Ambient Mass Spectrometry Techniques Research Articles

Molecular characterization of human peripheral nerves using desorption electrospray ionization mass spectrometry imaging.

Desorption electrospray ionization mass spectrometry imaging (DESI-MSI) is a molecular imaging method that can be used to elucidate the small-molecule composition of tissues and map their spatial information using two-dimensional ion images. This technique has been used to investigate the molecular profiles of variety of tissues, including within the central nervous system, specifically the brain and spinal cord. To our knowledge, this technique has yet to be applied to tissues of the peripheral nervous system (PNS). Data generated from such analyses are expected to advance the characterization of these structures. The study aimed to: (i) establish whether DESI-MSI can discriminate the molecular characteristics of peripheral nerves and distinguish them from surrounding tissues and (ii) assess whether different peripheral nerve subtypes are characterized by unique molecular profiles. Four different nerves for which are known to carry various nerve fiber types were harvested from a fresh cadaveric donor: mixed, motor and sensory (sciatic and femoral); cutaneous, sensory (sural); and autonomic (vagus). Tissue samples were harvested to include the nerve bundles in addition to surrounding connective tissue. Samples were flash-frozen, embedded in optimal cutting temperature compound in cross-section, and sectioned at 14 μm. Following DESI-MSI analysis, identical tissue sections were stained with hematoxylin and eosin. In this proof-of-concept study, a combination of multivariate and univariate statistical methods was used to evaluate molecular differences between the nerve and adjacent tissue and between nerve subtypes. The acquired mass spectral profiles of the peripheral nerve samples presented trends in ion abundances that seemed to be characteristic of nerve tissue and spatially corresponded to the associated histology of the tissue sections. Principal component analysis (PCA) supported the separation of the samples into distinct nerve and adjacent tissue classes. This classification was further supported by the K-means clustering analysis, which showed separation of the nerve and background ions. Differences in ion expression were confirmed using ANOVA which identified statistically significant differences in ion expression between the nerve subtypes. The PCA plot suggested some separation of the nerve subtypes into four classes which corresponded with the nerve types. This was supported by the K-means clustering. Some overlap in classes was noted in these two clustering analyses. This study provides emerging evidence that DESI-MSI is an effective tool for metabolomic profiling of peripheral nerves. Our results suggest that peripheral nerves have molecular profiles that are distinct from the surrounding connective tissues and that DESI-MSI may be able to discriminate between nerve subtypes. DESI-MSI of peripheral nerves may be a valuable technique that could be used to improve our understanding of peripheral nerve anatomy and physiology. The ability to utilize ambient mass spectrometry techniques in real time could also provide an unprecedented advantage for surgical decision making, including in nerve-sparing procedures in the future.

Historical Textile Dye Analysis Using DESI-MS

Desorption electrospray ionization mass spectrometry (DESI-MS) is an ambient mass spectrometry technique that shows great potential for the analysis of fragile heritage objects in situ. This article focuses on the application of a recently built DESI source to characterize natural dyestuffs in historical textiles and a presentation of initial imaging experiments. Optimization of the instrumental settings, geometrical parameters, and solvent system on the DESI-MS analysis was conducted on rhodamine B samples. Some variables, including an increased flow rate, a narrower range of optimized geometrical variables and a solvent system without additives, were applicable to both early synthetic and natural dyes. Direct dye turmeric (Curcuma longa L.) could be reliably analyzed on both silk and wool, as could anthraquinone standards without mordanting. These preliminary results suggest that the dye application process (direct, mordant, vat) has a large impact on the ionization efficiency of DESI-MS. Imaging trials highlighted the suitability of DESI-MS for the analysis of patterned textiles that are difficult to sample, such as calico fabrics, or other currently inaccessible objects.

POPs and PAHs in fish oil-based food supplements at the Czech market

ABSTRACT The objectives of this study were to assess concentrations of three groups of persistent organic pollutants (POPs) and polycyclic aromatic hydrocarbons (PAHs) in 44 fish oil-based food supplements, to estimate their daily intake by consumers and, to evaluate the compliance of the oil samples with the oil origin declarations (cod liver oil or fish oil). The concentrations of ∑PCBs (7 congeners), OCPs (19 compounds, represented mainly by ∑DDTs), ∑PBDEs (10 congeners), and ∑PAHs (16 compounds) found in samples ranged between 0.15–55.7 µg kg−1, 0.93–72.8 µg kg−1, 0.28–27.5 µg kg−1, and 0.32–51.9 µg kg−1, respectively. Besides, the authenticity of the oils was assessed based on the fingerprints obtained by DART–HRMS, an ambient mass spectrometry technique. Four samples declared as fish oil were probably prepared from cod liver oil, which is much cheaper. Furthermore, these samples contained elevated concentrations of halogenated POPs when compared to supplements produced from fish oil.

Atmospheric solids analysis probe-mass spectrometry (ASAP-MS) as a rapid fingerprinting technique to differentiate the harvest seasons of Tieguanyin oolong teas

Atmospheric solids analysis probe-mass spectrometry (ASAP-MS), an ambient mass spectrometry technique, was used to differentiate spring and autumn Tieguanyin teas. Two configurations were used to obtain their chemical fingerprints – ASAP attached to a high-resolution quadrupole time-of-flight mass spectrometer (i.e., ASAP-QTOF) and to a single-quadrupole mass spectrometer (i.e., Radian™ ASAP™ mass spectrometer). Then, orthogonal projections to latent structures-discriminant analysis was conducted to identify features that held promise in differentiating harvest seasons. Four machine learning models – decision tree, linear discriminant analysis, support vector machine, and k-nearest neighbour – were built using these features, and high classification accuracy of up to 100% was achieved. The markers were putatively identified using their accurate masses and MS/MS fragmentation patterns from ASAP-QTOF. This approach was successfully transferred to the Radian ASAP MS, which is more deployable in the field. Overall, this study demonstrated the potential of ASAP-MS as a rapid fingerprinting tool for differentiating spring and autumn Tieguanyin.

Rapid authentication of Chinese oolong teas using atmospheric solids analysis probe-mass spectrometry (ASAP-MS) combined with supervised pattern recognition models

Ambient mass spectrometry (AMS) is an emerging technique in food authenticity and traceability study due to the minimal sample preparation required and short analysis time. Herein, a non-targeted fingerprinting approach using an AMS technique, atmospheric solids analysis probe – mass spectrometry (ASAP-MS), was used to authenticate Chinese oolong teas. In the first part of the study, a total of 38 authentic samples from three main varieties – Guangdong Dancong, Taiwan Dongding, and Anxi Tieguanyin – were analysed and four discriminant analysis models were built using the fingerprint data from ASAP-MS. The principal component analysis-k nearest neighbour (PCA-kNN) model yielded the best classification outcome, where the classification accuracies of the training and validation sets were 100% and 92.6%, respectively. The second part of the study involved detecting possible adulteration of Anxi Tieguanyin, which is a high-value oolong tea under the register of protected geographical indication (PGI) of the European Union (EU). Adulteration of Anxi Tieguanyin was simulated by blending the authentic samples with 20–80% w/w of low-quality oolong teas. One-class modelling using data-driven soft independent modelling of class analogies (DD-SIMCA), with the Anxi Tieguanyin as the target class, was built using the fingerprint data of the authentic and adulterated samples. An excellent sensitivity of 100% and a high specificity of 98.1% were achieved, indicating that it is possible to detect substitution adulteration of Anxi Tieguanyin using ASAP-MS combined with one-class modelling. Overall, findings from this study exemplify the potential of ASAP-MS to be used for rapid, inexpensive, and high throughput classification of Chinese oolong tea varieties and screening for substitution adulteration of Anxi Tieguanyin oolong tea. • Feasibility of authenticating Chinese oolong teas using ASAP-MS was investigated. • Varieties of Chinese oolong teas accurately classified using ASAP-MS and PCA-kNN. • Adulterated Anxi Tieguanyin teas were detected by ASAP-MS and DD-SIMCA. • ASAP-MS could be used for rapid detection of adulteration in Chinese oolong teas.

Plasma-based ambient mass spectrometry: Recent progress and applications.

Ambient mass spectrometry (AMS) has grown as a group of advanced analytical techniques that allow for the direct sampling and ionization of the analytes in different statuses from their native environment without or with minimum sample pretreatments. As a significant category of AMS, plasma-based AMS has gained a lot of attention due to its features that allow rapid, real-time, high-throughput, in vivo, and in situ analysis in various fields, including bioanalysis, pharmaceuticals, forensics, food safety, and mass spectrometry imaging. Tens of new methods have been developed since the introduction of the first plasma-based AMS technique direct analysis in real-time. This review first provides a comprehensive overview of the established plasma-based AMS techniques from their ion source configurations, mechanisms, and developments. Then, the progress of the representative applications in various scientific fields in the past 4 years (January 2017 to January 2021) has been summarized. Finally, we discuss the current challenges and propose the future directions of plasma-based AMS from our perspective.

Rapid Evaporative Ionization Mass Spectrometry: A Review on Its Application to the Red Meat Industry with an Australian Context.

The red meat supply chain is a complex network transferring product from producers to consumers in a safe and secure way. There can be times when fragmentation can arise within the supply chain, which could be exploited. This risk needs reduction so that meat products enter the market with the desired attributes. Rapid Evaporative Ionisation Mass Spectrometry (REIMS) is a novel ambient mass spectrometry technique originally developed for rapid and accurate classification of biological tissue which is now being considered for use in a range of additional applications. It has subsequently shown promise for a range of food provenance, quality and safety applications with its ability to conduct ex vivo and in situ analysis. These are regarded as critical characteristics for technologies which can enable real-time decision making in meat processing plants and more broadly throughout the sector. This review presents an overview of the REIMS technology, and its application to the areas of provenance, quality and safety to the red meat industry, particularly in an Australian context.

Sample preparation and instrumental methods for illicit drugs in environmental and biological samples: A review

Detection of illicit drugs in the environmental samples has been challenged as the consumption increases globally. Current review examines the recent developments and applications of sample preparation techniques for illicit drugs in solid, liquid, and gas samples. For solid samples, traditional sample preparation methods such as liquid-phase extraction, solid-phase extraction, and the ones with external energy including microwave-assisted, ultrasonic-assisted, and pressurized liquid extraction were commonly used. The sample preparation methods mainly applied for liquid samples were microextraction techniques including solid-phase microextraction, microextraction by packed sorbent, dispersive solid-phase extraction, dispersive liquid-liquid microextraction, hollow fiber-based liquid-phase microextraction, and so on. Capillary microextraction of volatiles and airborne particulate sampling were primarily utilized to extract illicit drugs from gas samples. Besides, the paper introduced recently developed instrumental techniques applied to detect illicit drugs. Liquid chromatograph mass spectrometry and gas chromatograph mass spectrometry were the most widely used methods for illicit drugs samples. In addition, the development of ambient mass spectrometry techniques, such as desorption electrospray ionization mass spectrometry and paper spray mass spectrometry, created potential for rapid in-situ analysis.

Miniaturized sample preparation techniques and ambient mass spectrometry as approaches for food residue analysis

Analytical methods such as liquid chromatography (LC) and mass spectrometry (MS) are widely used techniques for the analyses of different classes of compounds. This is due to their highlighted capacity for separating and identifying components in complex matrices such food samples. However, in most cases, effective analysis of the target analyte becomes challenging due to the complexity of the sample, especially for quantification of trace concentrations. In this case, miniaturized sample preparation methods have been used as a strategy for analysis of complex matrices. This involves removing the interferents and concentrating the analytes in a sample. These methods combine simplicity and effectiveness and given their miniaturized scale, they are in accordance with green chemistry precepts. Besides, ambient mass spectrometry represents a new trend in fast and rapid analyses, especially for qualitative and screening analysis. However, for complex matrix analyses, sample preparation is still a difficult step and the miniaturized sample preparation techniques show great potential for an improved and widespread use of ambient mass spectrometry techniques. . This review aims to contribute as an overview of current miniaturized sample preparation techniques and ambient mass spectrometry methods as different approaches for selective and sensitive analysis of residues in food samples.

Analysis of food samples made easy by microextraction technologies directly coupled to mass spectrometry.

Because of the complexity and diversity of food matrices, their chemical analysis often entails several analytical challenges to attain accurate and reliable results, especially for multiresidue analysis and ultratrace quantification. Nonetheless, microextraction technology, such as solid-phase microextraction (SPME), has revolutionized the concept of sample preparation for complex matrices because of its nonexhaustive, yet quantitative extraction approach and its amenability to coupling to multiple analytical platforms. In recent years, microextraction devices directly interfaced with mass spectrometry (MS) have redefined the analytical workflow by providing faster screening and quantitative methods for complex matrices. This review will discuss the latest developments in the field of food analysis by means of microextraction approaches directly coupled to MS. One key feature that differentiates SPME-MS approaches from other ambient MS techniques is the use of matrix compatible extraction phases that prevent biofouling, which could drastically affect the ionization process and are still capable of selective extraction of the targeted analytes from the food matrix. Furthermore, the review examines the most significant applications of SPME-MS for various ionization techniques such as direct analysis in real time, dielectric barrier desorption ionization, and some unique SPME geometries, for example, transmission mode SPME and coated blade spray, that facilitate the interface to MS instrumentation.

Mass Spectrometry Techniques in Emerging Pathogens Studies: COVID-19 Perspectives.

As corona virus disease 2019 (COVID-19) is a rapidly growing public health crisis across the world, our knowledge of meaningful diagnostic tests and treatment for severe acute respiratory syndrome coronavirus 2 (SARS-COV-2) is still evolving. This novel coronavirus disease COVID-19 can be diagnosed using RT-PCR, but inadequate access to reagents, equipment, and a nonspecific target has slowed disease detection and management. Precision medicine, individualized patient care, requires suitable diagnostics approaches to tackle the challenging aspects of viral outbreaks where many tests are needed in a rapid and deployable approach. Mass spectrometry (MS)-based technologies such as proteomics, glycomics, lipidomics, and metabolomics have been applied in disease outbreaks for identification of infectious disease agents such as virus and bacteria and the molecular phenomena associated with pathogenesis. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF/MS) is widely used in clinical diagnostics in the United States and Europe for bacterial pathogen identification. Paper spray ionization mass spectrometry (PSI-MS), a rapid ambient MS technique, has recently open a new opportunity for future clinical investigation to diagnose pathogens. Ultra-high-pressure liquid chromatography coupled high-resolution mass spectrometry (UHPLC–HRMS)-based metabolomics and lipidomics have been employed in large-scale biomedical research to discriminate infectious pathogens and uncover biomarkers associated with pathogenesis. PCR-MS has emerged as a new technology with the capability to directly identify known pathogens from the clinical specimens and the potential to identify genetic evidence of undiscovered pathogens. Moreover, miniaturized MS offers possible applications with relatively fast, highly sensitive, and potentially portable ways to analyze for viral compounds. However, beneficial aspects of these rapidly growing MS technologies in pandemics like COVID-19 outbreaks has been limited. Hence, this perspective gives a brief of the existing knowledge, current challenges, and opportunities for MS-based techniques as a promising avenue in studying emerging pathogen outbreaks such as COVID-19.

Multiresidue pesticide quantitation in multiple fruit matrices via automated coated blade spray and liquid chromatography coupled to triple quadrupole mass spectrometry

Application of ambient mass spectrometry techniques to accelerate analysis of pesticides in produce, with technique validation via chromatographic separation, has not been explored extensively. In this work, coated blade spray (CBS) was used to provide freedom of instrumental choice for a multiresidue panel of pesticides in apple, blueberry, grape, and strawberry through direct-coupling with mass spectrometry (MS) and liquid chromatographic (LC) analyses. For all four matrices, >125 compounds were found to meet European Union guidelines concerning linearity, precision, and accuracy while both CBS-MS/MS and SPME-LC-MS/MS methods achieved limits of quantitation below their minimum regulatory limits. Additionally, results for samples containing residues (n = 57) yielded good agreement between instrumental methods (percent differences < 20% for 73% residues), supporting CBS as a stand-alone technique or complement to LC confirmation of pesticides in fruit matrices.

Fiber spray ionization mass spectrometry in forensic chemistry: A screening of drugs of abuse and direct determination of cocaine in urine.

Ambient mass spectrometry techniques are much required in forensic chemistry to evaluate evidence with low analytical interference, high confidence, and accuracy. However, traditional methodologies, such as paper spray ionization, have been shown to present low sensitivity in the analysis of illicit drugs from biological matrices. Fiber spray ionization mass spectrometry (FSI-MS) was developed using a capillary polypropylene (PP) hollow fiber. Seized samples of drugs, i.e. a tablet, blotter paper, hashish, and cocaine powder, were analyzed. Cocaine was quantified from whole urine by dipping the fiber directly into solution. FSI-MS was tested for the analysis of a sample of urine obtained from a drug abuse suspect. The FSI(+) analysis showed the detection of different types of synthetic drugs in tablet and blotter paper samples, e.g. amphetamine, cathinones, phenethylamines, and opioids, while pure cocaine and different types of coca alkaloids were identified from cocaine powder with good sensitivity and high mass accuracy. The hashish analysis by FSI(-) revealed signals of cannabinoids, cannabinoid acids, and cannabinoid derivatives, detected mainly as [M - H]- ions or chlorine adducts [M + Cl]- . The quantification of cocaine in whole urine showed good sensitivity and precision with limits of detection and quantification of 5.16 and 17.21 ng/mL, respectively, linearity above 0.999, and relative standard deviation below 2.71%. The evaluation of seized sample of urine showed the detection of cocaine with relative ion intensity greater than 36%, as well as the metabolites benzoylecgonine and cocaethylene with a relative intensity of 1.4% and 6%, respectively. The developed FSI-MS method has the potential to be applied to forensic sample evaluation as well as to determine illicit drugs from biological matrices in toxicological analysis. The use of a capillary PP fiber has advantages as an extractor agent and ionizing substrate, and also the feature of it being dipped directly into the sample, thus preserving the integrity of the sample, which makes this a very promising ambient mass spectrometry method and relevant to forensic chemistry.

Liquid Extraction Surface Analysis (LESA) High-Field Asymmetric Waveform Ion Mobility Spectrometry (FAIMS) Mass Spectrometry for In Situ Analysis of Intact Proteins.

Liquid extraction surface analysis (LESA) is an ambient mass spectrometry technique which enables direct analysis of analytes from solid substrates. LESA is particularly suitable for the analysis of intact proteins from biological substrates such as thin tissue sections and bacterial colonies growing on agar. Nevertheless, these substrates present a challenge for LESA protein analysis owing to their inherent complexity. It is therefore beneficial to hyphenate LESA with a gas phase separation technique. One such technique is high-field asymmetric waveform ion mobility (FAIMS), in which ions are separated according to their different mobilities in high and low electric fields. Here, we describe the protocols for LESA FAIMS mass spectrometry of intact proteins in thin tissue sections and bacterial colonies.

Chemical profiles of birch and alder bark by ambient mass spectrometry

Desorption atmospheric pressure photoionization (DAPPI) is an ambient mass spectrometry (MS) technique that allows the analysis of both polar and nonpolar compounds directly from the surfaces of various sample types. Here, DAPPI was used to study the chemical profiles in different parts of birch and alder tree barks. Four distinct fractions of Betula pendula (silver birch) bark were collected from three different developmental stages of the stem, after which the chemical profiles of the different tissue types were measured. Of special interest were triterpenoids, a class of important defensive substances, which are found in the bark of the silver birch. Additionally, the chemical profiles of lenticels and the surrounding surfaces in the phellem of B. pendula (silver birch), Alnus glutinosa (black alder), and Alnus incana (gray alder) were screened with DAPPI. Another ambient MS technique, laser ablation atmospheric pressure photoionization (LAAPPI), was further used for the mass spectrometry imaging of lenticels on the B. pendula phellem. All the studied birch bark fractions showed individual chemical profiles in DAPPI. The mass spectra from the young apical stem and the transition zone resembled each other more than the mature stem. Instead, the phellem was found to contain a high amount of triterpenoids in all the developmental stages of the stem. The most intense peaks in the DAPPI mass spectra of the birch bark fractions were those of betulin and lupeol. Betulinic and betulonic acid peaks were intense as well, and these compounds were detected especially in the lenticels of the tree samples.Graphical abstract

Optimisation of secondary ion transport in ambient pressure MeV SIMS

Ambient Pressure MeV SIMS (AP MeV SIMS) is a special application of MeV SIMS technique for molecular detection and imaging under ambient conditions. There are several advantages of using ambient over non-ambient techniques such as minimising or completely avoiding sample preparation that can contribute to the reducing of costs and shortening of analysis. Moreover, by performing analysis in ambient conditions negative vacuum influence on samples will be avoided. The emergence of ambient mass spectrometry techniques over the past decade has been enormous with a broad range of applications such as food quality, environmental analysis and life sciences [1,2]. On the other hand, the disadvantage of ambient pressure mass spectrometry techniques is the influence of the ambient background which can suppress the signal from the target. In AP MeV SIMS, molecular species present in ambient surrounding of the sampling site will also be ionised by ion beams hence secondary ions originating from the sample have to be transported in the most efficient manner from the site of interaction of ion beams and target into the mass spectrometer capillary and, finally, into the mass spectrometer [3]. In this work, we present the optimisation of the mass spectrometer capillary temperature, distances of mass spectrometer and sheath gas, in our case helium, with respect to the beam axis and angle of the helium flow capillary with respect to the sample.

Review and perspectives on the applications of mass spectrometry imaging under ambient conditions.

Ambient mass spectrometry (AMS)-based techniques are performed under ambient conditions in which the ionization and desorption occur in the open environment allowing the direct analysis of molecules with minimal or no sample preparation. A selected group of AMS techniques demonstrate imaging capabilities that can provide information about the localization of molecules on complex sample surfaces such as biological tissues. 2D, 3D, and multimodal imaging have unlocked an array of applications to systematically address complex problems in many areas of research such as drug monitoring, natural products, forensics, and cancer diagnostics. In the present review, we summarize recent advances in the field with respect to the implementation of new ambient ionization techniques and current applications in the last 5years. In more detail, we mainly focus on imaging applications in topics related to animal whole bodies and tissues, single cells, cancer diagnostics and biomarkers, microbial cultures and co-cultures, plant and natural product metabolomics, and forensic applications. Finally, we discuss new areas of research, future perspectives, and the overall direction that the field may take in the years to come.

Ambient mass spectrometry in foodomics studies

The current and future potential role of ambient mass spectrometry (AMS) in the fields of recently created discipline of foodomics is discussed. The main focus was set on the literature published between 2014 and 2018, although a few earlier papers of special interest have been included. Several examples for the successful application of AMS techniques including direct analysis in real time (DART), desorption electrospray ionization (DESI), easy ambient sonic spray ionization mass spectrometry (EASI-MS) and paper spray mass spectrometry (PS-MS) are presented.

Ambient mass spectrometry in the analysis of compounds of low polarity

Ambient mass spectrometry techniques that are capable of ionizing compounds of low polarity are discussed.

Analysis of nitrogen‐based explosives with desorption atmospheric pressure photoionization mass spectrometry

Fast methods that allow the in situ analysis of explosives from a variety of surfaces are needed in crime scene investigations and home-land security. Here, the feasibility of the ambient mass spectrometry technique desorption atmospheric pressure photoionization (DAPPI) in the analysis of the most common nitrogen-based explosives is studied. DAPPI and desorption electrospray ionization (DESI) were compared in the direct analysis of trinitrotoluene (TNT), trinitrophenol (picric acid), octogen (HMX), cyclonite (RDX), pentaerythritol tetranitrate (PETN), and nitroglycerin (NG). The effect of different additives in DAPPI dopant and in DESI spray solvent on the ionization efficiency was tested, as well as the suitability of DAPPI to detect explosives from a variety of surfaces. The analytes showed ions only in negative ion mode. With negative DAPPI, TNT and picric acid formed deprotonated molecules with all dopant systems, while RDX, HMX, PETN and NG were ionized by adduct formation. The formation of adducts was enhanced by addition of chloroform, formic acid, acetic acid or nitric acid to the DAPPI dopant. DAPPI was more sensitive than DESI for TNT, while DESI was more sensitive for HMX and picric acid. DAPPI could become an important method for the direct analysis of nitroaromatics from a variety of surfaces. For compounds that are thermally labile, or that have very low vapor pressure, however, DESI is better suited.