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Characterization of chemical composition in cigarette smoke is essential for establishing smoke-related exposure estimates. Currently used methods require complex sample preparation with limited capability for obtaining accurate chemical information. We have developed an in situ solid-phase microextraction (SPME) method for online processing of smoke aerosols and directly coupling the SPME probes with confined-space direct analysis in real time (cDART) ion source for high-resolution mass spectrometry (MS) analysis. In a confined space, the substances from SPME probes can be efficiently desorbed and ionized using the DART ion source, and the diffusion and evaporation of volatile species into the open air can be largely avoided. Using SPME-cDART-MS, mainstream smoke (MSS) and side-stream smoke (SSS) can be investigated and the whole analytical protocol can be accomplished in a few min. More than five hundred substances and several classes of compounds were detected and identified. The relative contents of 13 tobacco alkaloids were compared between MSS and SSS. Multivariate data analysis unveiled differences between different types of cigarette smoke and also discovered the characteristic ions. The method is reliable with good reproducibility and repeatability, and has the potential to be quantitative. This study provides a simple and high-efficiency method for smokeomics profiling of complex aerosol samples with in situ online extraction of volatile samples, and direct integration of extracted probes with a modified ambient ionization technique.

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Fentanyl analogs are a class of designer drugs that are particularly challenging to unambiguously identify due to the mass spectral and retention time similarities of unique compounds. In this paper, we use agglomerative hierarchical clustering to explore the measurement diversity of fentanyl analogs and better understand the challenge of unambiguous identifications using analytical techniques traditionally available to drug chemists. We consider four measurements in particular: gas chromatography retention indices, electron ionization mass spectra, electrospray ionization tandem mass spectra, and direct analysis in real time mass spectra. Our analysis demonstrates how simultaneously considering data from multiple measurement techniques increases the observable measurement diversity of fentanyl analogs, which can reduce identification ambiguity. This paper further supports the use of multiple analytical techniques to identify fentanyl analogs (among other substances), as is recommended by the Scientific Working Group for the Analysis of Seized Drugs (SWGDRUG).

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The current work is the first study on online coupling of matrix solid-phase dispersion (MSPD) to direct analysis in real time mass spectrometry (DART-MS) bridging with solid-phase analytical derivatization (SPAD) based on a graphene oxide nanosheets (GONs)-coated cotton swab. Proof-of-concept demonstrations were explored for high-throughput analysis of a diversity of regulated chemicals in consumer products such as textiles, toys, and cosmetics. On-demand sorbent combinations were blended with samples, packed into MSPD columns, and mounted on a homemade 3D-printed rack module for automated sample feeding. To achieve good synergy between MSPD and DART-MS, a cotton swab with a conical tip deposited with GONs was attached to the bottom of the MSPD column. The swabs serve as a solid-phase microextraction probe for convenient enrichment of the eluted analytes from MSPD, thermal desorption of the enriched analytes by DART, and sensitive detection by a hybrid quadrupole-Orbitrap mass spectrometer. Furthermore, the utility of an on-swab SPAD strategy was demonstrated for the detection of formaldehyde by use of the derivatizing reagent of dansyl hydrazine, contributing to improved ionization efficiency without compromising the overall coherence of the analytical workflow. The MSPD-DART-MS methodology was systematically optimized and validated, obtaining acceptable recovery (71.7-110.3%), repeatability (11.8-19.3%), and sensitivity (limits of detection and quantitation in the ranges of 6.2-19.5 and 23.7-75.9 µg/kg) for 32 target analytes. The developed protocol streamlined sample extraction, clean-up, desorption, ionization, and detection, highlighting the appealing potential for high-throughput analysis of samples with complex matrices.

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To systematically study the influence of host-guest interactions on the analytical performance of direct analysis in real time mass spectrometry (DART-MS), the interactions between cyclodextrins (CDs) and different Sudan dyes were investigated. The results showed that the host-guest interaction between CDs and Sudan dyes did not affect qualitative analysis of the target compounds, but led to a lower signal intensity for Sudan dyes, thus affecting quantitative analysis of the target compounds. The stronger the host-guest interaction, the weaker the signal intensity of target compound on DART-MS. The results also show that both in solution and in solid-phase microextraction (SPME), the addition of organic solvents can weaken the host-guest interaction between CDs and Sudan dyes, thus improving the signal intensity in DART-MS. In SPME, adding organic solvents has a certain practical value and can improve the efficiency of Sudan dye analysis. This study suggests that appropriate sample pretreatment is needed to weaken noncovalent interactions prior to DART-MS analysis to obtain more accurate quantitative results. The data provide some insight into the effects of other noncovalent interactions on the efficiency of DART-MS as an analytical tool, as well as the potential to study intermolecular interactions with DART-MS.

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Green analytical chemistry (GAC) represents a rapidly growing research field that aims at developing novel analytical approaches with minimal consumption of hazardous reagents and solvents. The current study reports on a GAC methodology exploiting the unique physicochemical properties of natural deep eutectic solvents (NADESs), a supposedly environmentally friendly class of solvents. Based on a temperature-mediated strategy, the NADESs were manipulated to undergo multiple phase transitions for favorable functionality and performance. As proof-of-concept demonstrations, both hydrophobic and hydrophilic NADESs were prepared for the extraction and analysis of eight phthalate esters in aqueous samples (food simulants) and three aflatoxins in oily samples (edible oils), respectively. NADES-based dispersive liquid-liquid microextraction (DLLME) was employed to achieve high-efficiency sample pretreatment. Afterward, the NADESs were transformed from liquids into solids by tuning the peripheral temperature for a convenient phase separation from the sample matrices. The solidified NADES extracts were melted and vaporized at elevated temperatures by transmission-mode direct analysis in real time (DART) for further quadrupole-Orbitrap high-resolution mass spectrometry (Q-Orbitrap HRMS) analysis. The developed protocol was validated, achieving good repeatability with relative standard deviations (RSDs) of less than 9% and satisfactory sensitivity with limits of detection (LODs) and quantitation (LOQs) ranging from 0.1 to 0.8 and 0.2 to 2.0 µg/kg, respectively. The greenness of the analytical methodology was assessed with the calculated scores of 0.66 and 0.57 for the hydrophobic and hydrophilic NADES-based protocols, respectively. The method was applied to marketed samples, highlighting the great potential for green chemical analysis.

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The characterization and quality control of natural herbal medicines, such as traditional Chinese medicines (TCMs), is of great significance to ensure their potential efficacy and avoid severe side effects. Thin-layer chromatography (TLC) is a simple and classic approach for examining quality marker of natural products. Nevertheless, it is more difficult to further characterize the compounds adsorbed on the TLC plate. Herein, we reported a simple setup of laser ablation-assisted direct analysis in real-time mass spectrometry (LA-DART-MS), in which the coupling of mass spectrometry information to provide a predominant dimension in the identification of unknown chemical compositions separated on standard TLC plates, and it was applied for rapid characterization of various kinds of natural herbal medicines. The results showed that the introduction of low-cost small laser pointer had significantly improved the desorption process. The system was successfully applied in the analysis of alkaloids, flavonoids, anthraquinones, volatile oils, glycosides, organic acids, and eight different TCMs including Sophorae Flavescentis Radix, Angelicae Sinensis Radix, Acori Tatarinowii Rhizoma, Phellodendri Chinensis Cortex, Picrasmae Ramulus et Folium, Gynura Japonica, Rhei Radix et Rhizoma and Dendrobii Caulis. The obtained limits of detection (LODs) of this method for various types of reference substances were in the range of 4.6-162.2 ng/band on TLC plates. Furthermore, the quality control and identification of different species of Dendrobii Caulis herb was achieved. This study combines the advantages of TLC and ambient mass spectrometry to provide a good choice for the screening and identification of active ingredients and the quality evaluation of botanical samples.

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Mass spectrometry-based molecular imaging has been utilized to map the spatial distribution of target metabolites in various matrixes. Among the diverse mass spectrometry techniques, matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS) is the most popular for molecular imaging due to its powerful spatial resolution. This unparalleled high resolution, however, can paradoxically act as a bottleneck when the bio-imaging of large areas, such as a whole plant, is required. To address this issue and provide a more versatile tool for large scale bio-imaging, direct analysis in real-time-time of flight-mass spectrometry (DART-TOF-MS), an ambient ionization MS, was applied to whole plant bio-imaging of a medicinal plant, Ephedrae Herba. The whole aerial part of the plant was cut into 10-20 cm long pieces, and each part was further cut longitudinally to compare the contents of major ephedra alkaloids between the outer surface and inner part of the stem. Using optimized DART-TOF-MS conditions, molecular imaging of major ephedra alkaloids of the whole aerial part of a single plant was successfully achieved. The concentration of alkaloids analyzed in this study was found to be higher on the inner section than the outer surface of stems. Moreover, side branches, which are used in traditional medicine, represented a far higher concentration of alkaloids than the main stem. In terms of the spatial metabolic distribution, the contents of alkaloids gradually decreased towards the end of branch tips. In this study, a fast and simple macro-scale MS imaging of the whole plant was successfully developed using DART-TOF-MS. This application on the localization of secondary metabolites in whole plants can provide an area of new research using ambient ionization mass spectroscopy and an unprecedented macro-scale view of the biosynthesis and distribution of active components in medicinal plants.

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Pyrrolizidine alkaloids (PAs) are naturally occurring plant toxins associated with severe liver damage if excessive ingestion. Herein, a novel analytical strategy on utilizing direct analysis in real-time mass spectrometry (DART-MS) was developed, and applied in analysis of six representative PAs. The calibration curves in the range of 10-1000 ng·mL-1 were established, and relative standard deviations (RSDs) were less than 10%. The limits of detection (LODs) and limits of quantitation (LOQs) were 0.55-0.85 ng·mL-1 and 1.83-2.82 ng·mL-1, respectively. The feasibility of method was indicated by analysing real samples including Gynura japonica, drug tablets, granules, and fresh cow's milk. Moreover, the results of DART-MS were in good agreement with those observed by high performance liquid chromatography mass spectrometry (HPLC-MS), but consumed less time without chromatographic separation. This research provides a facile fashion for safety assessment of herbal and food products containing PAs and presents promising applications in food, pharmaceutical and clinical analysis.

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There is a requirement for reliable real-time analytical tools for reaction monitoring to optimise chemical syntheses. We have developed a new technique which combines thermal analysis, digital microscopy and chemical identification using ambient ionisation mass spectrometry. We term this hot-stage microscopy-Direct Analysis in Real-Time mass spectrometry (HDM). The technique provides optical data as a function of temperature coupled with chemical characterisation of evolved species, including reactants, intermediates and products throughout the course of a reaction. In addition, only a few milligrams of sample are required with analyte detection down to the nanogram range. We demonstrate the benefits of HDM using a series of solvent-free reactions. Our results confirm the suitability of the technique as the reactions studied follow the same pathways as published previously. The accurate temperature control achieved with HDM could also be used to assess the optimum temperature at which thermally-driven reactions can proceed efficiently.

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Progesterone is the representative progestogens in five major classes of steroid hormones and plays important roles in mammalian pregnancy and animal growth and development. Conventional available analytical methods for progesterone involve immunoassay, gas chromatography-mass spectrometry (GC-MS), and high-performance liquid chromatography-mass spectrometry (HPLC-MS), which lack specificity or usually require sophisticated operations and relatively long time. Herein, we developed a novel strategy for rapid analysis of progesterone via direct analysis in real time mass spectrometry (DART-MS) combined with solid-phase extraction (SPE) using an amino functionalized metal-organic frameworks (MOFs). Under optimized conditions, a wide linear range of 0.5-500 ng mL-1 was achieved, with a satisfactory correlation coefficient (R2 = 0.9992). The relative standard deviations (RSDs) were in the range from 2.4 to 8.4%, demonstrating good precision. The applicability was then confirmed by analyzing spiked lake water and synthetic urine samples, and recoveries are between 92.0 and 117.8% in all three spiked levels (5, 25, and 100 ng mL-1). The sensitivity was notably improved compared with solely DART-MS and obtained detection limit decreased by about 50 times. This research provided a rapid, simple, highly sensitive, and efficient approach for analysis of hormones through combination of advantages of ambient mass spectrometry and porous nanomaterials. Graphical abstract.

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A sorbent and solvent co-enhanced direct analysis in real-time mass spectrometry (SSE-DART-MS) method was developed for high-throughput determination of trace pollutants in water. The use of sorbent for preconcentration and solvents for assisting desorption and ionization synergistically enhanced the signals from the trace pollutants detected by DART-MS. Phthalic acid esters (PAEs) were used as model analytes to validate the SSE-DART-MS method. Graphitic carbon nitride (g-C3N4)-based materials with two morphologies and six organic solvents were used to systematically evaluate the enhancement effect by the sorbent and solvent. A better analytical performance was achieved with the two-dimensional (2D) g-C3N4, compared to three-dimensional (3D) g-C3N4/C, indicating that the morphologies of sorbents played a key role in SSE-DART-MS analysis. The MS signals of all the analytes were increased by 10-100 times for the two materials in the presence of the selected solvents. With the SSE-DART-MS method, concentration limits of detection for water samples in the range 0.07-0.94 ng L-1, and recovery in the range 82.8-119% using g-C3N4, were obtained for the PAEs. This work not only provides a reliable method for the coupling of solid phase extraction technique with DART-MS, but also presents valuable information for conducting other DART-MS analyses.

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Herein, a dark-current discharge state created by combining argon flow with a needle electrode in ambient air is described that has an ionization efficiency and mechanism comparable to those of conventional helium direct analysis in real time (DART), without requiring dopants and DART glow discharge. Using this method, polar compounds such as α-amino acids were ionized in the dark-current argon discharge via (de)protonation, molecular anion formation, fragmentation, (de)protonation with the attachment of oxygen, deprotonation with hydrogen loss and negative ion attachment. In contrast, nonpolar compounds (e.g., n-alkanes) were detected as positive ions via hydride abstraction and oxidation. Major background ions observed were H3O+(H2O) n , O2 ·+, O2 ·-(H2O) n and CO3 ·-. These results indicate that the present dark-current discharge efficiently generates resonance-state argon with an internal energy of ∼14.2 eV, higher than that of the well-known metastable state (∼11.6 eV). It is therefore suggested that ionization reactions occurring there can be attributed to the Penning ionization of atmospheric H2O and O2 by resonance-state argon, analogous to helium DART.

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Cannabis has been cultivated as a source of food, fiber, and medicine globally, so the classification of Cannabis cultivars based on their chemical fingerprints is important to standardize and control the quality of Cannabis, ensure that patients receive a full and consistent spectrum of therapeutic benefits, and promote the further implementation of Cannabis-based products in clinical uses. In this study, a high-throughput analytical method, thermal desorption direct analysis in real time mass spectrometry (TD-DART-MS), was employed to classify various Cannabis hemp cultivars with multivariate analysis. Cannabis plant materials from four cultivars were analyzed directly by TD-DART-MS without solvent extraction. The total run time was 15 min including 8 min for data acquisition and 7 min for cooling down the thermal stage. Data preprocessing strategy such as data transformation was evaluated on the TD-DART-MS data set and cubic root transform has shown significant improvement to the classification. TD-DART-MS data was then processed by principal component analysis (PCA) and the results were compared with those from liquid chromatography-mass spectrometry (LC-MS) data. The samples were clustered based on cultivars by PCA, and the validation samples collected 2 months later were also grouped together with the original samples by cultivars after mean-centering the data sets. Partial least squares discriminant analysis (PLS-DA) models were constructed with the TD-DART-MS data sets and a 99.3 ± 0.3% classification accuracy was obtained from 100 independent bootstrapped Latin partition evaluations. Our results indicate that TD-DART-MS may be used as a screening tool for the classification of Cannabis cultivars. Graphical abstract.

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Direct analysis in real time mass spectrometry (DART-MS) was used to analyze an array of explosives including nitro-based explosives, peroxide explosives, and energetic heterocyclic compounds with different DART discharge gases (helium, argon, and nitrogen). Profound analyte oxidation was observed for particular compounds (TNT (9) and 2, 4-DNT (10)), whose mass spectra were completely dominated by the oxidation products when nitrogen was substituted for helium in DART analysis. This interesting phenomenon suggested that a highly oxidative environment provided by N2 DART ion source. A possible mechanism involved in nitrogen DART was proposed which may help further understanding the different chemistry involved in the ionization process. This work also presents a thermal desorption DART (TD-DART) configuration that can enable rapid, specific analysis of explosives from swipes. The screening of swipes with three different compositions (fiberglass, Hybond N+ membrane, and filter paper) showed that fiberglass swipe has the best performance which was then used for the subsequent TD-DART analysis. A direct comparison of TD-DART with traditional DART demonstrated that TD-DART indeed gives better response than traditional DART (provided that the distance between the DART source and mass spectrometer is the same) and will have wider applications than traditional DART.

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Plants that produce atropine and scopolamine fall under several genera within the nightshade family. Both atropine and scopolamine are used clinically, but they are also important in a forensics context because they are abused recreationally for their psychoactive properties. The accurate species attribution of these plants, which are related taxonomically, and which all contain the same characteristic biomarkers, is a challenging problem in both forensics and horticulture, as the plants are not only mind-altering, but are also important in landscaping as ornamentals. Ambient ionization mass spectrometry in combination with a hierarchical classification workflow is shown to enable species identification of these plants. The hierarchical classification simplifies the classification problem to primarily consider the subset of models that account for the hierarchy taxonomy, instead of having it be based on discrimination between species using a single flat classification model. Accordingly, the seeds of 24 nightshade plant species spanning 5 genera (i.e. Atropa, Brugmansia, Datura, Hyocyamus and Mandragora), were analyzed by direct analysis in real time-high resolution mass spectrometry (DART-HRMS) with minimal sample preparation required. During the training phase using a top-down hierarchical classification algorithm, the best set of discriminating features were selected and evaluated with a partial least square-discriminant analysis (PLS-DA) classifier to discriminate and visualize the data. The method yields species identity through a class hierarchy, and reveals the most significant markers for differentiation. The overall accuracy of the approach for species identification was 95% and 96% using 100X bootstrapping validation and test samples respectively. The method can be extended for the rapid identification of an infinite number of plant species.

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In this work, novel ionic liquid (IL) functionalized polyacrylonitrile nanofibers mat (IL/PAN-NFsM) was firstly prepared through thiol-ene "click" reaction and evaluated for the establishment of a sensitive and high-throughput screening method. Because of its excellent pre-separation efficiency, IL/PAN-NFsM can adsorb trace-level targets from complex sample matrix within tens of seconds by performing a solid-phase extraction (SPE) process, and then served as sampling modules of direct analysis real time mass spectrometry (DART-MS) without any additional processing. This means the target analytes concentrated on IL/PAN-NFsM were directly desorbed, ionized, and detected by DART-MS. To verify the feasibility of the proposed method, three illegal added synthetic drugs (gliclazide, glimepiride, and gliquidone) were screened in six types of antidiabetic health-care tea samples. The results indicated that the sensitivity is in the level of ng g-1, while total analysis time does not exceed 1.0 min per sample. Moreover, the stability expressed as relative standard deviation (RSD) varies from 1.7% to 17.3%. We proposed a new screening mode based on the direct combination of functionalized NFsM and DART-MS, which is expected to become a universal method in food safety analysis.

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A high throughput, and eco-friendly method based on solid-phase microextraction (SPME) combined with direct analysis in real time mass spectrometry (DART-MS) was established for the determination of trace pollutants in water. A laboratory-made SPME device coated with a metal organic framework (MIL-100 (M)) was fabricated for the on-site enrichment of triazine herbicides in environmental water, and the device was directly subjected to DART ionization (<20 s) for high resolution MS. The interactions between the target analytes and sorbents were investigated to improve the SPME device targeting specific pollutants, as well as to improve the desorption and ionization processes with DART-MS. Other factors were also systematically studied to obtain the optimal conditions, including pH, salinity, extraction temperature, pressure at the Vapur® interface, linear rail moving speed, gas temperature, extraction time, and sample volume. The limit of detection of target compounds were 5.0-50.0 ng L-1 and the recoveries ranged from of 92.4%-125.7%.

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A simple, rapid and high throughput analytical approach with combination of mechanochemical extraction (MCE) and direct analysis in real time mass spectrometry (DART-MS) analysis was developed for the simultaneous determination of multiple chemical components in cigarette fillers. Different kinds of substances including nicotine, cigarette alkaloids, carbohydrates, organic acids, humectants and other additives were successfully extracted using MCE and detected by high resolution DART-MS. Six solvents of various polarities were compared during MCE process and significant differences were observed. Different brands of cigarettes as well as standard research cigarette exhibited distinctive chemical features and DART-MS fingerprints. Principle component analysis showed clear differentiation among different cigarettes extracted with the same solvent and different solvent extracts of the same type of cigarette. The putative chemical formulas were proposed based on accurate m/z values with <10 ppm mass errors. The relative contents of nicotine and other identified substances were compared and significant differences were observed among cigarettes of different locations. The whole procedure of MCE combined with DART-MS only takes minutes from raw cigarette fillers to obtaining the semi-quantitative results. The operation is simple and high throughput, providing an efficient method to analyze cigarette composition, and to establish a methodology to acquire the rapid cigarette fingerprints for quality control.

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BACKGROUND: Areca nut (AN) chewing is carcinogenic and biomarkers reflecting it are urgently needed to determine the effectiveness of emergent cessation programs. Buccal cells (BCs) may serve as an ideal matrix to measure such biomarkers; however, their utility for this purpose is unknown. Direct analysis in real time-mass spectrometry (DART-MS) is a sensitive technique that analyzes materials in the open air and requires minimal/no sample preparation. We utilized DART-MS to analyze BCs to test the usefulness of this method in measuring areca alkaloids as biomarkers for AN chewing. METHODS: We applied DART-MS in positive-ion mode to quantitate over time human BCs: (a) exposed ex vivo to betel quid extracts (BQE) consisting of young AN, Piper betle L. leaf, slaked lime, and tobacco; and (b) obtained from seven chewers before and after BQ chewing. Quantification was performed by normalizing DART-MS alkaloid signal intensities to cholesterol intensities. RESULTS: Signals for areca alkaloids arecoline and arecaidine-guvacoline were detected in BCs exposed ex vivo to BQE up to 7 days (the last day tested) after exposure and in BCs from chewers up to 3 days (the last day tested) post chewing. DISCUSSION: The presence of alkaloid signals in BQ-exposed BCs verified BCs as a valid matrix and DART-MS as a suitable technique to measure biomarkers for AN chewing and provided reliable information on AN chewing timing. CONCLUSION: DART-MS analyses of BCs can be used to accurately determine areca alkaloids as AN chewing biomarkers up to 3 days post chewing and possibly longer.

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Conventional Gas Chromatography-Mass Spectrometry (GC-MS) methods for the analysis of ignitable liquids (ILs) are usually time-consuming, and the data produced are difficult to interpret. A fast IL screening method using direct analysis in real time mass spectrometry (DART-MS) is proposed in this study. GC-MS, QuickStrip DART-MS, and thermal desorption DART-MS methods were used to analyze neat ILs and thermal desorption DART-MS without extraction was used to analyze ILs on five substrates (e.g., carpet, wood, cloth, sand, and paper). Compared to GC-MS, DART-MS methods generated different spectral profiles for neat ILs with more peaks in the higher mass range and also provided better detection of less volatile compounds. ILs on substrates were successfully classified (98 ± 1%) using partial least squares discriminant analysis (PLS-DA) models based on thermal desorption DART-MS data. This study shows that DART-MS has great potential for the high-throughput screening of ILs on substrates.