution accurate mass data acquired with an LTQ-Orbitrap mass spectrometer. The two-dimensional (2D) automated DESI ion source creates images using the ions that are collected under high-resolution conditions. The use of high-resolution mass detection significantly improves the image quality due to exclusion of interfering ions. The use of a heated nebulizing gas increases the signal intensity observed at lower gas pressure. The technique developed is highly compatible with soft tissue imaging due to the minimal surface destruction.

Trace detection of non-uniformly distributed analytes on surfaces using mass transfer and large-area desorption electrospray ionization (DESI) mass spectrometry

Ambient ionization methods such as desorption electrospray ionization (DESI) allow the analysis of chemicals adsorbed at surfaces without the need for sample (or surface) pretreatment. A limitation of current implementations of these ionization sources is the small size of the area that can be sampled. This makes examination of surfaces of large areas time-consuming because of the need to raster across the surface. This paper describes a DESI source that produces a spray plume with an effective desorption/ionization area of 3.6 cm(2), some 200 times larger than given by conventional DESI sources. Rhodamine 6G and several drugs of abuse (codeine, heroin and diazepam) were used to demonstrate the ability to use large-area DESI MS to perform rapid (a few seconds) representative sampling of areas of the order of several square centimetres without scanning the probe across the surface. The large area ion source displayed high sensitivity (limits of detection in the high nanogram range) and high reproducibility (approximately 20 to 35% relative standard deviation). The rapid analysis of even larger surfaces (hundreds of cm(2)) for traces of explosives is possible using a sorbent surface wipe followed by large-area DESI interrogation performed directly on the wipe material. The performance of this mass transfer dry wipe method was examined by determination of the limits of detection of several explosives. Surfaces with different topographies and compositions were also tested. Using this method, absolute limits of detection observed for HMX and RDX from plastic surfaces and skin were found to be as low as 10 ng cm(-2). The concentration of residue from large surface areas in this technique allowed the detection of 100 ng of explosives from surfaces with areas ranging from 1.00 x 10(3) cm(2) to 1.40 x 10(4) cm(2).

Ambient Aerodynamic Ionization Source for Remote Analyte Sampling and Mass Spectrometric Analysis

The use of aerodynamic devices in ambient ionization source development has become increasingly prevalent in the field of mass spectrometry. In this study, an air ejector has been constructed from inexpensive, commercially available components to incorporate an electrospray ionization emitter within the exhaust jet of the device. This novel aerodynamic device, herein termed remote analyte sampling, transport, and ionization relay (RASTIR) was used to remotely sample neutral species in the ambient and entrain them into an electrospray plume where they were subsequently ionized and detected using a linear ion trap Fourier transform mass spectrometer. Two sets of experiments were performed in the ambient environment to demonstrate the device's utility. The first involved the remote (approximately 1 ft) vacuum collection of pure sample particulates (i.e., dry powder) from a glass slide, entrainment and ionization at the ESI emitter, and mass spectrometric detection. The second experiment involved the capture (vacuum collection) of matrix-assisted laser desorbed proteins followed by entrainment in the ESI emitter plume, multiple charging, and mass spectrometric detection. This approach is in principle a RASTIR-assisted matrix-assisted laser desorption electrospray ionization source (Sampson, J. S.; Hawkridge, A. M.; Muddiman, D. C. J. Am. Soc. Mass Spectrom. 2006, 17, 1712-1716; Rapid Commun. Mass Spectrom. 2007, 21, 1150-1154.). A detailed description of the device construction, operational parameters, and preliminary small molecule and protein data are presented.