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Solid Phase Microextraction (SPME) is a commonly used, robust method for characterization of aroma profiles in food matrices. However, challenges such as saturation, swelling, and competition can occur when sampling such complex matrices, resulting in decreased accuracy in the quantitation of polar compounds. In this study, sequential thin film micro-extraction (TFME) was employed to study the aroma profile of sparkling wine, with a focus to evaluate the displacement of polar analytes at extraction times longer than their corresponding equilibrium time. This investigation also describes advancements in the production of TFME devices, specifically the overcoating of hydrophilic-lipophilic balance/polydimethylsiloxane (HLB/PDMS) thin films to increase their matrix compatibility. Sequential thin film micro-extraction and overcoated HLB/PDMS thin films were evaluated for characterization of sparkling wine samples. The results were encouraging, showing that these advancements can decrease competition phenomena and increase the calibration linearity range compared to traditional micro-extraction approaches more commonly used for the characterization of such samples. In addition, multiphase equilibria investigation involving micellar systems enabled by the microextraction technology provides better understanding between wine aroma and its composition.
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A simple, sustainable, and sensitive monitoring approach of micro/nanoplastics (MNPs) in aqueous samples is crucial since it helps in assessing the extent of contamination and understanding the potential risks associated with their presence without causing additional stress to the environment. In this study, a novel strategy for qualitative and quantitative determination of MNPs in water by direct solid-phase microextraction (SPME) coupled with gas chromatography-mass spectrometry (GC-MS) was proposed for the first time. Spherical poly(methyl methacrylate) (PMMA) and irregularly shaped polyvinyl dichloride (PVDC) were used to evaluate the feasibility and performance of the proposed method. The results demonstrated that both PMMA and PVDC MNPs were efficiently extracted by the homemade SPME coating of nitrogen-doped porous carbons (N-SPCs) and exhibited sufficient thermal decomposition in the GC-MS injection port. Excellent extraction performances of N-SPCs coating for MNPs are attributed to hydrophobic cross-linking, electrostatic forcing, hydrogen bonding, and pore trapping. Methyl methacrylate was identified as the marker for PMMA, while 1,3-dichlorobenzene and 1,3,5-trichlorobenzene were the indicators for PVDC. Under the optimal extraction and decomposition conditions, the proposed method exhibited ultrahigh sensitivity, with a limit of detection of 0.0041 µg/L for PMMA and 0.0054 µg/L for PVDC. Notably, a programmed temperature strategy for the GC-MS injector was developed to discriminate and eliminate the potential interferences of intrinsic indicator compounds. Owing to the integration of sampling, extraction, injection, and decomposition into one step by SPME, the proposed method demonstrates exceptional sensitivity, eliminating the necessity for complex sample pretreatment procedures and the use of organic solvents. Finally, the proposed method was successfully applied in the determination of PMMA and PVDC MNPs in real aqueous samples.
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Introduction: Normothermic ex vivo kidney perfusion (NEVKP) is designed to replicate physiological conditions to improve graft outcomes. A comparison of the impact of hypothermic and normothermic preservation techniques on graft quality was performed by lipidomic profiling using solid-phase microextraction (SPME) chemical biopsy as a minimally invasive sampling approach. Methods: Direct kidney sampling was conducted using SPME probes coated with a mixed-mode extraction phase in a porcine autotransplantation model of the renal donor after cardiac death, comparing three preservation methods: static cold storage (SCS), NEVKP, and hypothermic machine perfusion (HMP). The lipidomic analysis was done using ultra-high-performance liquid chromatography coupled with a Q-Exactive Focus Orbitrap mass spectrometer. Results: Chemometric analysis showed that the NEVLP group was separated from SCS and HMP groups. Further in-depth analyses indicated significantly (p < 0.05, VIP > 1) higher levels of acylcarnitines, phosphocholines, ether-linked and longer-chain phosphoethanolamines, triacylglycerols and most lysophosphocholines and lysophosphoethanolamines in the hypothermic preservation group. The results showed that the preservation temperature has a more significant impact on the lipidomic profile of the kidney than the preservation method's mechanical characteristics. Conclusion: Higher levels of lipids detected in the hypothermic preservation group may be related to ischemia-reperfusion injury, mitochondrial dysfunction, pro-inflammatory effect, and oxidative stress. Obtained results suggest the NEVKP method's beneficial effect on graft function and confirm that SPME chemical biopsy enables low-invasive and repeated sampling of the same tissue, allowing tracking alterations in the graft throughout the entire transplantation procedure.
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Simultaneous rapid screening of multiple drugs of abuse in environmental water facilitates effective monitoring and trend assessments. Herein, a novel porphyrin-based metal organic frameworks modified Ti3C2Tx nanosheets (Cu-TCPP/Ti3C2Tx) composite was prepared and utilized as solid-phase microextraction (SPME) coating for the simultaneous analysis of 21 drugs from water samples. The composite was embedded with matrix-compatible polyacrylonitrile binder to prepare a coated blade with thin and uniform coating layer. Ambient mass spectrometry (MS) technique was used to create a coated blade spray-MS (CBS-MS) method for the quantitative determination of drugs in water samples. High throughput and automated sample preparation were achieved with the use of a Concept 96-well plate system, enabling analysis of 21 drugs of abuse within 1 min per sample, while using only 8 µL of organic solvent for desorption and CBS-MS detection. The developed method showed favorable linearity (R2 ≥ 0.9983) in the range of 0.05 to 10 ng mL-1, low limits of detection (1.5-9.0 ng L-1), sufficient recovery (67.6-133.2%), as well as satisfactory precision (RSDs≤13.5%). This study not only delivers a novel and efficient SPME coating composite, but also demonstrates the excellent performance of a high-throughput, efficient, and green analytical method for determination of drugs in environmental water.
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Espectrometria de Massas , Estruturas Metalorgânicas , Microextração em Fase Sólida , Poluentes Químicos da Água , Poluentes Químicos da Água/análise , Microextração em Fase Sólida/métodos , Estruturas Metalorgânicas/química , Espectrometria de Massas/métodos , Titânio/química , Limite de Detecção , Drogas Ilícitas/análise , Monitoramento Ambiental/métodos , Preparações Farmacêuticas/análise , Preparações Farmacêuticas/químicaRESUMO
Experimental and theoretical assessments of a graphene oxide-based polymer as adsorbent for thin film microextraction (TFME) were conducted as part of this research. Graphene oxide (GO) was embedded in the organic polymer poly(styrene-co-divinylbenzene) (PS-DVB) to prepare a sorbent suitable for direct-immersion TFME. A TFME membrane coating prepared with the GO/PS-DVB sorbent and polydimethylsiloxane (PDMS) as binder was then applied for extraction of organic pollutants from aqueous and gaseous samples. The surface morphology of the TFME coating was examined by scanning electron microscopy (SEM). Various TFME parameters influencing extraction efficiency, such as extraction time and temperature, desorption temperature, and ionic strength, were investigated and optimized. In a comparison of TFME membranes, the GO/PS-DVB/PDMS TFME membrane was shown to yield higher extraction efficiencies for the targeted analytes than the pure PDMS and DVB/PDMS TFME membranes. The calibration graphs of the organic pollutants displayed linearity for most of the target analytes within the 10-2000 ng L-1 concentration range. The repeatability (RSD %, n = 5) and reproducibility (RSD %, n = 3) of the method were in the ranges of 2.2-5.9 %, and 3.2-8.5 %, respectively, at a concentration level of 500 ng L-1, whereas accuracy (%) ranged between 79.8 and 119 %. The developed method was successfully applied for determinations of organic pollutants in tap water, lake water, and wastewater samples. Furthermore, the impact of mass transfer kinetics on extractions by the GO/PS-DVB/PDMS TFME membrane from gaseous samples was theoretically discussed and experimentally verified. The results of this work demonstrate that the GO/PS-DVB/PDMS TFME method is a simple, efficient, and environmentally friendly method for pre-treatment of organic pollutants.
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Proteomics of human saliva samples was achieved for the first time via biocompatible solid-phase microextraction (bio-SPME) devices. Upon introduction of a porogen to a conventional C18 coating, porous C18/polyacrylonitrile (PAN) SPME blades were able to extract peptides up to 3.0 kDa and more peptides than commercial SPME blades. Following Trypsin digestion, salivary proteomic analysis was achieved via SPME-LC-MS/MS. Seven endogenous proteins were consistently identified in all saliva samples via bio-SPME. Taking advantage of this strategy, untargeted peptidomics was applied for the comparison of saliva samples between healthy and SARS-CoV-2 positive individuals. The results showed clear peptidomic differences between the viral and healthy saliva samples. This proof-of-concept study demonstrates the potential of bio-SPME-LC-MS/MS for peptidomics and proteomics in biomedical applications.
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Espectrometria de Massa com Cromatografia Líquida , Espectrometria de Massas em Tandem , Humanos , Cromatografia Líquida/métodos , Espectrometria de Massas em Tandem/métodos , Microextração em Fase Sólida/métodos , Saliva/química , Proteômica , Peptídeos/análiseRESUMO
Adjuvant chemotherapy improves the survival outlook for patients undergoing operations for lung metastases caused by colorectal cancer (CRC). However, a multidisciplinary approach that evaluates several factors related to patient and tumor characteristics is necessary for managing chemotherapy treatment in metastatic CRC patients with lung disease, as such factors dictate the timing and drug regimen, which may affect treatment response and prognosis. In this study, we explore the potential of spatial metabolomics for evaluating metabolic phenotypes and therapy outcomes during the local delivery of the anticancer drug, oxaliplatin, to the lung. 12 male Yorkshire pigs underwent a 3 h left lung in vivo lung perfusion (IVLP) with various doses of oxaliplatin (7.5, 10, 20, 40, and 80 mg/L), which were administered to the perfusion circuit reservoir as a bolus. Biocompatible solid-phase microextraction (SPME) microprobes were combined with global metabolite profiling to obtain spatiotemporal information about the activity of the drug, determine toxic doses that exceed therapeutic efficacy, and conduct a mechanistic exploration of associated lung injury. Mild and subclinical lung injury was observed at 40 mg/L of oxaliplatin, and significant compromise of the hemodynamic lung function was found at 80 mg/L. This result was associated with massive alterations in metabolic patterns of lung tissue and perfusate, resulting in a total of 139 discriminant compounds. Uncontrolled inflammatory response, abnormalities in energy metabolism, and mitochondrial dysfunction next to accelerated kynurenine and aldosterone production were recognized as distinct features of dysregulated metabolipidome. Spatial pharmacometabolomics may be a promising tool for identifying pathological responses to chemotherapy.
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Determinations of micro/nanoplastics (MNPs) in environmental samples are essential to assess the extent of their presence in the environment and their potential impact on ecosystems and human health. With the aim to provide a sensitive method with simplified pretreatment steps, cooling-assisted solid-phase microextraction (CA-SPME) coupled to gas chromatography-mass spectrometry (GC-MS) is proposed as a new approach to quantify mass concentrations of MNPs in water and soil samples. The herein proposed CA-SPME method offers the unique advantage of integrating the thermal decomposition of MNPs and enrichment of signature compounds into one step. Poly(methyl methacrylate) (PMMA) was used as a model substance to verify the method performance in this work. Theoretical insights demonstrated that pyrolysis is the rate-determining step during the extraction process and that PMMA is effectively decomposed at 350 °C with an estimated incubation time of 13 min. Eight compounds were identified in the pyrolysis products by CA-SPME-GC-MS with the use of a DVB/CAR/PDMS coating, wherein methyl methacrylate was considered as the best indicator and dimethyl 2-methylenesuccinate was selected as the confirmation compound. Under the optimized conditions, the proposed method exhibited wide linearity (0.5-2000 µg for water and 5-1000 µg for soil) and high sensitivity, with limits of detection of 0.014 and 0.28 µg for water and soil, respectively. Finally, the proposed method was successfully applied for determinations of PMMA MNPs in real water and soil samples with satisfactory recoveries attained. The method only required the employment of a filter membrane for water analysis, while soil samples were analyzed directly without any pretreatment. The solvent-free approach, straightforward operation, and high sensitivity of the proposed method show great potential for the analysis of MNPs in different environmental samples.
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The direct coupling of solid-phase microextraction (SPME) with mass spectrometry (MS) offers rapid analysis with high sensitivity and low matrix effects by benefiting from the integration of sampling, high enrichment, and clean-up functions of SPME. Eliminating chromatographic separation reduces the amount of gas/solvent needed for analysis, while direct desorption in SPME-MS consumes none or few microliters of organic solvents per sample, further enhancing the greenness of the SPME technology. Over the past two decades, the rapid evolution of SPME-MS has given rise to numerous novel technologies that employ diverse ionization techniques and interfaces, several of which have already been commercialized. Drawing from an extensive review published earlier this year and our research experience, we provide perspectives on three aspects of these technologies: interface design and automation, integration with state-of-art MS instrumentation, and anticipated future developments.
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The displacement effect can be an issue for the quantitation of analytes with low affinity towards the extraction phase in solid-phase microextraction (SPME) for food samples that have low level of binding matrix or high level of hydrophobic compounds. In this communication, automated sequential SPME-GC-MS strategy was developed for addressing the displacement issue. The SPME thin film with PDMS coating was firstly used for the extraction of hydrophobic components in the sample which cause displacement and then SPME fiber with DVB/CAR/PDMS coating was applied in the second step for the extraction of the remain compounds. This new strategy was investigated by using 10 key food odorants as target analytes and tested in commercial beer samples. The results suggested that sequential SPME can decrease the displacement effect and improve the extraction efficiency for polar analytes.
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Odorantes , Microextração em Fase Sólida , Microextração em Fase Sólida/métodos , Cromatografia Gasosa-Espectrometria de MassasRESUMO
Solid-phase microextraction (SPME) is a simple and highly effective sample-preparation technique for water analysis. However, the extraction coverage of a given SPME device with a specific coating can be an issue when analyzing multiple environmental contaminants. Therefore, instead of synthesizing one sorbent material with dual or multiple functions, we investigated a new strategy of preparing SPME blades using a homogeneous slurry made by mixing three different sorbent particlesânamely, hydrophobic/lipophilic balanced (HLB), HLB-weak cationic exchange (HLB-WCX), and HLB-weak anionic exchange (HLB-WAX)âwith a polyacrylonitrile (PAN) binder. The developed coating is matrix compatible, as the binder functions not only as a glue for immobilizing the sorbent particles but also as a porous filter, which only allows small molecules to enter the pores and interact with the particles, thus avoiding contamination from large elements. The results confirmed that the proposed mixed-coating SPME device provides good extraction performance for polar and nonpolar as well as positively and negatively charged compounds. Based on this device, three comprehensive analytical methodologiesâhigh-throughput SPME-LC-MS/MS (for the quantitative analysis of targeted drugs of abuse and artificial sweeteners), in-bottle SPME-LC-high resolution MS (HRMS) (for the untargeted screening of organic contaminants), and on-site drone sampling SPME-LC-HRMS (for on-site sampling and untargeted screening)âwere developed for use in environmental water analysis. The resultant data confirm that the proposed strategies enable comprehensive water quality assessment by using a single SPME device.
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Microextração em Fase Sólida , Espectrometria de Massas em Tandem , Cromatografia Líquida/métodos , Microextração em Fase Sólida/métodos , Espectrometria de Massa com Cromatografia LíquidaRESUMO
Fentanyl and its analogues are potent opioids that pose a significant threat to society. Over the last several years, considerable focus has been on the concerning trend of increasing fentanyl usage among drug users. Fentanyl analogues are mainly synthesized to evade analytical detection or increase their potency; thus, very low concentrations are sufficient to achieve a therapeutic effect. In an effort to help combat the synthetic opioid epidemic, developing targeted mass spectrometric methods for quantifying fentanyl and its analogues at ultralow concentrations is incredibly important. Most methods used to analyze fentanyl and its analogues from whole blood require manual sample preparation protocols (solid-phase extraction or liquid-liquid extraction), followed by chromatographic separation and mass spectrometric detection. The main disadvantages of these methods are the tedious sample preparation workflows, resulting in lengthy analysis times. To mitigate these issues, we present a targeted method capable of analyzing 96 samples containing fentanyl, several fentanyl analogues, and a common fentanyl (analogue) precursor simultaneously in 2.4 min per sample. This is possible by using a high-throughput solid phase microextraction workflow on the Concept96 autosampler followed by manual coupling of solid-phase microextraction fibers to the microfluidic open interface for tandem mass spectrometry analysis. Our quantitative method is capable of extremely sensitive analysis, with limits of quantification ranging from 0.002 to 0.031 ng mL-1 and linearity ranging from 0.010 to 25.0 ng mL-1. The method shows very good reproducibility (1-18%), accuracy (81-100%) of calibration and validation points, and good interday reproducibility (6-15%).
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Fentanila , Microextração em Fase Sólida , Fentanila/análise , Microextração em Fase Sólida/métodos , Microfluídica , Reprodutibilidade dos Testes , Analgésicos Opioides/análiseRESUMO
In vivo lung perfusion (IVLP) is a novel isolated lung technique developed to enable the local, in situ administration of high-dose chemotherapy to treat metastatic lung cancer. Combination therapy using folinic acid (FOL), 5-fluorouracil (F), and oxaliplatin (OX) (FOLFOX) is routinely employed to treat several types of solid tumours in various tissues. However, F is characterized by large interpatient variability with respect to plasma concentration, which necessitates close monitoring during treatments using of this compound. Since plasma drug concentrations often do not reflect tissue drug concentrations, it is essential to utilize sample-preparation methods specifically suited to monitoring drug levels in target organs. In this work, in vivo solid-phase microextraction (in vivo SPME) is proposed as an effective tool for quantitative therapeutic drug monitoring of FOLFOX in porcine lungs during pre-clinical IVLP and intravenous (IV) trials. The concomitant extraction of other endogenous and exogenous small molecules from the lung and their detection via liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS) enabled an assessment of FOLFOX's impact on the metabolomic profile of the lung and revealed the metabolic pathways associated with the route of administration (IVLP vs. IV) and the therapy itself. This study also shows that the immediate instrumental analysis of metabolomic samples is ideal, as long-term storage at -80 °C results in changes in the metabolite content in the sample extracts.
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Binders are critical components used in the preparation of a range of extraction devices, including solid-phase microextraction (SPME) devices. While the main role of a binder is to affix the sorbent particles to the selected support, it is critical to select the optimal binder to ensure that it does not negatively impact the coating's particle sorption capability. This work presents the first comprehensive investigation of the interactions between binders and solid sorbent particles as these interactions can significantly impact the performance of the coating. Specifically, the findings presented herein provide a better understanding of the extraction mechanisms of composite coatings and new rules for predicting the particle adhesion forces and binder distribution in the coating. The influence of binder chemistry on coating performance is investigated by examining a selection of the most used binders, namely, polydimethylsiloxane (PDMS), polyacrylonitrile (PAN), poly(vinylidene difluoride) (PVDF), polytetrafluoroethylene amorphous fluoroplastics (PTFE AF 2400), and polybenzimidazole (PBI). The solid particles (e.g., hydrophilic-lipophilic balanced (HLB) and C18) used in this work were selected for their ability to provide optimal extraction coverage for a broad range of analytes. The results show that PDMS does not change the properties of the solid particles and that the binder occupies a negligible volume due to shrinking after polymerization, resulting in the solid particles making up most of the coating volume. Hence, the coating sorption characteristics correspond closely to the properties of the selected solid particles. On the other hand, the results also showed that PTFE AF 2400 can interact with the active surface of the sorbent, leading to the deactivation of the sorbent particles. Therefore, the extraction performance and permeability coefficients decrease as the size of the penetrant increases, indicating a rigid porous structure. The results of this study can aid in the optimization of SPME devices as they provide reference values that can be used to determine the optimal binder and the sorbent affinity for the targeted compounds. Finally, the present work also provides the broader scientific community with a strategy for investigating the properties of sorbent particle/binder structures and defines the characteristics of a good coating/membrane by analyzing all parameters such as kinetics, thermodynamic equilibria, and morphology.
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The release of metabolites from their bound to free forms is the main regulatory path in living species. Therefore, the ability to determine the free concentrations of small molecules is highly critical in many biological samples. The main challenges in achieving this task are the interferences inherent to complex matrices and the ability to distinguish between the free and total concentrations. This paper presents a non-invasive microextraction method that enables the determination of endocannabinoids in brain tissue. The proposed method is based on two key principles: the availability of the free concentration of endocannabinoids for partitioning to the solid-phase microextraction (SPME) fiber; and negligible depletion enabled by the small volume of extraction phase on the fiber. These features allow the presented SPME method to provide information about the free concentration of analytes without disturbing the binding equilibrium between the analytes and the matrix. The determination of spiked samples with known concentrations enables the percentage of analyte bound to the tissue to be calculated, which can then be applied to calculate the total concentration from the determined free concentration. This manuscript focuses on the determination of the free concentration and tissue binding percentages of endocannabinoids in brain tissue. Significantly, SPME's small size and potential for non-invasive sampling enable its application in live animal subjects with minimal tissue damage.
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Encéfalo , Endocanabinoides , Animais , Microextração em Fase SólidaRESUMO
A novel solid-phase microextraction (SPME) coating is presented that uses polybenzimidazole (PBI) as a binder to immobilize micro-size sorbent particles onto a support. An evaluation of the developed binder's thermal and solvent desorption capabilities demonstrated its compatibility with both gas and liquid chromatography (GC and LC). The incorporation of hydrophilic-lipophilic balanced (HLB) particles provided optimal extraction coverage for an array of chemically diverse analytes possessing a range of hydrophobicities and molecular weights. The developed binder's performance was assessed by comparing it to a selection of binders commonly used in the literature, including polydimethylsiloxane (PDMS) and polyacrylonitrile (PAN), as well as the more recently developed polyvinylidene fluoride (PVDF) and polytetrafluoroethylene amorphous fluoroplastic (PTFE AF 2400). The results revealed that PBI provides better performance compared to PVDF and PTFE AF 2400 in terms of its environmental impact, while also being convenient for use in coating preparation and offering good matrix compatibility. The thermal analysis revealed that PBI exhibited more than 93% weight retention at 550 °C, which is superior to PVDF's 80.07% weight retention at 393.78 °C. To the best of our knowledge, this work is the first to use PBI as a particle binder in SPME coatings. The PBI coating maintained high extraction efficiencies under extreme conditions with pH values of 3 and 12. The performance of PBI in combination with HLB was assessed by employing it to extract several drugs of abuse and McReynolds compounds for LC and GC analysis, respectively. The results indicated that PBI performs similarly to PAN for LC but is outperformed by PDMS in GC applications with respect to extraction and desorption kinetics. Nonetheless, the thermal and solvent desorption results indicated that PBI can be used for both applications, as it remains stable at temperatures over 350 °C and is stable when solvent desorption is applied.
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There is high demand for rapid screening of toxics in food analysis. In this study, a new high-throughput and automated solid-phase microextraction (SPME) system was employed for the sample preparation of mycotoxins in beers. Matrix compatible SPME blades with thin coating layer were used, which significantly decreased the matrix effects in beer samples (≤ 12%). This SPME system allows 96 samples to be processed automatically and simultaneously with average preparation time of 57 s per sample. After sample preparation, the 96-well plate with desorption solution was sealed with a thin film and put into the LC-MS sampler for analysis via positive/negative ESI switching mode. The results also showed good sensitivity (limits of detection between 0.02 and 3 ng/mL) with R2≥ 0.9971, reproducibility (intra- and inter-day ≤ 8% and ≤ 13%, respectively), and accuracy (recoveries between 79% and 121%).
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Cerveja , Micotoxinas , Espectrometria de Massas em Tandem/métodos , Microextração em Fase Sólida/métodos , Reprodutibilidade dos Testes , Cromatografia Líquida/métodosRESUMO
A solid-phase microextraction (SPME) pin device with a biocompatible coating on the tip was developed for direct coupling to mass spectrometry (MS) via a vertical dipping-and-spray strategy using an automated probe electrospray ionization (PESI) interface. The developed method provides superior sensitivity compared to standard PESI-MS due to the enrichment effects of SPME and the significant increase in the volume of sample and/or solvent collected during dipping due to the SPME pin's notably larger size. The tips of the SPME pins were coated with a biocompatible coating consisting of small sorbent particles embedded into a polyacrylonitrile (PAN) binder. This coating enables the extraction of small molecules, while preventing larger molecules such as tissue fragments, proteins, and cell matter from coming into the sorbent. The developed SPME pin-PESI-MS method also features much lower matrix effects compared to PESI-MS for the analysis of complex biology samples. When applied for the analysis of 8 drugs of abuse in urine samples, the SPME pin-PESI-MS method provided good linearity (R2 ≥ 0.9997), high sensitivity with limits of detection between 0.003 to 0.03 ng/mL, and good reproducibility with RSD% ≤ 6%. The vertical design of the SPME-PESI-MS direct-coupling interface allows the potential fully automation of the system using a conventional autosampler.
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There is great demand for analytical methods capable of providing high-throughput and rapid screening, especially for anti-doping and clinical point-of-care applications. In this work, automated microfluidic open interface-mass spectrometry (MOI-MS) was used for coupling with high-throughput, automated solid-phase microextraction (SPME) to achieve this objective. The design of the MOI-MS interface provides a continuous and stable electrospray fluid flow to the MS without introducing any bubble, a feature that we exploit to introduce the concept of multi-segment injection for the determination of multiple samples in a single MS run. By eliminating the need to start a new MS run between sample assays, the developed approach provides significantly simplified protocols controlled by programmed software and increased reproducibility. Furthermore, the biocompatible SPME device, which utilizes coating consisting of hydrophilic-lipophilic balanced particles embedded in a polyacrylonitrile (PAN) binder, can be directly used for biological sample analysis, as the PAN acts as both a binder and a matrix-compatible barrier, thus enabling the enrichment of small molecules while eliminating interferences associated with the presence of interfering macromolecules. The above design was employed to develop a fast, quantitative method capable of analyzing drugs of abuse in saliva samples in as little as 75 s per sample. The findings indicate that the developed method provides good analytical performance, with limits of detection ranging between 0.05 and 5 ng/mL for analysis of 16 drugs of abuse, good calibration linear correlation coefficients (R2 ≥ 0.9957), accuracy between 81 and 120%, and excellent precision (RSD% < 13%). Finally, a proof-of-concept experiment was performed to demonstrate the method's suitability for real-time analysis in anti-doping applications.