bims-metlip 2024-10-27 papers

bims-metlip

Biomed News

on Methods and protocols in metabolomics and lipidomics

Issue of 2024–10–27
25 papers selected by
Sofia Costa, Matterworks

Development of microflow ultra high performance liquid chromatography-mass spectrometry metabolomic assays for analysis of mammalian biofluids.
[Simultaneous determination of 17 perfluoroalkyl substances in beef by EMR-Lipid dispersive solid-phase extraction and ultra performance liquid chromatography-tandem mass spectrometry].
Simultaneous Quantification of Serum Symmetric Dimethylarginine, Asymmetric Dimethylarginine and Creatinine for Use in a Routine Clinical Laboratory.
Comprehensive Coverage of Glycolysis and Pentose Phosphate Metabolic Pathways by Isomer-Selective Accurate Targeted Hydrophilic Interaction Liquid Chromatography-Tandem Mass Spectrometry Assay.
[Determination of three methylimidazole compounds in cosmetics by high performance liquid chromatography-tandem mass spectrometry].
Development of an automated immunologic mass spectrometry (iMS) method to overcome matrix effect for quantification: Steroid hormones as the example.
Nanospray Desorption Electrospray Ionization Mass Spectrometry Imaging (nano-DESI MSI): A Tutorial Review.
[Determination of 42 antimicrobials in disinfection products by dispersive solid phase extraction-high performance liquid chromatography-tandem mass spectrometry].
Rapid QC-MS: Interactive Dashboard for Synchronous Mass Spectrometry Data Acquisition Quality Control.
Introducing Molecular Hypernetworks for Discovery in Multidimensional Metabolomics Data.
COLMAR1d: A Web Server for Automated, Quantitative One-Dimensional Nuclear Magnetic Resonance-Based Metabolomics at Arbitrary Magnetic Fields.
A novel quantitative method for the determination of 10B-carrier boronophenylalanine in rat plasma by UHPLC-MS/MS and comparison with ICP-MS.
[Advances in the application of liquid chromatography tandem mass spectrometry for therapeutic drug monitoring].
Leveraging the potential of 1.0-mm i.d. columns in UHPLC-HRMS-based untargeted metabolomics.
Quantification of guanidine in environmental samples using benzoin derivatization and LC-MS analysis.
MALDI versus DESI mass spectrometry imaging of lipids in atherosclerotic plaque.
Liquid Chromatography-Tandem Mass Spectrometry Method for Therapeutic Drug Monitoring of Dalbavancin in Plasma of Pediatric and Young Adult Patients.
METASPACE-ML: Context-specific metabolite annotation for imaging mass spectrometry using machine learning.
Current status of MSI research in Japan to measure the localization of natural products in plants.
High-Resolution Acoustic Ejection Mass Spectrometry for High-Throughput Library Screening.
Bioanalytical method development and validation of docetaxel and carvacrol in mice plasma using LC-QqQ-MS/MS.
Rapid and sensitive liquid chromatographic-tandem mass spectrometric methods for the quantitation of dolutegravir in human plasma and breast milk.
Characterization of etomidate and emerging analogs in human hair using UHPLC-MS/MS and confirmation in real forensic cases.
Recent Advances in Metabolomics and Lipidomics Studies in Human and Animal Models of Multiple Sclerosis.
A Versatile Ultra-High-Performance Liquid Chromatography-Full-Scan High-Resolution Mass Spectrometry Method to Quantify Wine Polyphenols.

Metabolomics. 2024 Oct 25. 20(6): 120

Development of microflow ultra high performance liquid chromatography-mass spectrometry metabolomic assays for analysis of mammalian biofluids.

Annie J Harwood-Stamper, Caroline A Rowland, Warwick B Dunn.

   INTRODUCTION AND OBJECTIVES: The application of untargeted metabolomics assays using ultra high performance liquid chromatography-mass spectrometry (UHPLC-MS) to study metabolism in biological systems including humans is rapidly increasing. In some of these studies there is a requirement to collect and analyse low sample volumes of biofluids (e.g. tear fluid) or low cell and tissue mass samples (e.g. tissue needle biopsies). The application of microflow, capillary or nano liquid chromatography (≤ 1.0 mm column internal diameter (i.d.)) theoretically should accomplish a higher assay sensitivity compared to analytical liquid chromatography (2.1-5.0 mm column internal diameter). To date, there has been limited research into microflow UHPLC-MS assays that can be applied to study samples of low volume or mass.
METHODS: This paper presents three complementary UHPLC-MS assays (aqueous C18 reversed-phase, lipidomics C18 reversed-phase and Hydrophilic Interaction Liquid Chromatography (HILIC)) applying 1.0 mm internal diameter columns for untargeted metabolomics. Human plasma and urine samples were applied for the method development, with porcine plasma, urine and tear fluid used for method assessment. Data were collected and compared for columns of the same length, stationary phase and stationary phase particle size but with two different column internal diameters (2.1 mm and 1.0 mm).
RESULTS AND CONCLUSIONS: All three assays showed an increase in peak areas and peak widths when applying the 1.0 mm i.d. assays. HILIC assays provide an advantage at lower sample dilutions whereas for reversed phase (RP) assays there was no benefit added. This can be seen in the validation study where a much higher number of compounds were detected in the HILIC assay. RP assays were still appropriate for small volume samples with hundreds of compounds being detected. In summary, the 1.0 mm i.d. column assays are applicable for small volume samples where dilution is required during sample preparation.

Keywords:  Metabolomics; Microflow liquid chromatography; Plasma; Tears; UHPLC-MS; Urine

DOI:  https://doi.org/10.1007/s11306-024-02187-y
Se Pu. 2024 Nov;42(11): 1032-1041

[Simultaneous determination of 17 perfluoroalkyl substances in beef by EMR-Lipid dispersive solid-phase extraction and ultra performance liquid chromatography-tandem mass spectrometry].

Qiao-Li Qiu, Sheng-Dong Pan, Li Wang, Lan-Yun Fang, Xiao-Hong Chen, Mi-Cong Jin.

  The ability to accurately analyze perfluoroalkyl substance (PFAS) levels in beef is imperative in order to effectively assess food-safety risks and ensure consumer safety because PFASs are harmful and prevalent in beef. In this study, we developed a rapid and accurate method for the simultaneously determination of the 17 PFASs in beef using dispersive solid-phase extraction (d-SPE) and ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), and optimized the mobile phase system, extraction solvent, and d-SPE materials. Samples were finally extracted using 0.1% (v/v) formic acid in acetonitrile, cleaned using d-SPE with PSA, C18, GCB, and EMR-Lipid, separated using an Acquity Premier BEH C18 column (100 mm×2.1 mm, 1.7 μm) with 0.5 mmol/L ammonium fluoride aqueous solution and methanol as the mobile phases at a flow rate of 0.3 mL/min. Analytes were detected in negative ion switching mode (ESI-) with multiple reaction monitoring (MRM) scanning, and quantitatively analyzed using the internal standard method. The 17 PFASs exhibited linearity in the 0.2-20.0 μg/L range under the optimal experimental conditions, with correlation coefficients of 0.9915-0.9999. The method delivered limits of detection (LODs) of 0.003-0.007 μg/kg and limits of quantification (LOQs) of 0.01-0.02 μg/kg. The 17 PFASs exhibited recoveries of 71.1%-127.4% with RSDs of 0.6%-14.4% when spiked at three levels (0.05, 0.5, and 1.8 μg/kg). We optimized the mobile phase system, which revealed that, compared with 2.0, 5.0, and 10.0 mmol/L ammonium formate or ammonium acetate in aqueous methanol, 0.5 mmol/L ammonium fluoride in aqueous methanol exhibited higher sensitivities for all the 17 PFASs, with PFASs bearing long-chain carboxylic acids (C10-C18) showing 1-2 fold increases in sensitivity. PFASs do not dissociate in acidic environments, favoring their entry into the organic phase. Therefore, we investigated the effect of extractant acidity, which revealed that the 17 PFASs were better extracted using 0.1% (v/v) formic acid in acetonitrile. The beef matrix has a complex composition; consequently, d-SPE adsorbents were required to purify samples and reduce matrix effects. The purification effects of four adsorbents (PSA, C18, GCB, and EMR-Lipid) toward the 17 PFASs and the amount of EMR-Lipid used were investigated, which revealed that 100 mg PSA+80 mg C18+40 mg GCB+150 mg EMR-Lipid exhibited superior matrix-purification behavior. We also investigated the effects of various injection solutions and types of syringe filter, with pure methanol selected for reconstitution and high-speed supernatant centrifugation applied prior to injection. The developed method is simple, rapid, sensitive, and reproducible, and can be used to simultaneously, rapidly, and accurately determine various perfluoroalkyl compounds in beef.

Keywords:  beef; dispersive solid-phase extraction (d-SPE); perfluoroalkyl substances (PFASs); ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS)

DOI:  https://doi.org/10.3724/SP.J.1123.2024.02010
Ann Clin Biochem. 2024 Oct 23. 45632241298161

Simultaneous Quantification of Serum Symmetric Dimethylarginine, Asymmetric Dimethylarginine and Creatinine for Use in a Routine Clinical Laboratory.

David John Marshall, James M Hawley, Brian G Keevil.

  Background Symmetric dimethylarginine (SDMA) and asymmetric dimethylarginine (ADMA) are naturally occurring amino acids classed as uremic toxins by the EUTOX working group. SDMA is principally excreted through the kidneys and is a well-known renal function marker, ADMA is a potent inhibitor of nitric oxide production. Here, we describe the development of a rapid and sensitive liquid chromatography tandem mass spectrometry method for simultaneous measurement of SDMA, ADMA and creatinine. Method Serum samples were prepared by protein precipitation and dilution with acetonitrile prior to injection onto a Waters TQS-Micro. Multiple reaction monitoring was used to detect SDMA, ADMA, creatinine, and their corresponding internal standard transitions after separation with a HILIC analytical column. Sample stability and intra-individual variation studies were also assessed following ethical approval. Results The retention time for creatinine was 0.43, SDMA 1.10 and ADMA 1.14 minutes. Mean recovery for creatinine was 103%, SDMA was 100% and ADMA was 103%, matrix effects were minimal (<6%). Lower limit of quantitation for creatinine and SDMA/ADMA was 17.5 µmol/L and 0.1 µmol/L respectively. Analytical imprecision showed a coefficient of variation <10% for all analytes across the working range of the assays. Intra-individual variation for creatinine was 4.7%, SDMA 7.5% and ADMA 7.6%. Discussion We have developed a rapid assay for LC-MS/MS measurement of SDMA, ADMA and creatinine in a routine clinical laboratory. It is simple, reproducible, and easy to perform. The stability of SDMA and ADMA pre- and post-centrifugation allows for their routine use without any special sample handling requirements.

Keywords:  Analytes; Clinical studies; Creatinine; Laboratory methods; Mass spectrometry; Renal disease

DOI:  https://doi.org/10.1177/00045632241298161
Anal Chem. 2024 Oct 19.

Comprehensive Coverage of Glycolysis and Pentose Phosphate Metabolic Pathways by Isomer-Selective Accurate Targeted Hydrophilic Interaction Liquid Chromatography-Tandem Mass Spectrometry Assay.

Kristian Serafimov, Michael Lämmerhofer.

The accurate liquid chromatography-tandem mass spectrometry analysis of phosphorylated isomers from glycolysis and pentose phosphate pathways is a challenging analytical problem in metabolomics due to extraction problems from the biological matrix, adherence to stainless steel surfaces leading to tailing in LC, and incomplete separation of hexose and pentose phosphate isomers. In this study, we present a targeted HILIC-ESI-MS/MS method based on a BEH amide fully porous 1.7 μm particle column with an inert surface coating of column hardware and multiple reaction monitoring (MRM) acquisition fully covering the glycolysis and pentose phosphate pathway metabolites. To minimize contact of the phosphorylated analytes with stainless steel surfaces, a μ-ESI-MS probe with a hybrid electrode made of PEEKsil was employed. Optimized HILIC gradient elution conditions with 100 mM ammonium formate (pH 11) provided the separation of hexose monophosphate and pentose phosphate isomers. To ensure good retention time repeatability in HILIC, perfluoroalkoxy alkane bottles were used for the mobile phase (with sd over 60 runs between 0.01 and 0.02 min). For the quantitative assay, the U-13C-labeled cell extract was spiked prior to extraction by metal oxide-based affinity chromatography (MOAC) with TiO2 beads. The concentrations of the 24 targets were quantified in HeLa and human embryonic kidney (HEK293) cells. Erastin-induced ferroptosis in HEK293 cells was accompanied by enhanced levels of fructose-1,6-bis-phosphate, 2- and 3-phosphoglycerate, and 2,3-bis-phosphoglycerate.

DOI: https://doi.org/10.1021/acs.analchem.4c03490
Se Pu. 2024 Nov;42(11): 1052-1058

[Determination of three methylimidazole compounds in cosmetics by high performance liquid chromatography-tandem mass spectrometry].

Cui-Ling Cai, Ju Li, Jing Xi, Ying-Ye Hou, Guang-Feng Zeng, Jian-Jun Xie, Shu-Yue Wu, Lu Wang.

  Methylimidazole compounds are byproducts formed during the caramel-coloring process and are used in various cosmetics. In addition metronidazole is an antibacterial and anti-inflammatory drug commonly used in modern medicine and is used in cosmetics to treat acne in the short-term. The illegal addition of metronidazole during cosmetics production can result in residual 2-methylimidazole (2-MEI), which, along with 4-methylimidazole (4-MEI), is a class 2B carcinogen. Therefore, establishing efficient, accurate, and sensitive analytical techniques for analyzing methylimidazole compounds in cosmetics is an urgent objective. In this study, a high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method for simultaneously determining 1-methylimidazole (1-MEI), 2-MEI, and 4-MEI in cosmetics was developed. Cosmetics samples were extracted via ultrasonication in acetonitrile and purified using a mixed cation-exchange (MCX) solid-phase extraction (SPE) column, with subsequent drying under a stream of nitrogen and redissolution in acetonitrile. The resulting solution was then filtered through a 0.22 μm organic filter membrane for further testing. The analytes were separated using an XBridge® shield RP18 chromatographic column (150 mm×4.6 mm, 3.5 μm) and isocratically eluted with 20 mmol/L ammonium formate solution (containing 0.1% formic acid)-acetonitrile (98∶2, v/v). The target compounds were ionized by electrospray ionization (ESI) source, analyzed in multi-reaction monitoring (MRM) mode, and quantified using the external standard method, with the peak area of the quantitative ion and the mass concentration of the compound taken as the longitudinal and transverse coordinates, respectively. Matrix-matching working curves were also constructed. 1-MEI exhibited good linear relationships in the range of 5-200 μg/L, with correlation coefficients (r2)≥0.9994, while 2-MEI and 4-MEI showed good linearities in the range of 2-100 μg/L with r2≥0.9984. The three methylimidazole compounds exhibited limits of detection (LODs) and quantification (LOQs) of 10-30 μg/kg and 25-100 μg/kg, respectively. Under three spiked levels (LOQ, 2LOQ, 10LOQ), the recoveries of three methylimidazole compounds were 80.9%-107.9%, with relative standard deviations (RSDs, n=6) of 1.2%-12.8%. The practicability of the method was examined using 48 cosmetic samples; 4-MEI was detected in nine samples at contents of 26-1000 μg/kg, while two samples contained 240 and 267 μg/kg of 2-MEI, respectively. 1-MEI was not detected in any of the 48 samples tested. The developed method is simple, fast, and highly sensitive, and provides methodological support for assessing risks and monitoring the three methylimidazole compounds in cosmetics through screening.

Keywords:  1-methylimidazole (1-MEI); 2-methylimidazole (2-MEI); 4-methylimidazole (4-MEI); cosmetics; high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS)

DOI:  https://doi.org/10.3724/SP.J.1123.2023.11011
Talanta. 2024 Oct 12. pii: S0039-9140(24)01420-6. [Epub ahead of print]282 127041

Development of an automated immunologic mass spectrometry (iMS) method to overcome matrix effect for quantification: Steroid hormones as the example.

Xiaoyi Yi, Xijiu Li, Huanchang Luo, Guanfeng Lin, Jianwei Zhou, Yufeng Xiong, Yingsong Wu.

  Liquid chromatography-tandem mass spectrometry (LC-MS/MS) shows great promise in clinical application for its high specificity, high sensitivity and wide linear range for the determination of small molecules. However, its application in clinical laboratory is hampered by matrix effect of clinical samples which could greatly affect quantification accuracy and the difficulty to be automated for the traditional sample preparation procedures. Thus, new techniques which could achieve selective enrichment to minimize matrix effect and automatic sample preparation of mass spectrometry are needed. We developed an immunologic mass spectrometry (iMS) method to overcome matrix effect and its clinical application was demonstrated for automatic analysis of testosterone (T), progesterone (P) and estradiol (E2) in human serum simultaneously. Firstly, three monoclonal antibodies were coupled to magnetic beads for selective enrichment of target hormones from serum. The immunomagnetic beads were separated, washed and eluted automatically for LC-MS/MS analysis. Analytical performance of the iMS method was validated and compared with traditional LC-MS/MS and chemiluminescence immunoassay (CLIA). Hormone levels were measured for 160 pregnancy women at different gestational weeks. Results showed that target hormones could be selectively captured with absolute recoveries of 93.9%-110.8 %. Relative responses for high, medium and low concentrations of the hormones between serum and methanol solution were 98.0%-109.7 %, 92.2%-105.3 % and 91.7%-96.0 % for T, P and E2, respectively. Calibration curves prepared in methanol solution, BSA solution and blank serum showed good consistency for the iMS method. The automated iMS method could overcome matrix effect of LC-MS/MS and cross-reaction of CLIA. Matrix effect of the iMS method was negligible as high specificity of target hormone enrichment before LC-MS/MS analysis. Matrix-matched calibration standards were no longer necessary for accurate quantification, which was of great benefit for the clinical application of mass spetrometry.

Keywords:  Automation; Immunologic mass spectrometry; Liquid chromatography-tandem mass spectrometry; Matrix effect; Monoclonal antibody

DOI:  https://doi.org/10.1016/j.talanta.2024.127041
ACS Meas Sci Au. 2024 Oct 16. 4(5): 475-487

Nanospray Desorption Electrospray Ionization Mass Spectrometry Imaging (nano-DESI MSI): A Tutorial Review.

Mushfeqa Iqfath, Syeda Nazifa Wali, Sara Amer, Emerson Hernly, Julia Laskin.

Nanospray desorption electrospray ionization (nano-DESI) is a liquid-based ambient mass spectrometry imaging (MSI) technique that enables visualization of analyte distributions in biological samples down to cellular-level spatial resolution. Since its inception, significant advancements have been made to the nano-DESI experimental platform to facilitate molecular imaging with high throughput, deep molecular coverage, and spatial resolution better than 10 μm. The molecular selectivity of nano-DESI MSI has been enhanced using new data acquisition strategies, the development of separation and online derivatization approaches for isobar separation and isomer-selective imaging, and the optimization of the working solvent composition to improve analyte extraction and ionization efficiency. Furthermore, nano-DESI MSI research has underscored the importance of matrix effects and established normalization methods for accurately measuring concentration gradients in complex biological samples. This tutorial offers a comprehensive guide to nano-DESI experiments, detailing fundamental principles and data acquisition and processing methods and discussing essential operational parameters.

DOI: https://doi.org/10.1021/acsmeasuresciau.4c00028
Se Pu. 2024 Nov;42(11): 1077-1086

[Determination of 42 antimicrobials in disinfection products by dispersive solid phase extraction-high performance liquid chromatography-tandem mass spectrometry].

Jia-Qi Tong, Gu-Huan Zhu, Hang-Zhen Lan, Hong-Lan Shi, Xiao-Yan Zhu, Yao Sun.

  Antimicrobials inhibit the growth and reproduction of microorganisms thereby alleviating skin and other problems caused by microorganisms. Antimicrobials are classified into different categories, including antibacterials, antifungals, and antivirals, among others, and include azoles, sulfonamides, tetracyclines, quinolones, and many other classes of synthetic and natural compound. The inappropriate or excessive use of antimicrobials can damage skin and other human organs and increase antimicrobial resistance. Relevant regulations and standards clearly state that antimicrobials are prohibited for use as ingredients in disinfection products. However, since antimicrobials enhance the disinfection or antibacterial effect of a product, with a significant short-term effect, antimicrobials are occasionally illegally added to disinfectant products, including those intended for human use. Therefore, establishing testing methods that provide technical support for enforcing regulations is an urgent objective. Herein, a method was established for the analysis of 42 antimicrobials in disinfection products, that is applicable to common types of disinfection-product matrix, including creams, gels, and aqueous solutions, using high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) combined with dispersive solid phase extraction. The 42 antimicrobials comprise antibacterials, antifungals, and antivirals, and include seven sulfonamides, ten quinolones, three lincosamides, five tetracyclines, three macrolides, eight azoles, three purine nucleoside analogs, one furan, one nonpolyene antifungal, and one steroid. Briefly, 0.2 g of a sample was first dispersed in 2 mL of water and then extracted with 10 mL of 0.5% formic acid in acetonitrile, with 3 g of anhydrous Na2SO4 added to remove water. After centrifugation, 5 mL of the supernatant was cleaned using dispersive solid phase extraction with EMR-Lipid as the adsorbent. Lipids, waxes, surfactants, and moisturizing lubricants are commonly used as cream and gel matrices. Matrix substances containing long carbon chains dissolved in acetonitrile were removed using the EMR-Lipid adsorbent. Target analytes were separated on a Poroshell 120 EC-C18 analytical chromatography column (150 mm×3.0 mm, 2.7 μm), with 0.1% formic acid in acetonitrile and 0.1% formic acid aqueous solution used as mobile phases under gradient-elution conditions. The target analytes in the test solution were detected in positive ionization (ESI+) and multi-reaction-monitoring (MRM) modes. Analytes were characterized in terms of their retention times and selected ions, and quantified using the external-standard method. The main factors affecting method response, recovery, and sensitivity, such as the extraction method and solvent, purification method and adsorbent, mobile phase, and MS conditions, were examined during sample pretreatment and instrumental analysis. The 42 antimicrobials were effectively separated under the optimized experimental conditions; the target compounds exhibited linear working curves in the 0.25-5.0 mg/kg concentration range, with correlation coefficients (r) greater than 0.99. Limits of detection (LODs) for the 42 antimicrobials were determined from the signal-to-noise ratios (S/N) of their chromatographic peaks. LODs of 0.03-0.10 mg/kg were determined for the three matrices using 0.2-g samples and 10-mL test solution. Recoveries of 80.3-109.8%, with relative standard deviations (RSDs) of less than 9.8%, were obtained by determining three levels of each target analyte added to the three blank matrices; this process was repeated for six parallel samples. The developed method was used to analyze antimicrobials in commercially available disinfection products, with two sample batches testing positive. The established method is simple, accurate, precise, and suitable for the rapid screening and quantification of antimicrobials in disinfection products. This study provides powerful technical support for regulating the illegal addition of related antimicrobials to disinfection products.

Keywords:  antimicrobials; disinfection products; dispersive solid phase extraction; high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS)

DOI:  https://doi.org/10.3724/SP.J.1123.2024.02018
Anal Chem. 2024 Oct 25.

Rapid QC-MS: Interactive Dashboard for Synchronous Mass Spectrometry Data Acquisition Quality Control.

Wasim Sandhu, Ira J Gray, Sarah Lin, Joshua E Elias, Brian C DeFelice.

Consistently collecting high-quality liquid chromatography-coupled tandem mass spectrometry (LC-MS/MS) data is a time-consuming hurdle for untargeted workflows. Analytical controls such as internal and biological standards are commonly included in high-throughput workflows, helping researchers recognize low-integrity specimens regardless of their biological source. However, evaluating these standards as data are collected has remained a considerable bottleneck─in both person-hours and accuracy. Here we present Rapid QC-MS, an automated, interactive dashboard for assessing LC-MS/MS data quality. Minutes after a new data file is written, a browser-viewable dashboard is updated with quality control results spanning multiple performance dimensions such as instrument sensitivity, in-run retention time shifts, and mass accuracy drift. Rapid QC-MS provides interactive visualizations that help users recognize acute deviations in these performance metrics, as well as gradual drifts over periods of hours, days, months, or years. Rapid QC-MS is open-source, simple to install, and highly configurable. By integrating open-source Python libraries and widely used MS analysis software, it can adapt to any LC-MS/MS workflow. Rapid QC-MS runs locally and offers optional remote quality control by syncing with Google Drive. Furthermore, Rapid QC-MS can operate in a semiautonomous fashion, alerting users to specimens with potentially poor analytical integrity via frequently used messaging applications. Initially developed for integration with Thermo Orbitrap workflows, Rapid QC-MS offers a fast, straightforward approach to help users collect high-quality untargeted LC-MS/MS data by eliminating many of the most time-consuming steps in manual data curation. Download for free: https://github.com/czbiohub-sf/Rapid-QC-MS.

DOI: https://doi.org/10.1021/acs.analchem.4c00786
J Proteome Res. 2024 Oct 22.

Introducing Molecular Hypernetworks for Discovery in Multidimensional Metabolomics Data.

Sean M Colby, Madelyn R Shapiro, Andy Lin, Aivett Bilbao, Corey D Broeckling, Emilie Purvine, Cliff A Joslyn.

  Orthogonal separations of data from high-resolution mass spectrometry can provide insight into sample composition and address challenges of complete annotation of molecules in untargeted metabolomics. "Molecular networks" (MNs), as used in the Global Natural Products Social Molecular Networking platform, are a prominent strategy for exploring and visualizing molecular relationships and improving annotation. MNs are mathematical graphs showing the relationships between measured multidimensional data features. MNs also show promise for using network science algorithms to automatically identify targets for annotation candidates and to dereplicate features associated with a single molecular identity. This paper introduces "molecular hypernetworks" (MHNs) as more complex MN models able to natively represent multiway relationships among observations. Compared to MNs, MHNs can more parsimoniously represent the inherent complexity present among groups of observations, initially supporting improved exploratory data analysis and visualization. MHNs also promise to increase confidence in annotation propagation, for both human and analytical processing. We first illustrate MHNs with simple examples, and build them from liquid chromatography- and ion mobility spectrometry-separated MS data. We then describe a method to construct MHNs directly from existing MNs as their "clique reconstructions", demonstrating their utility by comparing examples of previously published graph-based MNs to their respective MHNs.

Keywords:  feature annotation; hypergraphs; mass spectrometry; metabolomics; molecular hypernetworks; molecular networks; spectral similarity

DOI:  https://doi.org/10.1021/acs.jproteome.3c00634
Anal Chem. 2024 Oct 20.

COLMAR1d: A Web Server for Automated, Quantitative One-Dimensional Nuclear Magnetic Resonance-Based Metabolomics at Arbitrary Magnetic Fields.

Da-Wei Li, Rodrigo Cabrera Allpas, Munki Choo, Lei Bruschweiler-Li, Alexandar L Hansen, Rafael Brüschweiler.

The field of metabolomics, which is quintessential in today's omics research, involves the large-scale detection, identification, and quantification of small-molecule metabolites in a wide range of biological samples. Nuclear magnetic resonance spectroscopy (NMR) has emerged as a powerful tool for metabolomics due to its high resolution, reproducibility, and exceptional quantitative nature. One of the key bottlenecks of metabolomics studies, however, remains the accurate and automated analysis of the resulting NMR spectra with good accuracy and minimal human intervention. Here, we present the COLMAR1d platform, consisting of a public web server and an optimized database, for one-dimensional (1D) NMR-based metabolomics analysis to address these challenges. The COLMAR1d database comprises more than 480 metabolites from GISSMO enabling a database query of spectra measured at arbitrary magnetic field strengths, as is demonstrated for spectra acquired between 1H resonance frequencies of 80 MHz and 1.2 GHz of mouse serum, DMEM cell growth medium, and wine. COLMAR1d combines the GISSMO metabolomics database concept with the latest tools for automated processing, spectral deconvolution, database querying, and globally optimized mixture analysis for improved accuracy and efficiency. By leveraging advanced computational algorithms, COLMAR1d offers a user-friendly, automated platform for quantitative 1D NMR-based metabolomics analysis allowing a wide range of applications, including biomarker discovery, metabolic pathway elucidation, and integration with multiomics strategies.

DOI: https://doi.org/10.1021/acs.analchem.4c02688
J Pharm Biomed Anal. 2024 Oct 20. pii: S0731-7085(24)00580-6. [Epub ahead of print]253 116538

A novel quantitative method for the determination of 10B-carrier boronophenylalanine in rat plasma by UHPLC-MS/MS and comparison with ICP-MS.

Yang Hu, Xin Jiang, Xiefeng Zhang, Yuxin Lan, Shaohui Cai, Taotao Xu, Xinyue Zhuang, Morili Asheng, Jing Zeng, Yongping Qin, Guangsheng Qian.

  L-Boronophenylalanine (BPA), a widely used 10B carrier for clinical boron neutron capture therapy (BNCT), was quantified in rat plasma through a simple, effective and stable ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method. Chromatographic separation was performed on an ACQUITY UPLC HSS T3 (100 mm × 2.1 mm, 1.8 μm) column with the mobile phase of 0.5 % formic acid aqueous solution and acetonitrile. For the detector, the m/z ion pairs used for quantification were 209.1→120.1 for BPA and 210.1→120.1 for internal standard in a positive mode by electrospray ionization (ESI) using multiple reaction monitoring (MRM). The method is specific and robust with rare affection by endogenous substances in the matrix. A good linear relationship was observed over 80-80000 ng/mL (r2 = 0.9993). The values of inter- and intra-day accuracy and precision were within the acceptance criteria of ±15 %. BPA was found to be stable under different experimental conditions. This developed method was successfully applied on a pharmacokinetic experiment on Sprague-Dawley rats (intravenous injection, 125 mg/kg) and a comparation between UHPLC-MS/MS and ICP-MS for BPA was carried out.

Keywords:  Boron neutron capture therapy; Boronophenylalanine; ICP-MS; Pharmacokinetics; UHPLC-MS/MS

DOI:  https://doi.org/10.1016/j.jpba.2024.116538
Zhonghua Yu Fang Yi Xue Za Zhi. 2024 Oct 06. 58(10): 1604-1609

[Advances in the application of liquid chromatography tandem mass spectrometry for therapeutic drug monitoring].

J X Liu, W Guo.

Therapeutic drug monitoring is a good interpretation of personalized medicine, which helps to improve the safety and effectiveness of patient medication. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) has gradually been widely accepted by clinical laboratories due to its characteristics of specificity, sensitivity, and flexibility in method development. This article introduces the importance and analytical techniques for therapeutic drug monitoring, describes the application and development of liquid chromatography tandem mass spectrometry for therapeutic drug monitoring, new advances in the detection of different drug types and sample types, and challenges in automation, convenience, and standardization.

DOI: https://doi.org/10.3760/cma.j.cn112150-20240419-00328
Anal Bioanal Chem. 2024 Oct 24.

Leveraging the potential of 1.0-mm i.d. columns in UHPLC-HRMS-based untargeted metabolomics.

Danila La Gioia, Emanuela Salviati, Manuela Giovanna Basilicata, Claudia Felici, Oronza A Botrugno, Giovanni Tonon, Eduardo Sommella, Pietro Campiglia.

  Untargeted metabolomics UHPLC-HRMS workflows typically employ narrowbore 2.1-mm inner diameter (i.d.) columns. However, the wide concentration range of the metabolome and the need to often analyze small sample amounts poses challenges to these approaches. Reducing the column diameter could be a potential solution. Herein, we evaluated the performance of a microbore 1.0-mm i.d. setup compared to the 2.1-mm i.d. benchmark for untargeted metabolomics. The 1.0-mm i.d. setup was implemented on a micro-UHPLC system, while the 2.1-mm i.d. on a standard UHPLC, both coupled to quadrupole-orbitrap HRMS. On polar standard metabolites, a sensitivity gain with an average 3.8-fold increase over the 2.1-mm i.d., along with lower LOD (LODavg 1.48 ng/mL vs. 6.18 ng/mL) and LOQ (LOQavg 4.94 ng/mL vs. 20.60 ng/mL), was observed. The microbore method detected and quantified all metabolites at LLOQ with respect to 2.1, also demonstrating good repeatability with lower CV% for retention times (0.29% vs. 0.63%) and peak areas (4.65% vs. 7.27%). The analysis of various samples, in both RP and HILIC modes, including different plasma volumes, dried blood spots (DBS), and colorectal cancer (CRC) patient-derived organoids (PDOs), in full scan-data dependent mode (FS-DDA) reported a significant increase in MS1 and MS2 features, as well as MS/MS spectral matches by 38.95%, 39.26%, and 18.23%, respectively. These findings demonstrate that 1.0-mm i.d. columns in UHPLC-HRMS could be a potential strategy to enhance coverage for low-amount samples while maintaining the same analytical throughput and robustness of 2.1-mm i.d. formats, with reduced solvent consumption.

Keywords:  Mass spectrometry; Metabolomics; Microbore; UHPLC; Untargeted

DOI:  https://doi.org/10.1007/s00216-024-05588-z
MethodsX. 2024 Dec;13 102972

Quantification of guanidine in environmental samples using benzoin derivatization and LC-MS analysis.

Richard Gruseck, Marton Palatinszky, Michael Wagner, Thilo Hofmann, Michael Zumstein.

  The recent discovery of guanidine-dependent riboswitches in many microbes raised interest in the biological function and metabolism of this nitrogen-rich compound. However, very little is known about the concentrations of guanidine in the environment. Several methods have been published for quantifying guanidine and guanidino compounds in human urine and blood, often relying on derivatization followed by fluorescence detection. We adapted this analytical approach using benzoin as the derivatization agent to sensitively and selectively quantify guanidine in environmental samples, thereby facilitating future research on the biological and environmental roles of guanidine. This adapted method was applied to human urine, raw wastewater, and biological growth media as relevant matrices. Our liquid chromatography-tandem mass spectrometry analyses of the derivatized solutions identified a different major derivatization product than previously reported. This product was consistently observed across various substrates (guanidine, methylguanidine, and arginine) and derivatization agents (benzoin and anisoin). We observed a constant background signal, restricting our analyses to a lower limit of quantification of 50 nM. Despite this limitation, our method allowed for the quantification of guanidine concentrations significantly lower than those reported in previous derivatization-based studies.•Selective and sensitive detection of guanidine by LC-MS.•Method development and validation for robust detection of guanidine in environmental samples.•Reduction of sample preparation steps and reduced usage of toxic chemicals compared to previous methods.

Keywords:  Environmental and biological matrices; Guanidino compounds; Liquid chromatography coupled to mass spectrometry; Quantification of pre-column derivatized guanidine with LC-MS/MS; Urine

DOI:  https://doi.org/10.1016/j.mex.2024.102972
Rapid Commun Mass Spectrom. 2025 Jan 15. 39(1): e9927

MALDI versus DESI mass spectrometry imaging of lipids in atherosclerotic plaque.

Nuria Slijkhuis, Mark Towers, Emmanuelle Claude, Gijs van Soest.

Mass spectrometry imaging (MSI) is a powerful tool for detecting lipids in tissue sections, with matrix-assisted laser desorption/ionization (MALDI) and desorption electrospray ionization (DESI) as its key ionization techniques. In this study, we examine how MALDI compares with state-of-the-art DESI ionization in identifying lipids in heterogeneous samples, specifically atherosclerotic plaques. Carotid plaques (n = 4) from patients undergoing endarterectomy were snap-frozen, stored at -80°C, and then sectioned for MSI analysis and H&E staining. Measurements were conducted using a SYNAPT XS mass spectrometer in positive ion mode, employing MALDI with a 2,5-dihydroxybenzoic acid (DHB) matrix and DESI with a methanol: water (98:2) (v/v) solvent. Our comparison covered spectral profiles, sensitivity, and image quality generated by these two techniques. We found that both MALDI and DESI are highly suitable techniques for detecting a wide range of lipids in atherosclerotic plaque sections. DESI-MSI exhibited higher ion counts for most lipid classes than MALDI-MSI and provided sharper images. MALDI detected larger amounts of ceramide and hexosylceramide species, possibly due to its efficient generation of dehydrated ions. In contrast, DESI showed greater peak intensities of cholesteryl ester and triacylglyceride species than MALDI, consistent with reduced fragmentation. These findings establish the relative merits of DESI and MALDI and demonstrate their complementarity as techniques for lipid research in MSI.

DOI: https://doi.org/10.1002/rcm.9927
Ther Drug Monit. 2024 Oct 10.

Liquid Chromatography-Tandem Mass Spectrometry Method for Therapeutic Drug Monitoring of Dalbavancin in Plasma of Pediatric and Young Adult Patients.

Alessia Cafaro, Marcello Mariani, Federica Pigliasco, Giammarco Baiardi, Sebastiano Barco, Margherita Biondi, Alessio Mesini, Chiara Russo, Carolina Saffioti, Francesca Mattioli, Elio Castagnola, Giuliana Cangemi.

BACKGROUND: Dalbavancin, an antimicrobial lipoglycopeptide, is authorized in Europe for treating acute bacterial infections of the skin and skin structures in adults and pediatric patients aged 3 months and older. However, off-label dosing regimens have been proposed for various indications beyond acute bacterial infections of the skin and skin structures. This study presents a novel bioanalytical method using liquid chromatography-tandem mass spectrometry to quantify dalbavancin in low-volume plasma samples (50 μL).
METHODS: The method underwent validation in accordance with international guidelines for bioanalytical method validation and was applied to 9 clinical samples obtained from pediatric and young adult patients undergoing dalbavancin therapy. Liquid chromatography-tandem mass spectrometry analyses were conducted at the G. Gaslini Institute in Genoa, Italy, utilizing an Ultimate 3000 ultra high performance liquid chromatography system coupled to a TSQ Quantiva Triple Quadrupole system (Thermo Fisher Scientific, Milan, Italy). The analytical procedure involved the addition of deuterated dalbavancin as internal standard and a rapid extraction from 50 µL of human plasma, followed by chromatographic separation on a Thermo Scientific Accucore Polar Premium column. Accurate quantification of the analyte was achieved through multiple reaction monitoring detection.
RESULTS: The assay exhibited linearity within the concentration range of 0.66-400 mcg/mL in plasma, demonstrating accuracy and reproducibility in the absence of matrix effects. Stability testing was conducted on both quality controls and real samples to establish a robust protocol under real-life conditions.
CONCLUSIONS: This fast and reliable dalbavancin quantitation method could improve current pediatric clinical practice by enabling data collection for future dose recommendations in special patient populations.

DOI: https://doi.org/10.1097/FTD.0000000000001260
Nat Commun. 2024 Oct 22. 15(1): 9110

METASPACE-ML: Context-specific metabolite annotation for imaging mass spectrometry using machine learning.

Bishoy Wadie, Lachlan Stuart, Christopher M Rath, Bernhard Drotleff, Sergii Mamedov, Theodore Alexandrov.

Imaging mass spectrometry is a powerful technology enabling spatial metabolomics, yet metabolites can be assigned only to a fraction of the data generated. METASPACE-ML is a machine learning-based approach addressing this challenge which incorporates new scores and computationally-efficient False Discovery Rate estimation. For training and evaluation, we use a comprehensive set of 1710 datasets from 159 researchers from 47 labs encompassing both animal and plant-based datasets representing multiple spatial metabolomics contexts derived from the METASPACE knowledge base. Here we show that, METASPACE-ML outperforms its rule-based predecessor, exhibiting higher precision, increased throughput, and enhanced capability in identifying low-intensity and biologically-relevant metabolites.

DOI: https://doi.org/10.1038/s41467-024-52213-9
Curr Opin Plant Biol. 2024 Oct 19. pii: S1369-5266(24)00142-0. [Epub ahead of print]82 102651

Current status of MSI research in Japan to measure the localization of natural products in plants.

Kotaro Yamamoto, Mai Uzaki, Katsutoshi Takahashi, Tetsuro Mimura.

  To understand biological functions in organisms, it is important to investigate what is happening in different locations in cells and tissues. The conventional approach is to extract compounds from whole tissue, and then to measure their concentrations or other characteristics using equipment tailored to the different molecules. Recent advances in mass spectrometry have made it possible to measure trace amounts of compounds. Mass spectrometry imaging (MSI), which uses positional information and mass spectrometry data to show where and how much of each compound is present in tissues, has been in the spotlight. Improvements in MSI over the past few decades have enabled its use for visualizing the localization of small molecules including drugs, lipids, and many other compounds in a range of organisms. MSI has also been used to clarify the localization of natural products in plant tissues. This review summarizes the recent research related to MSI technology in Japan.

Keywords:  DESI; ESI; MALDI; Mass spectrometry imaging (MSI); Natural products; SIMS; Secondary metabolite

DOI:  https://doi.org/10.1016/j.pbi.2024.102651
SLAS Technol. 2024 Oct 18. pii: S2472-6303(24)00081-5. [Epub ahead of print] 100199

High-Resolution Acoustic Ejection Mass Spectrometry for High-Throughput Library Screening.

Nate Hoxie, David R Calabrese, Zina Itkin, Glenn Gomba, Min Shen, Meghav Verma, John S Janiszewski, Jonathan H Shrimp, Kelli M Wilson, Sam Michael, Matthew D Hall, Lyle Burton, Tom Covey, Chang Liu.

  An approach is described for high-throughput quality assessment of drug candidate libraries using acoustic ejection high-resolution mass spectrometry (AEMS). Sample introduction from 1536-well plates is demonstrated for this application using 2.5 nL acoustically dispensed sample droplets into an Open Port Interface (OPI) with pneumatically assisted electrospray ionization at a rate of one second per sample. Both positive and negative ionization are shown to be essential to extend the compound coverage of this protease inhibitor-focused library. Specialized software for efficiently interpreting this data in 1536-well format is presented. A new high-throughput method for quantifying the concentration of the components (HTQuant) is proposed that neither requires adding an internal standard to each well nor further encumbers the high-throughput workflow. This approach for quantitation requires highly reproducible peak areas, which is shown to be consistent within 4.4% CV for a 1536-well plate analysis. An approach for troubleshooting the workflow based on the background ion current signal is also presented. The AEMS data is compared to the industry standard LC/PDA/ELSD/MS approach and shows similar coverage but at 180-fold greater throughput. Despite the same ionization process, both methods confirmed the presence of a small percentage of compounds in wells that the other did not. The data for this relatively small, focused library is compared to a larger, more chemically diverse library to indicate that this approach can be more generally applied beyond this single case study. This capability is particularly timely considering the growing implementation of artificial intelligence strategies that require the input of large amounts of high-quality data to formulate predictions relevant to the drug discovery process. The molecular structures of the 872-compound library analyzed here are included to begin the process of correlating molecular structures with ionization efficiency and other parameters as an initial step in this direction.

Keywords:  AE-MS; AEMS; HT-MS; HTMS; QA/QC; acoustic droplet ejection; high-throughput mass spectrometry

DOI:  https://doi.org/10.1016/j.slast.2024.100199
Eur J Mass Spectrom (Chichester). 2024 Oct 21. 14690667241289001

Bioanalytical method development and validation of docetaxel and carvacrol in mice plasma using LC-QqQ-MS/MS.

Shiva Kumar Gogikar, Sibu Sen, Sandeep Daravath, Mayur Aalhate, Srushti Mahajan, Mohd Aman Mohd Ateeq, Pankaj Kumar Singh, Amol G Dikundwar.

  Present work describes the development of a liquid chromatography tandem mass spectrometry-based bioanalytical method for the reliable simultaneous quantification of docetaxel (DXL) and carvacrol (CVL) in the mice plasma. A rapid and sensitive bioanalytical method was developed and optimized in mice plasma using Paclitaxel as an internal standard. Validation of the bioanalytical method was performed according to the ICH M10 guideline covering the range of 9.62-1923.08 ng/mL in the mice plasma milleu at the low, mid, and high-quality control concentrations of 28.86 ng/mL, 961.54 ng/mL, and 1346.15 ng/mL, respectively for both the analytes. Validation parameters such as accuracy, precision, carryover-test, matrix effect, and reinjection reproducibility were carried out and were found in limits. Stability studies (Benchtop, autosampler, freeze-thaw, and long-term) were performed and found to be within limits. The developed bioanalytical method was found to be suitable for the simultaneous quantification of DXL and CVL in the mice plasma.

Keywords:  Docetaxel; LC-QqQ-MS/MS; carvacrol; paclitaxel; validation

DOI:  https://doi.org/10.1177/14690667241289001
J Mass Spectrom Adv Clin Lab. 2024 Nov;34 1-7

Rapid and sensitive liquid chromatographic-tandem mass spectrometric methods for the quantitation of dolutegravir in human plasma and breast milk.

Ashley R Rackow, Aashish Pandey, Amelia L Price, Mark A Marzinke.

   Background: Dolutegravir (DTG) is part of a first-line antiretroviral therapy (ART) for HIV management in drug-naïve individuals and is recommended for the treatment of HIV during pregnancy. Robust analytical tools to quantify DTG are necessary to support clinical trials that characterize its multi-compartment drug distribution.
Methods: Potassium EDTA (K2EDTA) plasma or whole breast milk was spiked with DTG and an isotopically labeled internal standard. Samples were prepared via protein precipitation prior to LC-MS/MS analysis. The assays were validated in accordance with regulatory recommendations.
Results: Analytical measuring ranges for DTG quantitation in plasma and breast milk were 100-10,000 ng/mL and 0.500 to 1000 ng/mL, respectively. Inter-assay precision and accuracy were 2.73 % to 3.41 % and -10.6 % to -5.37 % for plasma, and 4.24 % to 12.4 % and -5.63 % to 7.49 % for breast milk, respectively. DTG was stable for three freeze-thaw cycles and for at least 72 h at room temperature in matrix (plasma or breast milk). Additionally, whole blood was stable for 24 h at room temperature and 2 h under conditions of extended heat and humidity. Matrix effects for DTG in plasma and breast milk ranged from 101 % to 108 % and 78.2 % to 99.3 %, respectively. Quantitation in remnant plasma samples yielded measurable concentrations within the primary linearity of the assay.
Conclusions: Methods to quantify DTG in human plasma and breast milk have been developed and validated. These assays were designed to satisfy all criteria for implementation in clinical and clinical trial settings.

Keywords:  Antiretroviral; Dolutegravir; HIV; LC–MS/MS; Pharmacokinetics; Validation

DOI:  https://doi.org/10.1016/j.jmsacl.2024.09.001
J Chromatogr B Analyt Technol Biomed Life Sci. 2024 Oct 16. pii: S1570-0232(24)00349-0. [Epub ahead of print]1247 124340

Characterization of etomidate and emerging analogs in human hair using UHPLC-MS/MS and confirmation in real forensic cases.

Lina Pei, Shuo Yang, Chaodan Cui, Xin Wang, Ping Xiang, Yonghui Dang, Yan Shi.

  The regulation of etomidate, a widely used drug for anesthesia induction and short surgical procedures, has led to the emergence of etomidate analogs such as metomidate, propoxate, and isopropoxate. This study introduces and validates a simple, rapid, and cost-effective ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method for the determination and quantification of etomidate, etomidate acid, metomidate, propoxate, and isopropoxate in human hair. Using a five-minute gradient elution on a Phenomenex Kinetex Biphenyl column, the method achieves low limits of quantification (LOQs), ranging from 5 to 20 pg/mg. Method validation confirms robust linear calibration curves for the target substances in hair samples within the range of LOQs to 1000 pg/mg, with average correlation coefficients (r) all exceeding 0.999. The method also achieves acceptable intra-day and inter-day precision (<15 %) and trueness(bias, -10.9 % to 14.4 %). The matrix effect ranges from 46.9 % to 94.2 %, and the extraction recovery rate ranges from 84.5 % to 105 %. When applied to authentic cases, this method successfully identified 56 positive samples. The concentrations of etomidate, etomidate acid, metomidate, propoxate, and isopropoxate in positive samples ranged from 27 to 1.5 × 105 pg/mg, 21 to 1.5 × 103 pg/mg, 18 to 8.7 × 104 pg/mg, 25 to 1.6 × 104 pg/mg, and 22 to 5.0 × 105 pg/mg, respectively.

Keywords:  Analogs; Etomidate; Etomidate acid; Hair analysis; Isopropoxate; Metomidate; Propoxate; UHPLC-MS/MS

DOI:  https://doi.org/10.1016/j.jchromb.2024.124340
Metabolites. 2024 Oct 13. pii: 545. [Epub ahead of print]14(10):

Recent Advances in Metabolomics and Lipidomics Studies in Human and Animal Models of Multiple Sclerosis.

Petros Pousinis, Olga Begou, Marina Kleopatra Boziki, Nikolaos Grigoriadis, Georgios Theodoridis, Helen Gika.

  Multiple sclerosis (MS) is a neurodegenerative and inflammatory disease of the central nervous system (CNS) that leads to a loss of myelin. There are three main types of MS: relapsing-remitting MS (RRMS) and primary and secondary progressive disease (PPMS, SPMS). The differentiation in the pathogenesis of these two latter courses is still unclear. The underlying mechanisms of MS are yet to be elucidated, and the treatment relies on immune-modifying agents. Recently, lipidomics and metabolomics studies using human biofluids, mainly plasma and cerebrospinal fluid (CSF), have suggested an important role of lipids and metabolites in the pathophysiology of MS. In this review, the results from studies on metabolomics and lipidomics analyses performed on biological samples of MS patients and MS-like animal models are presented and analyzed. Based on the collected findings, the biochemical pathways in human and animal cohorts involved were investigated and biological mechanisms and the potential role they have in MS are discussed. Limitations and challenges of metabolomics and lipidomics approaches are presented while concluding that metabolomics and lipidomics may provide a more holistic approach and provide biomarkers for early diagnosis of MS disease.

Keywords:  GC-MS; LC-MS; NMR; biomarkers; lipidomics; meta-analysis; metabolomics; multiple sclerosis; pathway analysis; review

DOI:  https://doi.org/10.3390/metabo14100545
Methods Protoc. 2024 Oct 10. pii: 82. [Epub ahead of print]7(5):

A Versatile Ultra-High-Performance Liquid Chromatography-Full-Scan High-Resolution Mass Spectrometry Method to Quantify Wine Polyphenols.

Damien Flores, Emmanuelle Meudec, Aécio Luís de Sousa Dias, Nicolas Sommerer.

  Polyphenols are responsible for wine colour and astringency, and, as antioxidants, they also have beneficial health properties. In this work, we developed a robust full-scan high-resolution mass spectrometry method for the quantification of 90 phenolic compounds in wine samples (either red, rosé, or white wine), using a UHPLC-OrbitrapTM system. With this method, we could conduct a detailed analysis of phenolic compounds in red, rosé, and white wines with great selectivity due to sub-ppm mass accuracy. Moreover, accessing the full-scan spectrum enabled us to monitor all the other compounds detected in the sample, facilitating the adaptability of this method to new phenolic compounds if needed.

Keywords:  Orbitrap mass spectrometry; UHPLC-HRMS; anthocyanins; flavonoids; flavonols; tannins

DOI:  https://doi.org/10.3390/mps7050082