bims-metlip Biomed News
on Methods and protocols in metabolomics and lipidomics
Issue of 2025–10–12
thirty-six papers selected by
Sofia Costa, Matterworks



  1. Drug Des Devel Ther. 2025 ;19 8903-8917
       Background: Oxazolidinone antimicrobials, which are effective against multidrug-resistant gram-positive pathogens, face challenges of variable efficacy and safety owing to patient pharmacokinetic differences.
    Purpose: This study aimed to establish a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method to simultaneously quantify multiple oxazolidinone antimicrobials, including linezolid, tedizolid, and contezolid, for therapeutic drug monitoring (TDM) applications.
    Methods: Chromatographic separation was achieved on a C18 column (100 × 2.1 mm, 3.5 μm) with gradient elution. Detection was performed via positive electrospray ionization (ESI+) in multiple reaction monitoring (MRM) mode, targeting transitions: m/z 338.14→162.8 (linezolid); m/z 371→343.1 (tedizolid) and m/z 409.15→269.14 (contezolid), with voriconazole-d3 as the internal standard.
    Results: The method was validated using Bioanalytical Method Validation (M10). The method demonstrated high selectivity and wide linear ranges of 50.0-15,000.0 ng/mL for linezolid and contezolid, and 25.0-7500.0 ng/mL for tedizolid, respectively, with a good linearity (R2 > 0.993). The intra- and inter-day accuracy and precision were within acceptable limits. Recovery ranged from 94.4% to 104.2% in plasma, and matrix effects were negligible (CV%<3.6%). Stability experiments confirmed analyte integrity under short-term (8 h at room temperature), long-term (34 days at -80°C for linezolid; 40 days for tedizolid and contezolid), and freeze-thaw conditions. No carry-over contamination was exhibited. This method has been successfully applied to monitor the concentrations of both drugs during the transition between linezolid and contezolid therapy.
    Conclusion: This validated LC-MS/MS method enables the simultaneous determination of linezolid, tedizolid, and contezolid in human plasma, rendering it promising for pharmacokinetic studies and TDM, and contributing to optimized patient care in complex therapeutic scenarios.
    Keywords:  LC-MS/MS; contezolid; linezolid; oxazolidinone; tedizolid
    DOI:  https://doi.org/10.2147/DDDT.S547979
  2. Acc Chem Res. 2025 Oct 07.
      ConspectusMass spectrometry imaging (MSI) has transformed our ability to explore molecular distributions in biological tissues with high chemical specificity and sensitivity. Despite significant advances in this field, the absence of separation prior to analysis leads to isomeric and isobaric overlaps, posing a major analytical challenge. To enhance chemical specificity and enable isomer differentiation, tandem mass spectrometry, ion mobility spectrometry, chemical complexation, and derivatization strategies are increasingly integrated into MSI workflows.Ambient ionization MSI techniques provide both chemical and spatial information under native or near-native conditions, enabling rapid, label-free molecular imaging of complex biological samples with minimal sample pretreatment. Among the most promising ambient MSI techniques is nanospray desorption electrospray ionization (nano-DESI), a method that relies on localized liquid extraction directly from biological tissue sections. We have successfully implemented custom-designed nano-DESI platforms on multiple commercial mass spectrometers to enable molecular identification at each pixel of the image and facilitate isomer-selective mass spectrometry imaging (iMSI).This Account highlights recent advances in iMSI using nano-DESI. Key developments include the integration of nano-DESI with multiple reaction monitoring on a triple quadrupole mass spectrometer to differentiate isomeric lipids in biological tissues. We also describe the integration of photoinitiated derivatization and metal ion complexation strategies to enable isomer-selective imaging using structure-specific fragments generated by collision induced dissociation. Furthermore, high-resolution separation of lipid isomers was achieved by coupling nano-DESI with trapped ion mobility spectrometry, demonstrating the value of gas-phase separation for iMSI. These innovations have significantly expanded the analytical capabilities of MSI critical to probing the spatial organization of isomeric lipids and metabolites in biological systems. We also discuss future directions, including new complexation strategies and the integration of nano-DESI with data-independent acquisition and parallel accumulation serial fragmentation technologies. Collectively, these advances establish nano-DESI iMSI as a powerful and versatile tool in the evolving field of spatial metabolomics and lipidomics.
    DOI:  https://doi.org/10.1021/acs.accounts.5c00532
  3. J Chromatogr B Analyt Technol Biomed Life Sci. 2025 Oct 01. pii: S1570-0232(25)00357-5. [Epub ahead of print]1267 124803
      A highly sensitive and specific liquid chromatography-tandem mass spectrometry method was developed, fully validated, and successfully implemented for routine analysis to simultaneously quantify Bictegravir, Emtricitabine, Doravirine, Cabotegravir, Lenacapavir, Fostemsavir, Tenofovir alafenamide, and their metabolites, Temsavir and Tenofovir, in human plasma. The sample preparation employed a commercial liquid-liquid extraction kit optimized for low plasma volumes (50 μL), which also included the Internal Standard. The method demonstrated excellent precision, accuracy, and robustness, making it suitable for pharmacokinetic and therapeutic drug monitoring applications. Analyte separation was carried out using a gradient elution program over a total run time of seven minutes, with a flow rate of 0.35 mL/min. The mobile phase consisted of solvent A (water containing 0.1 % formic acid) and solvent B (acetonitrile containing 0.1 % formic acid). Detection was performed using a QTRAP® 5500 triple quadrupole mass spectrometer (SCIEX) equipped with an electrospray ionization source operating in positive ion mode. Ion monitoring was performed in multiple reaction monitoring (MRM) mode for all analytes. The method was validated in accordance with European Medicines Agency (EMA) guidelines across clinically relevant concentration ranges. The proposed method was successfully implemented in routine analysis. Following the initial months of application, biological samples from 165 patients were analyzed primarily to assess therapy adherence and confirm that drug blood concentrations reached the minimum threshold. Additionally, data on drug pharmacokinetics were obtained. Our findings indicate that the proposed method is a reliable and accurate tool for high-throughput screening that could be readily used by the clinicians to optimize therapeutic treatments, verify patients' adherence and reduce drug-related toxicities.
    Keywords:  Antiretroviral; HIV; Long-acting injectable antiretroviral; Pharmakokinetic; Tandem-mass spectrometry
    DOI:  https://doi.org/10.1016/j.jchromb.2025.124803
  4. J Pharm Biomed Anal. 2025 Oct 03. pii: S0731-7085(25)00519-9. [Epub ahead of print]268 117178
      The folate cycle is essential for regulating metabolic processes. Simultaneous measurement of folate cycle intermediates is crucial for understanding metabolic disruptions in hematopoietic, nervous, renal and cardiovascular diseases. Currently, liquid chromatography-tandem mass spectrometry (LC-MS/MS) methods for folate cycle metabolites showed poor retention for highly polar compounds in reversed-phase separations with long analytical run time (30 min). Herein, we developed a novel LC-MS/MS method using hydrophilic interaction liquid chromatography (HILIC) mode for simultaneous measurement of 10 key folate cycle metabolites in human plasma, including 5 folate intermediates, 4 related amino acids, and a cofactor (VB12), with enhanced chromatographic retention and reduced analysis time (8.5 min) without derivatization. Through further method validation, all analytes demonstrated acceptable linearity (R² > 0.989), precision (intra-day precision: 1.3-11.3 %; inter-day precision: 3.4-14.6 %), recovery (89.5-113.8 %) and reasonable matrix effect (81.6-115.8 %). The results presented that all intermediates were stable for 5 h at 5°C (autosampler), 12 h at -40°C and 24 h at -80°C. Moreover, the method was successfully applied in clinical plasma from critically ill patients, revealing distinct metabolic perturbations in acute kidney injury (AKI) inpatients compared with non-AKI controls (NAKI). Levels of 5-MTHF and Gly were significantly elevated in the AKI group. Correlation analysis revealed that SCr levels were positively correlated with both 5-MTHF (r = 0.26, p = 0.04) and hCys (r = 0.27, p = 0.04) concentrations. The study is promising to evaluate folate nutritional status to mitigate the risks of folate-related diseases, such as megaloblastic anemia and neural tube defects.
    Keywords:  Folate cycle; HILIC; LC-MS/MS; Plasma
    DOI:  https://doi.org/10.1016/j.jpba.2025.117178
  5. Biomed Chromatogr. 2025 ;39(11): e70236
      Validated assays are vital to support the accurate reporting of pharmacokinetics for parent drug/metabolite(s), regardless of the stage of drug development. One of the recent nuances in the field has focused on the selection of an appropriate stable isotopically labeled internal standard (SIL-IS) with a sufficient mass difference from the target analyte as a panacea to render unambiguous quantitation of the target analyte(s) in liquid chromatography-tandem mass spectrometry methods (LC-MS/MS). Although the intent of using SIL-IS is well supported, there are potential issues that may arise because of cross-signal contributions due to various factors, which could potentially lead to nonlinearity in the standard curves and further contribute to wider assay biases. This perspective article presents the available knowledge in the field pertaining to potential issues with the use of SIL-IS and provides insights/commentary on these situations, as a means to both understand and manage such issues during the development of assays.
    DOI:  https://doi.org/10.1002/bmc.70236
  6. Methods Mol Biol. 2026 ;2988 103-117
      Under natural conditions, cold and freezing stress is one of the detrimental factors plants face during their life cycle. For acclimatization, adaptation, and defense, plants accumulate specialized metabolites such as flavonoids, phenolics, alkaloids, saponins, and tannins. Identification of metabolites is especially important to study the impact and resilience toward stress conditions. The present chapter briefly describes metabolite profiling from a plant sample, including sample harvesting, metabolite extraction, identification, and quantification. The first and most crucial step in metabolomics is sample preparation (sample harvesting, drying, metabolite extraction, and preparation for analysis), which impacts the accuracy of the result and largely depends on analytical tools and the class of metabolites. Liquid solvent extraction of alkaloids, saponins, and tannins has been discussed. Advanced extraction methods for volatile compounds, like headspace analysis and solid-phase microextraction (SPME), are also reviewed. We also discussed liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS) based protocols for metabolite profiling.
    Keywords:  Cold stress; GC-MS; LC-MS; Metabolites; Metabolomics
    DOI:  https://doi.org/10.1007/978-1-0716-4981-7_10
  7. J Vis Exp. 2025 Sep 16.
      Single-cell mass spectrometry (SCMS) has become an indispensable tool for studying cellular metabolism. Owing to advancements in modern mass spectrometry (MS) techniques and demand in studies of cell heterogeneity in fundamental biological sciences and human diseases, a variety of different SCMS techniques have been developed and applied in laboratory research. As metabolites can accurately reflect cell status, SCMS metabolomics analysis of live cells is regarded as a powerful tool to provide molecular information about cells. However, a major challenge in SCMS analysis of live cells is preserving the endogenous metabolite profiles during sample preparation, transport, and measurement. Cellular metabolites undergo rapid turnover and are highly sensitive to environmental changes, making them susceptible to degradation or transformation prior to analysis. To address this limitation, we present a robust and reproducible cell preparation protocol designed to preserve cellular metabolite integrity for SCMS. The protocol integrates cell washing with a volatile ammonium formate (AF) solution, rapid quenching with liquid nitrogen (LN2), vacuum freeze-drying, and storage at -80 °C. This approach minimizes cell membrane damage while effectively halting metabolic activity. The results indicate that rapid cell quenching is vital; however, limiting storage time at -80 °C is necessary to preserve cell metabolites. The proposed protocol can potentially be used for other existing SCMS techniques for broad applications.
    DOI:  https://doi.org/10.3791/68995
  8. Analyst. 2025 Oct 07.
      Comprehensive metabolomics requires robust and efficient analytical techniques capable of addressing the chemical diversity, complexity, and high sample throughput demands characteristic of large-scale studies. We introduce a rapid, mixed-mode liquid chromatography method that uniquely integrates anion exchange and hydrophobic interactions within a single stationary phase. Employing an optimized ternary gradient, our method achieves comprehensive separation of diverse metabolite classes over a wide range of polarities within only 4 minutes per run. The performance was tested with standards for ca. 1000 metabolites. For two-thirds of 94 isomeric sets, we could achieve a separation of 2 or more seconds, which is sufficient for correct identification. We demonstrate robustness over 500 consecutive injections of bacterial extracts and with the analysis of complex matrices like plasma, cecum extracts, and urine. Throughout, retention time drifts were <1 s. Our mixed-mode LC-MS approach offers a routine throughput of 360 samples per day per instrument and is ideally suited for studies that require rapid and comprehensive metabolic profiling.
    DOI:  https://doi.org/10.1039/d5an00641d
  9. Anal Chim Acta. 2025 Nov 22. pii: S0003-2670(25)00850-5. [Epub ahead of print]1376 344456
       BACKGROUND: In recent years, there has been growing interest in the development of advanced lipidomic techniques capable of resolving lipid isomers. The Paternò-Büchi (PB) reaction, coupled with tandem mass spectrometry (MS/MS), has emerged as a powerful tool for analysis of unsaturated lipids.
    RESULTS: This review introduces basic principles of PB-MS/MS for identification and quantitation of CC location isomers of lipids and its utilization in determining sn-position and the geometry of CC. Then, the approaches for integrating PB-MS/MS into lipidomic workflows are discussed, including shotgun analysis, direct analysis, online and offline coupling with liquid chromatography-MS, single-cell analysis, and mass spectrometry imaging. Examples are provided to illustrate how deep profiling enabled by PB-MS/MS offers crucial insights into lipid metabolism at the isomer level and facilitates lipidomic phenotyping of diseased tissues and single cells. Finally, the challenges and future directions for the advancement of PB-MS/MS are discussed.
    SIGNIFICANCE: This review summarizes recent advancements in PB-MS/MS, an important tool for structural lipidomics, with a focus on aiding researchers in selecting an appropriate strategy for their specific applications in both fundamental and translational research.
    Keywords:  Isomers; Lipid derivatization; Lipidomics; Liquid chromotography; Paternò−Büchi reaction; Tandem mass spectrometry
    DOI:  https://doi.org/10.1016/j.aca.2025.344456
  10. J Chromatogr A. 2025 Oct 06. pii: S0021-9673(25)00773-3. [Epub ahead of print]1763 466429
      Liquid chromatography-tandem mass spectrometry (LC-MS/MS) provides high sensitivity and specificity, yet its complexity restricts its widespread use in clinical testing. Magnetic bead-assisted extraction (MBE) technology holds promise for automated sample preparation, but research in this area is still limited. This study developed an automated MBE method for the simultaneous quantification of aldosterone, cortisol, deoxycorticosterone, and cortisone in human plasma. Method validation included assessments of linearity, limit of quantification (LOQ), accuracy, precision, and matrix effects. Comparative analysis was performed on samples from 40 patients who underwent adrenal vein sampling (AVS). Results showed that the MBE method exhibited analytical performance comparable to conventional supported liquid extraction (SLE), with linear responses over the reportable range. The LOQs for aldosterone, cortisol, deoxycorticosterone, and cortisone were 4.09 pg/mL, 1.08 μg/mL, 8.20 pg/mL, and 0.45 ng/mL, respectively. The method achieved excellent reproducibility, with intra-day and total coefficients of variation ranging from 0.34% to 14.37% for all four hormones. Relative recoveries for the four steroid hormones were within the range of 80% to 120%, with biases within ±15%. No significant matrix effects were detected for aldosterone and cortisone. After correction with an internal standard, matrix effects for deoxycorticosterone and cortisol were effectively compensated. Additionally, a comparative analysis of 40 AVS samples using the MBE method yielded results comparable to those of the traditional SLE method, thereby validating the clinical consistency of our approach. Our method enables the simultaneous detection of aldosterone, cortisol, deoxycorticosterone, and cortisone, and is suitable for routine clinical diagnostics. This method may facilitate the broader application of LC-MS/MS in clinical testing by streamlining the workflow and saving manpower.
    Keywords:  Automation; LC/MS; Magnetic bead-assisted extraction; Primary aldosteronism; Steroid hormones
    DOI:  https://doi.org/10.1016/j.chroma.2025.466429
  11. J Chromatogr A. 2025 Oct 01. pii: S0021-9673(25)00776-9. [Epub ahead of print]1763 466432
      An efficient and highly sensitive analytical method was developed for the simultaneous determination of neonicotinoids, benzopyrazoles, diamide insecticides and chlorothalonil fungicide and their metabolites in biological samples (urine, serum and breast milk). The method combines centrifugal-assisted cold-induced phase separation (CIPS) with liquid chromatography and high-resolution mass spectrometry (LCHRMS) in multiplexed-targeted single-ion monitoring (MSX-tSIM) mode to ensure high sensitivity and accuracy. Sample preparation parameters such as solvent selection and acetonitrile/water ratio were optimized to improve analyte recovery and minimize matrix effects. The method exhibited excellent accuracy, precision, and low limit of quantification (LLOQ) in the range of 0.01-0.2 µg/L, with recoveries ranging from 72.6 % to 109.6 % in a variety of biological matrices. The method showed good linearity (R² > 0.993) and was suitable for the detection of trace pesticide levels in complex biological samples. Biomonitoring of pooled samples revealed widespread neonicotinoids contamination, with fipronil metabolites detected only in serum and breast milk, raising concerns about the potential accumulation of pesticide metabolites in the human body, especially in susceptible populations. This method provides a cost-effective and environmentally friendly alternative to traditional methods, facilitates large-scale human biomonitoring studies, and supports pesticide exposure risk assessment.
    Keywords:  Advanced instrumental analysis; Biomonitoring; Centrifuge; Multiplexed method; Sample preparation
    DOI:  https://doi.org/10.1016/j.chroma.2025.466432
  12. Anal Chem. 2025 Oct 07.
      Untargeted metabolic profiling of plasma and serum by liquid chromatography-mass spectrometry (LC-MS) is becoming increasingly important in clinical and translational research; however, sample preparation protocols can have a significant impact on study outcomes, and there is currently a lack of standardized approaches. In this study we demonstrate that pretreatment of serum and plasma samples with 1% formic acid (FA, v/v) prior to acetonitrile (MeCN)-induced protein precipitation significantly enhances analytical performance in untargeted metabolomics using reversed-phase liquid chromatography (RPLC)-MS. We show an increase in sample preparation reproducibility and signal intensity across both positive and negative ionization modes. In two independent serum cohorts (OPTIMA and VITACOG), FA-based extraction improved multivariate modeling (orthogonal partial least-squares discriminant analysis, OPLS-DA), with consistently higher classification accuracy, sensitivity, and specificity, alongside reduced variability and increased fold-changes in discriminatory compound-features. We investigated factors potentially involved in the enhanced performance and observed outcomes consistent with the disruption of noncovalent protein-metabolite interactions and the stabilization of labile species. We found no correlation with either protein depletion or differential adduct formation. The results were also not attributable to lowering pH after metabolite extraction. In summary, we demonstrate that FA pretreatment of plasma and serum, prior to protein precipitation, significantly improves sample reproducibility and detection sensitivity in untargeted RPLC-MS metabolomics. This optimized sample preparation strategy offers clear advantages for clinical and translational metabolomics, with the potential to enhance biomarker discovery and metabolic phenotyping.
    DOI:  https://doi.org/10.1021/acs.analchem.5c03725
  13. J Pharm Biomed Anal. 2025 Sep 26. pii: S0731-7085(25)00503-5. [Epub ahead of print]267 117162
      Organophosphorus flame retardants (OPFRs) are widely used chemicals with significant health risks to humans. OPFRs are metabolized and excreted primarily through urine, making urine a key matrix for assessing human exposure levels. Therefore, this study developed a method combining the Quick, Easy, Cheap, Effective, Rugged, Safe (QuEChERS) approach with ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) for the simultaneous determination of 11 OPFRs and 6 organophosphorus flame retardant metabolites (mOPFRs) in human urine. All target compounds exhibited excellent linearity, with correlation coefficients (r²) exceeding 0.9988. The limits of detection (LODs) and the limits of quantification (LOQs) ranged from 0.01 ng/mL to 0.05 ng/mL and 0.03 ng/mL to 0.16 ng/mL, respectively. Except for tricresyl phosphate (<50 %), the spiked recoveries for the other target compounds were 51.4-117 %, 52.4-100 %, 63.9-128 %, and 89.0-112 % at four concentration levels. All analytes showed intra-day and inter-day precision with relative standard deviations (RSDs) of 0.8-18.8 % and 1.4-12.2 %, respectively. Analysis of children's urine revealed distinct metabolic patterns: triphenyl phosphate and tris(1,3-dichloro-2-propyl) phosphate were not detected, while their metabolites, diphenyl phosphate and bis(1,3-dichloro-2-propyl) phosphate, were found in the urine. In contrast, tris(2-butoxyethyl) phosphate, tributyl phosphate, tri(2-chloroethyl) phosphate, and tris(1-chloro-2-propyl) phosphate suggested possible co-occurrence of parent compounds and metabolites. The developed method is simple, sensitive and robust, and has the advantage of high throughput for screening 17 targets including parent compounds and metabolites. These features make it suitable for assessing the exposure risk of OPFRs in urine.
    Keywords:  Metabolites; Organophosphorus flame retardants; QuEChERS; UPLC-MS/MS; Urine
    DOI:  https://doi.org/10.1016/j.jpba.2025.117162
  14. J Food Drug Anal. 2025 Sep 18. 33(3): 339-347
      Bongkrekic acid (BKA) poisoning is a severe foodborne illness with a high mortality rate. This study aimed to identify BKA in postmortem tissues from poisoning victims in Taiwan and to develop a reliable analytical method for detecting BKA in biofluids to aid clinical diagnosis and treatment. BKA was identified in postmortem samples using high-resolution mass spectrometry (HRMS) and confirmed with an independent ultrahigh-performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS) method. To meet clinical needs, a UHPLC-MS/MS method was developed and validated for BKA detection in plasma and urine. Method optimization included adjustments to ion source conditions for multiple reaction monitoring (MRM) transitions and avoidance of glass vials due to BKA adsorption onto free silanol groups. Chromatographic separation was achieved using a 50-mm Hypersil Gold C18 column within a 6-min run time. The validated UHPLC-MS/MS method successfully detected BKA in biofluids, enabling its application in identifying victims of foodborne poisoning. The method demonstrated high accuracy and efficiency, facilitating timely diagnosis and aiding in treatment strategies for critically ill patients. The developed UHPLC-MS/MS method provides a reliable approach for detecting BKA in clinical and forensic settings. Its implementation enhances diagnostic capabilities, improves patient outcomes, and supports monitoring of toxin elimination in cases of BKA poisoning.
    DOI:  https://doi.org/10.38212/2224-6614.3549
  15. Anal Chim Acta. 2025 Nov 22. pii: S0003-2670(25)01009-8. [Epub ahead of print]1376 344615
       BACKGROUND: Untargeted drug-metabolite identification continues to be challenged by the tradeoff between comprehensive coverage and acceptable false-positive rates. Our previously developed two-dose-difference platform combined with stable isotope tracing (SIT) achieved highly comprehensive and accurate metabolite detection. However, this approach still produced a large false-positive rate. Thus, it is critical to develop strategies that reduce the false-positive burden.
    RESULTS: We benchmarked four data-processing workflows-original two-dose-difference + SIT, modified two-dose-difference + SIT (with a mass shift defect filter), dose-response + SIT, and mass defect filtering + SIT-using nifedipine (NIF) as a probe. UPLC-MS data were acquired under three incubation setups: coincubation of NIF with isotope-labeled analog (D4-NIF), separate incubations, and postreaction mixing of supernatants. Targeted MS/MS validation confirmed 65 putative NIF metabolites, including three previously reported. Among the four data-processing workflows, the original and modified two-dose-difference + SIT workflows proved to be the most comprehensive for NIF metabolite identification. Compared with the original two-dose-difference + SIT workflow, the modified workflow identified all putative NIF metabolites and improved the true-positive rate from 36.9 % to 71.0 % in the coincubation setup. Separate incubation yielded the most comprehensive profile (56 features) compared to coincubation (44) or mixed supernatants (38), indicating coincubation may obscure certain metabolites. Performance of the modified workflow remained consistent irrespective of dosing levels.
    SIGNIFICANCE: By incorporating a mass shift defect filter into the two-dose-difference + SIT workflow, we more than doubled the true-positive discovery rate-from 36.9 % to 71.0 %-without sacrificing metabolite coverage. This streamlined, dose-independent method reduces false positives and accelerates reliable metabolite identification, offering a practical, resource-efficient platform for early-stage drug metabolism studies and mechanistic pharmacology.
    Keywords:  Mass defect filtering; Mass shift defect; Stable isotope filtering; Two-dose difference
    DOI:  https://doi.org/10.1016/j.aca.2025.344615
  16. Anal Chem. 2025 Oct 10.
      Spectral library searching is a key method for compound annotation in mass spectrometry; however, existing libraries often suffer from high data heterogeneity, varying spectral quality, or limited accessibility. These issues are particularly significant in food safety, where the lack of comprehensive reference data hampers the identification of hazardous compounds. To address these limitations, we developed the WFSR Food Safety Mass Spectral Library, a freely accessible tandem mass spectral library focused on food contaminants, residues, and hazardous compounds. This library contains 6993 manually curated spectra from 1001 compounds acquired in positive ionization mode using ultrahigh-performance liquid chromatography coupled to an Orbitrap IQ-X Tribrid mass spectrometer. Spectra were recorded at seven collision energies under standardized conditions. Comprehensive metadata are provided, including common names, CAS, SMILES, InChIKeys, retention times, and compound classes. The library is publicly available via a dedicated website (https://www.wur.nl/en/show/food-safety-mass-spectral-library.htm) and through the GNPS repository, adhering to FAIR data principles to facilitate community reuse. Comparisons with major repositories (GNPS, MassBank, MoNA, and MSnLib) showed that 216 compounds (22.2%) are unique to our library. Further analysis using molecular networking and MS2Query revealed that about 38% of the compounds lack reliable matches in public libraries. The WFSR spectral library is designed to improve the annotation of food toxicants and facilitate the identification of structural analogues using computational tools. This library is part of an ongoing initiative with future updates planned to include negative ionization mode spectra and an expanded compound repertoire, aiming to advance food safety monitoring.
    DOI:  https://doi.org/10.1021/acs.analchem.5c03020
  17. Anal Bioanal Chem. 2025 Oct 06.
      Chemical derivatization is a powerful strategy for enhancing the chromatographic behavior and mass spectrometric sensitivity of lipids, which play an essential role in cellular processes and show high potential in cancer biomarker research. In this study, we describe a targeted and validated method that combines benzoyl chloride derivatization with reversed-phase ultrahigh-performance liquid chromatography tandem mass spectrometry (RP-UHPLC/MS/MS) for the quantitative analysis of the human serum lipidome. In total, 450 lipid species from 19 lipid subclasses were identified based on a combination of multiple reaction monitoring transitions, retention dependencies, dilution series, and derivatization tags. The developed methodology increases the sensitivity for most investigated lipid classes in comparison to conventional methods, but the highest improvement was observed for monoacylglycerols, diacylglycerols, sphingoid bases, and free sterols. The method's accuracy was confirmed using NIST SRM 1950, as the determined concentrations were in agreement with the consensus values from ring trials. Lipidomic profiling of clinical samples revealed a significant dysregulation of lipid metabolism in pancreatic cancer patients compared to healthy controls. Key findings included the upregulation of most monoacylglycerols and sphingosine, and a pronounced downregulation of sphingolipids with very long saturated N-acyl chains and phospholipids containing fatty acyl compositions 18:2 and 20:4. This targeted approach is consistent with the trends previously seen with other methods and also provides new findings and more detailed structural insights into metabolic alterations in pancreatic cancer.
    Keywords:  Derivatization; Human serum; Lipidomic quantitation; Liquid chromatography; Mass spectrometry; Pancreatic cancer
    DOI:  https://doi.org/10.1007/s00216-025-06151-0
  18. Anal Chem. 2025 Oct 06.
      Parathyroid hormone (PTH), an 84-amino acid polypeptide critical for calcium/phosphorus homeostasis, exhibits significant analytical challenges in clinical quantification, particularly in chronic kidney disease (CKD) patients due to its low circulating concentrations, biological matrix complexity, and interference from circulating PTH fragments. Traditional immunoassays may either overestimate the PTH level due to cross-reactivity with the PTH 7-84 or fail to quantify the antagonistic fragment. Highly sensitive and selective mass spectrometry (MS)-based methods could be used as the reference measurement procedure (RMP) for PTH assays, once the limitations of quantification thresholds and antibody-dependent workflows are addressed. Here, we introduce the first inline weak cation-exchange microsolid-phase extraction-tandem mass spectrometry (WCX-μSPE-MS/MS) method for simultaneous quantification of PTH 1-84 and its antagonist PTH 7-84 in clinical serum samples. A carboxyl-functionalized polystyrene nanosphere-modified capillary μSPE column with dual weak cation exchange (WCX) and nonpolar retention mechanisms is integrated with electrospray ionization-MS/MS, enabling online purification, enrichment, and detection in a single analysis. The nanoliter-scale capillary extraction can minimize matrix effects and improve sensitivity while greatly eliminating offline sample transfer steps. A limit of detection (LOD) as low as 6.0 pg/mL (PTH 1-84) or 9.0 pg/mL (PTH 7-84) is achieved, with relative standard deviations less than 10%. Our antibody-free strategy greatly reduces solvent/sample consumption, avoids manual errors, and has been successfully applied for accurate quantification of both PTH 1-84 and PTH 7-84 in clinical serum, demonstrating great potential to serve as an RMP for PTH assays, enhancing diagnostic accuracy for hyperparathyroidism, CKD, and renal bone diseases.
    DOI:  https://doi.org/10.1021/acs.analchem.5c03332
  19. J Chromatogr B Analyt Technol Biomed Life Sci. 2025 Oct 02. pii: S1570-0232(25)00359-9. [Epub ahead of print]1267 124805
      Tripchlorolide is a promising therapeutic compound with potent pharmacological activity and an improved safety profile compared to triptolide. However, its pharmacokinetics and tissue distribution remain poorly characterized. In this study, we developed and validated a rapid and sensitive liquid chromatography-mass spectrometry method for the quantification of tripchlorolide in biological matrices, using triptolide as the internal standard. Quantification was performed in selective ion monitoring mode, following liquid-liquid extraction with ethyl acetate. Chromatographic separation was achieved on a 3.5 μm Agilent ZORBAX Eclipse Plus-C18 column under isocratic elution with a methanol-water mobile phase. Calibration curves were linear over the range of 0.16-200 ng/mL in rat plasma. The method was successfully applied to a pharmacokinetic study in rats and tissue distribution analysis in mice. Tripchlorolide exhibited an absolute bioavailability of 72.97 % after intraperitoneal administration and a half-life of approximately 45 min, with no significant sex-based differences in pharmacokinetic parameters. Tissue distribution following intravenous administration (400 μg/kg) in mice revealed the highest accumulation in the liver, followed by the kidney, spleen, testis, heart, intestine, and brain. These findings provide essential preclinical data for further development of tripchlorolide as a safe and effective therapeutic candidate.
    Keywords:  Liquid chromatography-mass spectrometry; Pharmacokinetics; Tissue distribution; Tripchlorolide
    DOI:  https://doi.org/10.1016/j.jchromb.2025.124805
  20. Anal Chim Acta. 2025 Nov 22. pii: S0003-2670(25)01002-5. [Epub ahead of print]1376 344608
       BACKGROUND: Single-cell mass spectrometry (SCMS) deepens the insight into current bioanalytical science. Precise cell positioning is a critical step in SCMS workflow because it provides accurate spatial coordinates of the target cell for downstream analysis. However, conventional approaches rely on manual cell localization, resulting in compromised analysing throughput. Microfluidic techniques exhibit inherent advantages in rare cell isolation, whereas the encapsulation nature of the microfluidic chip confines the cells in a sealed chamber, making it incompatible with subsequent cellular extraction and mass spectrometry.
    RESULTS: In this study, we developed a reversibly-bonded microfluidic chip that achieves seamless integration with SCMS workflow. Our method features a flexible bonding strategy where the chip maintains bonding stability during cell isolating stage, followed by controlled disassembly to expose the entrapped cells into ambient environment for on-chip SCMS analysis. The results show that single-cells are patterned in geometrically defined positions within 4 min based on size-dependent trapping mechanics, enabling deterministic spatial addressing. In addition, the precisely-engineered cellular trap creates discrete microenvironments for single-cell sampling, and the compartmentalization of the extracting droplet prevents intercell cross-talk in SCMS procedure. The established platform demonstrates exceptional efficacy in single-cell metabolic analysis, as evidenced by the successful detection of 170 metabolites in bladder cancer cells and cellular subtyping is readily achieved based on metabolic fingerprints.
    SIGNIFICANCE: The integration of reversible microfluidics and SCMS bridges the gap between high-throughput cell manipulation and post-processing analysis, representing a novel way for single-cell metabolomics studies.
    Keywords:  Microfluidic chip; On-chip single-cell mass spectrometry; Reversible bonding; Single-cell positioning
    DOI:  https://doi.org/10.1016/j.aca.2025.344608
  21. J Mass Spectrom Adv Clin Lab. 2025 Dec;38 2-9
       Background: Epilepsy affects approximately 50 million people worldwide. Antiepileptic drugs (AEDs) are the mainstream treatment. Therapeutic drug monitoring (TDM) of AEDs is necessary to maximize efficacy and minimize toxicity. We report a simple, rapid, and cost-effective ultra-performance liquid chromatography-mass spectrometry method that can simultaneously measure seven AEDs/metabolites, including levetiracetam (LEV), lacosamide (LCM), zonisamide (ZON), lamotrigine (LMT), 10-hydroxycarbazepine (OXC-M1), clobazam (CLO), and N-desmethyl clobazam (N-CLB) in serum.
    Method: Only 20 µl of serum was used with simple protein precipitation and dilution. Analysis was performed on a SCIEX 6500 UHPLC-MS/MS in positive ion mode. Separation was performed on a C18 reversed-phase column using a gradient. The seven AEDs/metabolites were eluted in 4.5 min.
    Results: The assay was linear over the concentration ranges 0.4-100 µg/mL for LEV, 0.12-30 µg/mL for LMT, 0.12-30 µg/mL for LCM, 0.32-80 µg/mL for ZON, 0.28-70 µg/mL for OXC-M1, and 7.82-2000 ng/mL for CLO, 78.2-20000 ng/mL for N-CLB, respectively, with correlation coefficient greater than 0.99. Recovery was from 88 to 108 %. Intra and inter assay precision for three levels of quality controls were from 2.1 to 6.8 % and 4.2 to 10.9 %, respectively. The accuracy was evaluated by comparing with the College of American Pathologists survey results, and a correlation coefficient greater than 0.96 was observed. The absence of matrix effects was also confirmed.
    Conclusion: We have developed and validated a simple, rapid, and cost-effective UHPLC-MS/MS method for the simultaneous quantitation of seven AEDs/metabolites in serum within a 4.5-min analysis time. It has been implemented in our children's hospital with same-day turnaround time.
    Keywords:  Antiepileptic drugs (AEDs); Therapeutic drug monitoring (TDM); Ultra-high performance liquid chromatography–tandem mass spectrometry (UHPLC–MS/MS)
    DOI:  https://doi.org/10.1016/j.jmsacl.2025.09.001
  22. Microbiol Spectr. 2025 Oct 10. e0191225
      An essential aspect of population-based research is collecting samples outside of a clinical setting. This is crucial because microbial populations are highly dynamic, varying significantly across hosts, environments, and time points, a variability that clinical sample collection alone cannot fully capture. At-home sample collection enables the inclusion of a larger and more diverse group of participants, accounting for differences in ethnicity, age, and other factors. However, managing large studies is challenging due to the complexities involved in sample acquisition, processing, and analysis. Building on our previous work demonstrating the effectiveness of single 1 mL barcoded, racked Matrix Tubes in reducing sample processing time and well-to-well contamination for paired DNA and metabolite extraction, we further validate this method against a previously benchmarked plate-based approach using the same extraction reagents. This validation focuses on samples from the built environment, human skin, human saliva, and feces from mice and humans. Importantly, we explore the impact of using a mix of bead sizes during bead-beating for cell lysis, demonstrating that it enhances taxonomic recovery compared to a single bead size. Finally, we assess the potential of 95% isopropanol for room-temperature sample preservation. Our results show that isopropanol performs comparably to 95% ethanol in many cases, suggesting it is viable as an alternative when ethanol is unavailable. Beyond minimizing contamination, halving processing time, eliminating human error during sample plating, and streamlining metadata curation, the Matrix tube approach produces metabolomic, 16S, and shotgun metagenomic data consistent with the Plate-based Method for both high- and low-biomass samples.
    IMPORTANCE: Numerous studies have linked the microbiome to human and environmental health, yet many fundamental questions remain unanswered. Large-scale studies with robust statistical power are required to identify important covariates against a background of confounding factors. Cross-contamination, limited throughput, and human error have been identified as major setbacks when processing large numbers of samples. We present a streamlined method for sample accession and extraction of metabolites and DNA for both high- and low-biomass samples. This approach, previously shown to significantly reduce cross-contamination, employs an automation-friendly, single barcoded tube per sample. Additionally, we demonstrate that 95% isopropanol serves as an effective ambient-temperature storage solution for many sample types, providing an alternative in regions where ethanol is unavailable or restricted. This method has significant implications for the field, enabling large-scale studies to generate accurate insights with greater efficiency and expanded accessibility in situations in which ethanol is more costly or otherwise not available.
    Keywords:  16S rRNA gene; automation; contamination; large-scale studies; metabolomics; metagenomics; microbiome; sample storage; study design
    DOI:  https://doi.org/10.1128/spectrum.01912-25
  23. Environ Sci Technol. 2025 Oct 10.
      The exposome encompasses environmental exposures throughout life and significantly impacts health and disease. Exposure chemicals, present at trace levels, are frequently quantified using targeted LC-MS/MS. Many existing methods are limited to a narrow range of analyte classes or lack sufficient sensitivity for exposomic analyses, and applicability to large sample cohorts for exposome-wide association studies (ExWAS) remains to be demonstrated. Here, we present a scalable, fit-for-purpose next-generation human biomonitoring (HBM) workflow for analyzing >230 biomarkers in urine, plasma, and serum using solid-phase extraction in 96-well plates and LC-MS/MS. Moreover, a complementary conceptual framework for validation criteria of assays designed to analyze large panels of highly diverse compounds at trace levels is proposed. Method robustness was evaluated, demonstrating extraction recovery (60-130%), matrix effects (SSE, 60-130%), inter-/intraday precision (RSD <30%), and high sensitivity (limit of detection <0.1 ng/mL) for 59-80% of the analytes across the investigated biological matrices. To showcase the method's applicability in epidemiological studies, 200 urine samples from pregnant women in a longitudinal pregnancy cohort were analyzed. More than 100 analytes including PFAS, drugs, air pollutants, pesticides, flame retardants, mycotoxins, industrial products, food processing contaminants, plastics-related chemicals, and phytotoxins, were detected, several for the first time in a U.S. urinary biomonitoring study. With its broad analyte coverage, ultimate sensitivity, robustness, and high sample throughput, this method meets the performance requirements for future large-scale ExWAS applications in public and personalized prevention research.
    Keywords:  early life chemical exposure; exposome-wide association studies (ExWAS); mass spectrometry; next-generation human biomonitoring; public and environmental health
    DOI:  https://doi.org/10.1021/acs.est.5c04458
  24. Anal Bioanal Chem. 2025 Oct 08.
      The separation and characterization of phosphorothioate (PS) diastereomers in GalNAc-conjugated siRNA presents a significant analytical challenge due to the high number of isomers present. To tackle this challenge, we explore and optimize various separation techniques, including chromatographic methods (ion-pair reversed-phase, anion exchange, and hydrophilic interaction liquid chromatography) and ion mobility mass spectrometry (IMS) to assess their efficacy in diastereomer separation. Our results indicate that AEX provides the highest diastereomer selectivity among the chromatographic techniques, although none achieved complete diastereomer separation for the chosen antisense and sense strand reference compounds. IMS, applied within a fragment-based tandem mass spectrometry approach, allows separation of all diastereomers of the antisense strand and partial resolution of the sense strand in the gas phase. The comparison of relative LC-UV quantification with IMS data reveals a strong correlation and suggests that IMS can effectively characterize diastereomer ratios not only qualitatively but also quantitatively, establishing IMS as a promising complementary analytical technique for diastereomer separation besides more established LC-UV methods.
    Keywords:  Diastereomers; GalNAc-conjugated siRNA; Ion mobility-mass spectrometry; Liquid chromatography; Phosphorothioate; Therapeutic oligonucleotides
    DOI:  https://doi.org/10.1007/s00216-025-06123-4
  25. Xenobiotica. 2025 Oct 11. 1-16
      Metabolomics offers a sensitive and comprehensive approach to detect early biochemical changes induced by environmental contaminants, providing insights beyond traditional toxicity assays. In this study, we have developed a targeted metabolomics workflow using low-resolution tandem mass spectrometry (MS/MS) to identify metabolic alterations in zebrafish (Danio rerio) embryos exposed to lowest concentrations (1 µg/L) and highest concentration of (1mg/L) of the antibiotic's amoxicillin and clarithromycin. A library-assisted MRM-EPI (Multiple Reaction Monitoring Enhanced Product Ion) approach was employed using a Q-TRAP LC-MS/MS system, enabling the detection and structural confirmation of 108 endogenous metabolites. Based on the confirmed metabolites using library search, developed a targeted MRM-EPI method optimized for sensitivity, reproducibility, and specificity. Multivariate statistical analyses (PCA and PLS-DA) showed notable metabolic changes in exposed embryos compared to controls, which included significant changes in amino acid, purine, lipid, and energy metabolism. These alterations imply that even sub-lethal antibiotic exposures may affect vital physiological functions, potentially affecting an organism's development and survival. Using zebrafish embryos as a model organism provided a practical, sensitive, and ethically suitable system for environmental toxicity evaluation. This study offers a reproducible MRM-driven metabolomics approach that contributes to developing predictive toxicology, which impacts ecological risk assessment and environmental monitoring.
    Keywords:  LC-MS/MS; MRM–EPI workflow; MS/MS library; biomarkers exposure; environmental metabolomics
    DOI:  https://doi.org/10.1080/00498254.2025.2571653
  26. Anal Chim Acta. 2025 Nov 22. pii: S0003-2670(25)01033-5. [Epub ahead of print]1376 344639
       BACKGROUND: The accurate and efficient determination of nonsteroidal anti-inflammatory drugs (NSAIDs) in biological matrices is crucial for clinical monitoring. However, conventional sample preparation methods like liquid-liquid and solid-phase extraction are often time-consuming and rely on significant amounts of hazardous organic solvents, which conflicts with the principles of green chemistry. These challenges necessitate the development of greener and more efficient extraction techniques. Here, an electro-membrane extraction (EME) platform was developed that utilizes a novel natural deep eutectic solvent-based supramolecular solvent (NADES-SUPRAS) as a supported liquid membrane. This approach provides an effective and environmentally sustainable solution for extracting NSAIDs from biological samples.
    RESULTS: This green analytical chemistry approach, combined with high-performance liquid chromatography, enables the simultaneous and successful extraction of three drugs -diclofenac, mefenamic acid, and ibuprofen -from biological samples. Various parameters affecting the extraction efficiency of analytes were investigated, including the type and composition of the supported liquid membrane, voltage, pH of the donor and acceptor phases, extraction time, HF length, salt addition, and stirring speed. The method showed good linearity, with correlation coefficient values exceeding 0.9901. The detection limit for the analytes was 8 μg L-1, and the quantification limit was 25 μg L-1 in water. The method was successfully applied to the determination of NSAIDs in urine and plasma samples, with relative recoveries ranging from 88.3 % to 104.4 %, indicating its reliability and accuracy.
    SIGNIFICANCE: This work establishes for the first time a suitable and efficient analytical platform using a wholly fatty acid-based NADES-SUPRAS as a supported liquid membrane for EME of NSAIDs. The synergy of EME with this novel green solvent offers a highly sustainable solution, confirmed by an AGREE score of 0.72. It ensures high-throughput sample preparation with a rapid 20-min extraction time. The method's reliability in challenging clinical matrices makes it a significant advancement for therapeutic drug monitoring and environmental analysis.
    Keywords:  Electro-membrane extraction; Hollow fiber liquid phase microextraction; Natural deep eutectic solvent; Nonsteroidal anti-inflammatory drugs; Supramolecular solvents
    DOI:  https://doi.org/10.1016/j.aca.2025.344639
  27. J Chromatogr A. 2025 Sep 27. pii: S0021-9673(25)00764-2. [Epub ahead of print]1762 466420
      Chlorinated paraffins (CPs) are mainly comprised of polychlorinated alkanes (PCAs) and widely used in industrial and commercial purposes, such as flame retardants, plasticisers and high temperature lubricants for metallurgy. Analysis of PCAs remains a challenge in complex biological samples. A robust and sensitive analysis method was presently developed for quantitation of individual carbon chain homologue groups of C9 to C20 PCAs in lipid-rich samples based on gas chromatography (GC) with high-resolution mass spectrometry (HRMS). Samples were extracted and then subjected to a freeze removal step where > 95 % of lipid was removed. This was followed by a sulfuric acid silica gel/silica gel multilayer SPE cartridge clean-up and then subjected to GC with Orbitrap HRMS operated in negative ion chemical ionization (NCI). A deconvolution and quantification procedure was generated for the data analysis process using a program in R language. Matrix effects (ME) showed an enhancement effect for PCA quantitative analyses by GC but was rectified by using olive oil as an analyte protectant. Method limits of quantification for PCAs in the test samples ranged from 1.1 to 17.5 ng/g. Mean recoveries of C09ClX to C20ClX homologues ranged from 56 to 120 % and 79 to 160 % in 50 ng/g and 10 ng/g fortified sunflower oil, respectively, and with relative standard deviations < 11 % and < 19 %, respectively. Reliable method applicability was demonstrated as homologue groups C09ClX to C18ClX were detectable whereas C19ClX and C20ClX were not in all polar bear adipose test samples and with ΣPCA concentrations up to 48.2 ng/g.
    Keywords:  Chlorinated paraffins; High resolution mass spectrometry; Lipid-rich samples; Polar bear adipose; Polychlorinated alkanes
    DOI:  https://doi.org/10.1016/j.chroma.2025.466420
  28. Anal Chem. 2025 Oct 09.
      Robust high-throughput screening (HTS) approaches for discovering new chemical entities are desirable for research and translation. Applications for which high-throughput (HT) methods are particularly required also include the screening of potential therapeutics for drug discovery and development, profiling of biofluids for disease biomarker discovery, and clinical diagnostics. Complementing the demand for HTS from specific application areas are substantial technological advancements in the fields of automation, microfluidics, and ambient ionization that facilitate highly automated and sophisticated analytical workflows. The time period spanning 2000-2025 has witnessed a significant expansion in the mass spectrometry (MS) capabilities and technology. This has included novel ionization approaches that can achieve rapid analysis with minimal solvent and sample consumption, while retaining high sensitivity and specificity in the absence of chromatography. Despite the demand for HTS methods and the well-documented analytical capabilities of MS, optical methods dominate as the HTS detection methods of choice. This perspective provides an overview of the evolution of HTS-MS over the last 25 years, focusing on emerging approaches that also provide efficient and sustainable workflows that compete with optical detection. Additionally, this perspective will highlight challenges in the field that may hinder widespread adoption and consider lessons from the COVID-19 pandemic, as well as the impact of sustainability on the future of HTS-MS and analytical chemistry.
    DOI:  https://doi.org/10.1021/acs.analchem.5c02331
  29. J Sep Sci. 2025 Oct;48(10): e70289
      The introduction of mass spectrometry in the analysis of pesticide residues has significantly enhanced analytical efficiency, reduced analysis times, and enabled ultra-trace detection. However, the matrix effect-wherein target analytes experience interference from the matrix during ionization-remains a critical issue. In multiresidue pesticide analysis via LC-MS/MS, matrix effects are typically addressed by preparing calibration standards through the dilution of matrix extracts with buffers (organic solvents) or by diluting the sample, which must be manually performed by the analyst. This study developed an automated matrix dilution injection (AMDI) method that leverages the autosampler built-in automatic dilution injection feature in liquid chromatography (LC) to prepare matrix-corrected dilutions and quantify analytes without manual manipulation. The AMDI method was validated by analyzing 71 pesticides in four agricultural commodities, where linearity, accuracy, and precision were assessed using two LC systems with different performances (HPLC-MS/MS and UHPLC-MS/MS). The AMDI method exhibited superior linearity in UHPLC analyses compared with conventional matrix-matched calibration standards. Furthermore, most of the pesticides analyzed exhibited measurement accuracies of 70%-120% and precision with relative standard deviations below 10%.
    Keywords:  LC‐MS/MS; automated injection; matrix effect; pesticide
    DOI:  https://doi.org/10.1002/jssc.70289
  30. Arch Toxicol. 2025 Oct 07.
      The rapid emergence of synthetic cannabinoid receptor agonists (SCRAs) poses challenges for drug testing, particularly when analyzing urine samples due to the rapid metabolization of the parent compounds. In early 2023, two novel SCRAs were reported to the European Union Drugs Agency (EUDA): ADMB-3TMS-PrINACA and Cumyl-3TMS-PrINACA, which are both indazole SCRAs featuring a trimethylsilyl propyl moiety connected to the tertiary indazole nitrogen. Peaks corresponding to metabolites of ADMB-BINACA (also known as ADB-BUTINACA) and Cumyl-4CN-BINACA observed with retention time shifts in a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for detecting SCRAs were later identified as metabolites of ADMB- and Cumyl-3TMS-PrINACA. Pooled human liver microsome (pHLMs, 25 µmol/L) and pooled human hepatocyte (PHH, 20 µmol/L) assays were performed to generate metabolites. Additionally, human urine samples were analyzed by reversed phase liquid chromatography-quadrupole-time-of-flight-mass spectrometry (LC-QToF-MS), assisted by GLORYx and BioTransformer 3.0 for in silico metabolite prediction. Gas chromatography-mass spectrometry (GC-MS) was used to identify substances in seized materials. In total, 34 metabolites for ADMB-3TMS-PrINACA and 38 for Cumyl-3TMS-PrINACA were tentatively identified. Major biotransformations included side chain monohydroxylation (specific markers) and TMS-group cleavage, likely initiated by oxidative Si-demethylation followed by further hydroxylation resulting in an N-3-OH-propyl metabolite and further oxidation to the respective N-propionic acid. Most of these biomarkers were detected in the blood, urine, and stomach content of a deceased poly-drug user exposed to ADMB-3TMS-PrINACA. Overall, Cumyl-3TMS-PrINACA was more prevalent than ADMB-3TMS-PrINACA in Germany according to routine urine testing. This work provides the first investigation of the metabolic fate and suggests biomarkers for these new SCRAs.
    Keywords:  3-Trimethylsilyl propyl tail (3TMS-moiety); In silico metabolite prediction; LC-HRMS/MS; Metabolism; New psychoactive substances; Synthetic cannabinoids
    DOI:  https://doi.org/10.1007/s00204-025-04204-y
  31. Environ Sci Technol. 2025 Oct 09.
      Reliable quantification of polychlorinated alkanes (PCAs) remains a major challenge, hindering environmental research across diverse matrices. Each sample can contain over 500 homologue groups, collectively producing >1000 m/z ratios that require interference checks. High-resolution mass spectrometry methods vary in ionization signals and data formats and require specialized algorithms for quantification. CPxplorer streamlines data processing through the integration of three modules: (1) CPions generates target ion sets and isotopic thresholds for compound identification into the next module; (2) Skyline performs instrument-independent data integration, interference evaluation, and homologue profiling; and (3) CPquant deconvolves homologues and reports concentrations using reference standards and homologue profiles from Skyline. Evaluation of the workflow with NIST-SRM-2585 dust and ERM-CE100 fish tissue material yielded comparable results across raw data formats from different instruments. Further applications of CPxplorer across diverse matrices, including indoor dust, organic films, silicone wrist bands, and food samples, demonstrated the usefulness in biological and environmental monitoring. Compared to existing tools limited to qualitative detection, CPxplorer enables quantitative outputs, reduces processing time, and expands functionality to PCA-like substances (e.g., BCAs) and PCA degradation products (e.g., OH-PCAs). CPxplorer reduces learning barriers, empowers users to quantify PCAs across various analytical instruments, and contributes to generating comparable results in the field.
    Keywords:  analytical method; chlorinated paraffins; data harmonization; persistent organic pollutants; polychlorinated alkanes; quantification
    DOI:  https://doi.org/10.1021/acs.est.5c04928
  32. Toxicol Lett. 2025 Oct 07. pii: S0378-4274(25)02687-6. [Epub ahead of print]413 111741
      Exposure to methanethiol (MT) presents a significant challenge in public healthcare and could be a concern in the context of terrorist attacks. Therefore, reliable verification procedures for MT intoxication are essential for forensic, toxicological, and clinical purposes. We developed and validated a bioanalytical method for the simultaneous detection and identification of biomarkers indicative of MT exposure. Neat human serum albumin (HSA) and human plasma were incubated with MT to form adducts, which served as references. Subsequently, HSA and human plasma were subjected to proteolysis using two proteases, resulting in the formation of disulfide adducts detected as adducts of the single amino acid cysteine (MT-Cys), the dipeptide cysteine-proline (MT-Cys34Pro), and the tripeptides aspartic acid-isoleucine-cysteine (AspIleCys514-MT) and cysteine-proline-phenylalanine (MT-Cys34ProPhe). The adducts were analyzed using a sensitive ultra-performance liquid chromatography-quadrupole exactive orbitrap-high resolution mass spectrometry (UPLC-Q Exactive Orbitrap-HRMS) method operating in full scan mass spectrometry (Full MS) and parallel reaction monitoring (PRM) mode. Time- and concentration-dependent adduct formation during exposure was investigated. The limits of detection (LODs) for the adducts ranged from 20 ng/mL to 2 μg/mL, corresponding to the MT concentrations in plasma. Adducts at Cys34 exhibited the lowest LOD (20 ng/mL MT in plasma), the fastest adduct formation (20 min), and superior stability in plasma at 37 °C. The applicability of the method was demonstrated by the successful detection of adducts in sample from MT-poisoned patient, establishing the method as a reliable bioanalytical procedure for forensic and toxicological analysis.
    Keywords:  Biomarkers; High-resolution mass spectrometry; Human serum albumin-adducts; Methanethiol
    DOI:  https://doi.org/10.1016/j.toxlet.2025.111741
  33. Talanta. 2025 Sep 17. pii: S0039-9140(25)01358-X. [Epub ahead of print]298(Pt A): 128867
      Cardenolides are steroidal glycosides characterized by structural complexity and both medicinal and ecological relevance, necessitating precise and reliable analytical methods for their detection and quantitation. Although cardenolide MS/MS fragmentation has been extensively studied, no method has previously enabled simultaneous detection and quantitation of all glycosides derived from a given genin. In this study, we developed group-specific MS/MS methods for comprehensive screening of cardenolide glycosides containing 31 distinct genin backbones, i.e. aglycones. Application of these 31 genin-specific methods enabled detection of more than 300 glycosides in 23 plant species, several of which were represented in multiple tissue types. The approach successfully distinguished all genins from each other, including those with identical m/z values at the same time minimizing false positives from structurally related steroids such as bufadienolides and saponins. Method validations demonstrated low limits of detection (LOD) and limits of quantitation (LOQ), where the lowest limit of detection (LLOD) values varied between 1.5 and 74.6 ng/mL, apart from a single outlier exhibiting a substantially higher LLOD. Wide linear ranges were also achieved, with most upper limits of quantitation (ULOQ) between 1 and 5 μg/mL. Matrix effect and repeatability assessments indicated only minor variation for most methods. The genin-specific MS/MS strategy enables rapid, high-throughput analysis of cardenolide glycosides without loss of sensitivity or selectivity, where comparisons with compound-specific methods revealed only minor differences in analytical performance. These results highlight the robustness and effectiveness of the group-specific methodology for both qualitative and quantitative applications in cardenolide research.
    Keywords:  Cardenolide; Cardiac glycoside; Group-specific; LC-MS/MS; MRM; Mass spectrometry
    DOI:  https://doi.org/10.1016/j.talanta.2025.128867
  34. J Chromatogr Sci. 2025 Oct 07. pii: bmaf052. [Epub ahead of print]63(9):
      An Ultra Performance Liquid Chromatography - Mass Spectrometry/Mass Spectrometry (UPL-MS/MS) method for simultaneous determination of 8, 11, 12, 20- hydroxyeicosatetraenoic acids (HETEs) and 13 s-hydroxyoctadecadienoic acid (13 s-HODE) in plasma was developed and optimized. The chromatographic separation of 8, 11, 12, 20-HETEs and 13 s-HODE was achieved on a Peptide Bridged Ethylene Hybrid Particles (BEH) C18 column (2.1 mm × 150 mm, 1.7 μm) with mobile phase A (Water containing 0.1% formic acid) and mobile phase B (acetonitrile containing 0.1% formic acid). HETEs and 13 s-HODE were quantified using multiple reaction monitoring mode. The developed UPLC-MS/MS method was applied to determine the plasma samples of 32 paraquat (PQ) poisoning patients, 20 diquat (DQ) poisoning patients and 38 healthy subjects. The results showed that the 8, 11, 12, 20-HETEs and 13 s-HODE have good linearity (R2 > 0.99) from 0.1-500 ng/mL. The levels of HETEs and 13 s-HODE were dramatically increased in PQ and DQ poisoning patients. There were high correlation between 8, 11, 12, 20-HETEs and 13 s-HODE. Orthogonal partial least squares discrimination analysis showed that three groups were distributed in different areas and separated well. In conclusion, a sensitive UPLC-MS/MS method had been developed and validated for determination of 8, 11, 12, 20-HETEs and 13 s-HODE in plasma of PQ and DQ patients.
    DOI:  https://doi.org/10.1093/chromsci/bmaf052
  35. Analyst. 2025 Oct 06.
      Food contamination by phthalate esters (PAEs) is an emerging issue due to their ubiquitous behavior. They are present in foods as a result of migration from food packing. They are known as endocrine disruptors and present an environmental health risk. These characteristics pose analytical challenges in their assessment due to contamination during their analysis. In this work, we present a novel, highly functional analytical method for the analysis of six phthalates, namely dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butylphthalate (DBP), butyl benzyl phthalate (BBP), bis(2-ethylhexyl) phthalate (DEHP) and di-n-octyl phthalate (DNOP), in chicken fat tissues. For this purpose, we developed a simple but powerful extraction method without one of the major sources of analysis contamination, the clean-up with solid phase extraction cartridges. The innovation relies on the reduced steps of sample preparation, the minimal sample quantities and the minimal extraction solvent quantities by liquid-liquid extraction with methanol and detection by liquid chromatography with tandem mass spectrometry. The limits of quantification results for each target analyte in the chicken fat tissues were 0.25 μg kg-1 for DMP, 0.5 μg kg-1 for DEP, 1.25 μg kg-1 for DBP, 1.25 μg kg-1 for BBP, 2.5 μg kg-1 for DEHP and 2 μg kg-1 for DNOP, respectively. The calculated measurement uncertainty ranges from 7.2% to 16%. The present validated method was found to be precise, sensitive, and rapid to determine 6 PAEs in chicken fat tissues. This method also shows potential for application in other matrices such as water and food. This approach reduces solvent consumption, minimizes contamination risk, and aligns with the principles of Green Analytical Chemistry. Additionally, this method makes use of only 10 mg of sample, demonstrating that accurate quantification of trace contaminants is achievable with minimal sample amounts, as supported by recent miniaturized methodologies for fat-rich matrices.
    DOI:  https://doi.org/10.1039/d5an00465a
  36. Curr Res Food Sci. 2025 ;11 101205
      Anabolic steroid (AS) residues in animal-derived foods continues to pose a significant concern due to their potential risks to food safety and human health. In this study, we developed an integrated strategy combining targeted quantification and suspect screening for the comprehensive detection of AS residues in beef. The analytical workflow included optimized solid-phase extraction followed by Ultra-high-performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS) in scheduled Multiple Reaction Monitoring mode for targeted analysis, and UHPLC coupled with high resolution mass spectrometry (UHPLC-HRMS) in data-independent acquisition mode for suspect screening. Method validation confirmed satisfactory linearity (R2 > 0.97), low detection limits (0.003-3 μg/kg), and acceptable recoveries (52.4-126.8 %). 15 AS compounds were identified across beef products from diverse global sources. The developed strategy enables sensitive and efficient detection of structurally diverse AS residues in complex food matrices, which provide robust technical support for ensuring food safety.
    Keywords:  Anabolic steroids; Animal-derived food; Food safety; Liquid chromatography-tandem mass spectrometry (LC-MS/MS); Suspect screening
    DOI:  https://doi.org/10.1016/j.crfs.2025.101205