bims-metlip Biomed News
on Methods and protocols in metabolomics and lipidomics
Issue of 2024‒03‒10
25 papers selected by
Sofia Costa, Matterworks



  1. Anal Chim Acta. 2024 Apr 08. pii: S0003-2670(24)00149-1. [Epub ahead of print]1297 342348
      Signaling lipids (SLs) play a crucial role in various signaling pathways, featuring diverse lipid backbone structures. Emerging evidence showing the biological significance and biomedical values of SLs has strongly spurred the advancement of analytical approaches aimed at profiling SLs. Nevertheless, the dramatic differences in endogenous abundances across lipid classes as well as multiple isomers within the same lipid class makes the development of a generic analytical method challenging. A better analytical method that combines comprehensive coverage and high sensitivity is needed to enable us to gain a deeper understanding of the biochemistry of these molecules in health and disease. In this study, we developed a fast and comprehensive targeted ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method for profiling SLs. The platform enables analyses of 260 metabolites covering oxylipins (isoprostanes, prostaglandins and other oxidized lipids), free fatty acids, lysophospholipids, sphingoid bases (C16, C18), platelet activating factors (C16, C18), endocannabinoids and bile acids. Various validation parameters including linearity, limit of detection, limit of quantification, extraction recovery, matrix effect, intra-day and inter-day precision were used to characterize this method. Metabolite quantitation was successfully achieved in both NIST Standard Reference Material for human plasma (NIST SRM 1950) and pooled human plasma, with 109 and 144 metabolites quantitated. The quantitation results in NIST SRM 1950 plasma demonstrated good correlations with certified or previously reported values in published literature. This study introduced quantitative data for 37 SLs for the first time. Metabolite concentrations measured in NIST SRM 1950 will serve as essential reference data for facilitating interlaboratory comparisons. The methodology established here will be the cornerstone for in-depth profiling of signaling lipids across diverse biological samples and contexts.
    Keywords:  Bile acids; Endocannabinoids; Inflammation; Lysophospholipids; Oxylipins; SRM 1950
    DOI:  https://doi.org/10.1016/j.aca.2024.342348
  2. J Am Soc Mass Spectrom. 2024 Mar 06.
      For the simultaneous determination of monoamine neurotransmitters (NTs) like dopamine, serotonin, noradrenaline, and epinephrine, and their metabolites (metanephrine, normetanephrine, 3-methoxytyramine, vanillylmandelic acid, 3,4-dihydroxyphenylacetic acid, homovanillic acid, and 5-hydroxyindoleacetic acid), a robust liquid chromatography method coupled with tandem mass spectrometry (LC-MS/MS) was introduced as the analytical method. This analytical method proved to be accurate for the simultaneous measurement of the amounts of 11 NTs and their metabolites in biological samples. The method proved to be more efficient and better than the previously reported method in terms of precision, recovery, sample requirement, and extraction procedure. The reported method requires only 100 μL of blood and 200 μL of urine, and the extraction procedure requires acetonitrile precipitation, filtration, drying, and reconstitution in water. The separation of all analytes was performed on an C18 column (4.6 mm × 150 mm and 1.8 μm). A 10 min gradient elution program with a mobile phase consisting of phase A (0.2% formic acid in water) and phase B (methanol) was used. The positive ionization mode was used for the detection of all analytes in multiple reaction monitoring (MRM). The proposed method was validated with an internal standard and yielded lower limits of detection and quantification ranges of 0.0182-0.0797 ng/mL and 0.0553-0.2415 ng/mL, respectively, with a good linearity (R2) between 0.9959 and 0.9994. The recoveries ranged from 73.37% to 116.63% in blood and from 80.9% to 115.33% in urine. For the NTs and metabolites, the intra- and interday % CV were 0.24-9.36 and 0.85-9.67, respectively. The developed LC-MS/MS method was successfully used for the determination of trace amounts of endogenous compounds in human blood and urine samples.
    Keywords:  LC-MS/MS; biological samples; metabolites; method development; neurotransmitters
    DOI:  https://doi.org/10.1021/jasms.3c00326
  3. Anal Biochem. 2024 Feb 29. pii: S0003-2697(24)00040-X. [Epub ahead of print] 115496
      Disturbances in the diurnal pattern are associated with several clinical and psychological conditions, including depression and fatigue. Salivary sampling for melatonin, cortisol and cortisone provides a non-invasive method for frequent sampling and obtaining biochemical insight into the diurnal pattern of individuals. Therefore, a new liquid chromatography-tandem mass spectrometry-based method for the measurement of salivary melatonin, cortisol and cortisone was developed and validated. The method required 250 μl saliva, used isotope dilution methodology and was based on a liquid-liquid extraction for sample preparation, reversed-phase chromatography and multiple reaction monitoring on a mass spectrometer for quantitation. The lower limits of quantification obtained were 0.010 nmol/L for melatonin, 0.5 nmol/L for cortisol and 1.00 nmol/L for cortisone and the limits of detection were 0.003 nmol/L, 0.15 nmol/L and 0.1 nmol/L respectively. The method imprecision was ≤14% for all measurands, and the method comparison showed highly comparable results with high correlation coefficients (all ≥0.964). Potential interference of cortisol and cortisone by prednisolone was observed and could be detected by chromatogram review. Typical diurnal patterns for melatonin, cortisol and cortisone were observed in the saliva of 20 cancer survivors who collected saliva throughout the day.
    Keywords:  Cortisol; Cortisone; Diurnal rhythm; Melatonin; Salivary
    DOI:  https://doi.org/10.1016/j.ab.2024.115496
  4. Sci Rep. 2024 03 06. 14(1): 5545
      Quantitative analysis of the biologically-active metabolites of vitamin D (VitD), which are crucial in regulating various physiological and pathological processes, is important for clinical investigations. Liquid chromatography-tandem mass spectrometry (LC-MS) has been widely used for this purpose but existing LC-MS methods face challenges in achieving highly sensitive and accurate quantification of low-abundance VitD metabolites while maintaining high throughput and robustness. Here we developed a novel pipeline that combines a trapping-micro-LC-(T-µLC) with narrow-window-isolation selected-reaction monitoring MS(NWI-SRM) for ultra-sensitive, robust and high-throughput quantification of VitD metabolites in serum samples after derivatization. The selective-trapping and delivery approach efficiently removes matrix components, enabling high-capacity sample loading and enhancing sensitivity, throughput, and robustness. The NWI-SRM further improves the sensitivity by providing high selectivity. The lower limits of quantification (LOQs) achieved were markedly lower than any existing LC-MS methods: 1.0 pg/mL for 1,25(OH)2D3, 5.0 pg/mL for 24,25(OH)2D3, 30 pg/mL for both 25(OH)D2 and 25(OH)D3, all within a 9-min cycle. The method is applied to quantify VitD metabolites from 218 patients with multiple sclerosis. This study revealed negative correlations(r=- 0.44 to - 0.51) between the levels of 25(OH)D2 and all the three D3 metabolites in multiple sclerosis patients.
    DOI:  https://doi.org/10.1038/s41598-024-55939-0
  5. Curr Protoc. 2024 Mar;4(3): e992
      Oxylipins are oxidized metabolites of polyunsaturated fatty acids (PUFAs). They represent a class of risk markers and/or therapeutic targets for diseases associated with inflammation, including cardiovascular disease and brain disorders. Because the biological activities of free PUFAs and oxylipins depend on their chemical structures and concentrations, monitoring PUFAs and oxylipin levels in biological systems is critical for understanding their roles in health and disease. Traditionally, accurate quantification of free PUFAs and oxylipins in biological samples was performed separately, as PUFAs are often 1000-fold more abundant than the derived oxidized fatty acids (oxylipins). This article describes a liquid chromatography multiple reaction monitoring tandem mass spectrometry method for the quantitative analysis of five free PUFAs and 88 oxylipins in various biological fluids, including plasma, platelet supernatants, and tissues. The same approach can also be used in conjunction with an alkaline hydrolysis step to quantify total oxylipins in fish oils. We observed that in some samples, linoleic acid levels in plasma and eicosapentaenoic acid and arachidonic acid levels in brain tissue were above the upper limit of quantification. To address this issue, we developed a data analysis method to obtain PUFA and oxylipin concentrations in these samples without additional sample preparation, thus significantly saving time and labor. © 2024 Wiley Periodicals LLC. Basic Protocol: Quantification of polyunsaturated fatty acids (PUFAs) and oxylipins using liquid chromatography multiple reaction monitoring tandem mass spectrometry Support Protocol 1: Preparation of internal standard mixed working solution Support Protocol 2: Preparation of standard mixed stock solution Support Protocol 3: Preparation of standard mixed working solution Alternate Protocol 1: Extraction and quantitation of free PUFAs and oxylipins from mouse brain tissue Alternate Protocol 2: Extraction and quantitation of total PUFAs and oxylipins from fish oil.
    Keywords:  eicosanoids; multiple reaction monitoring mass spectrometry; oxylipins; polyunsaturated fatty acids; protectins; resolvins
    DOI:  https://doi.org/10.1002/cpz1.992
  6. BMC Biotechnol. 2024 Mar 07. 24(1): 12
      OBJECTIVE: The objective of this study was to establish a methodology for determining carboxymethyl lysine (CML) and carboxyethyl lysine (CEL) concentrations in human plasma using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The test results were also used for clinical aging research.METHODS: Human plasma samples were incubated with aqueous perfluorovaleric acid (NFPA), succeeded by precipitation utilizing trichloroacetic acid, hydrolysis facilitated by hydrochloric acid, nitrogen drying, and ultimate re-dissolution utilizing NFPA, followed by filtration. Cotinine-D3 was added as an internal standard. The separation was performed on an Agela Venusil ASB C18 column (50 mm × 4.6 mm, 5 μm) with a 5 mmol/L NFPA and acetonitrile/water of 60:40 (v/v) containing 0.15% formic acid. The multiple reaction monitoring mode was used for detecting CML, CEL, and cotinine-D3, with ion pairs m/z 205.2 > 84.1 (for quantitative) and m/z 205.2 > m/z 130.0 for CML, m/z 219.1 > 84.1 (for quantitative) and m/z 219.1 > m/z 130.1 for CEL, and m/z 180.1 > 80.1 for cotinine-D3, respectively.
    RESULTS: The separation of CML and CEL was accomplished within a total analysis time of 6 minutes. The retention times of CML, CEL, and cotinine-D3 were 3.43 minutes, 3.46 minutes, and 4.50 minutes, respectively. The assay exhibited linearity in the concentration range of 0.025-1.500 μmol/L, with a lower limit of quantification of 0.025 μmol/L for both compounds. The relative standard deviations of intra-day and inter-day were both below 9%, and the relative errors were both within the range of ±4%. The average recoveries were 94.24% for CML and 97.89% for CEL.
    CONCLUSION: The results indicate that the developed methodology is fast, highly sensitive, highly specific, reproducible, and suitable for the rapid detection of CML and CEL in clinical human plasma samples. The outcomes of the clinical research project on aging underscored the important indicative significance of these two indicators for research on human aging.
    Keywords:  CEL; CML; Human aging; Human plasma; LC-MS/MS
    DOI:  https://doi.org/10.1186/s12896-024-00838-5
  7. J Pharm Biomed Anal. 2024 Feb 27. pii: S0731-7085(24)00116-X. [Epub ahead of print]243 116076
      Recently we published in this journal an enantioselective high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the quantitative determination of 3,4-methylenedioxymethamphetamine (MDMA) and its major phase-1 metabolites, 4-hydroxy-3-methoxyamphetamine (HMA), 4-hydroxy-3-methoxymethamphetamine (HMMA) and 3,4-methylenedioxyamphetamine (MDA) in human plasma, sweat, oral fluid and urine. Since we did not achieve simultaneous enantioseparation of all 4 compounds with a single chiral column, two amylose-based chiral columns were used alternatively. Further optimization of the mobile phase in the present study enabled baseline separation of all four pairs of enantiomers on a single Lux AMP column. In addition, by optimization of the column dimension and applied flow-rate it became possible to complete the separation within 6 minutes. These new methods were applied to the analysis of human plasma, oral fluid and urine. While results on the concentration of MDMA and its metabolites in various biological fluids were reported in our recent publication, in the present study an attempt was made to hydrolyze glucuronides in urine samples by using alternatively, hydrochloric acid or glucuronidase and to evaluate the effect of hydrolysis on the concentration and enantiomeric distribution of hydroxy metabolites of MDMA such as HMA and HMMA.
    Keywords:  Chiral HPLC; Enantioselective metabolism; Enantioseparation; Hydrolysis of glucuronides; MDMA and metabolites
    DOI:  https://doi.org/10.1016/j.jpba.2024.116076
  8. Wei Sheng Yan Jiu. 2024 Jan;53(1): 95-101
      OBJECTIVE: An analytical method was developed for tetrodotoxin(TTX) in urine by liquid chromatography-tandem mass spectrometry(LC-MS/MS) with internal standard calibration.METHODS: TTX in the sample was extracted with the mixture of acetic acid/methanol/acetonitrile(0.005 mL/0.8 mL/1.8 mL), cleaned by solid phase extraction(SPE) with cation exchange cartridge, eluted with 50% acetonitrile/water containing 0.3% hydrochloric acid, and neutralized with ammonia. The extract was separated by a Waters XBridge~(TM) BEH Amide column(150 mm×3.0mm, 1.7 μm) and measured by MS/MS. By optimizing sample extraction and SPE cleanup conditions, the problems of low recovery and strong suppression effects of MS signal for TTX in urine were resolved when cleaned with cation exchange cartridge.
    RESULTS: Quantitatively calibrated by the internal standard of Kasugamycin, good linear relationship was found for TTX in urine at the range of 0.2-200 μg/L with the correlation coefficient(r~2) of 0.997. The limits of detection and quantitation for TTX in sample matrix were 0.1 and 0.2μg/L, respectively. The average recoveries at three spiking levels(0.2, 10.0 and 200 μg/L) were 89.3%-95.3% with relative standard deviation(n=6) less than 5.1%. The concentrations of TTX in urine from 11 poisoning patients were 0.4-138 μg/L. The detection rate was 100% in urine collected within 3 days after poisoning.
    CONCLUSION: The established method was simple, accurate and sensitive. It can provide reliable technical support for the rapid treatment of TTX poisoning events and the study of toxin metabolism in vivo.
    Keywords:  food poisoning; liquid chromatography-tandem mass spectrometry; solid phase extraction; tetrodotoxin; urine
    DOI:  https://doi.org/10.19813/j.cnki.weishengyanjiu.2024.01.015
  9. Proteomics. 2024 Mar 04. e2200436
      Ion mobility spectrometry-mass spectrometry (IMS-MS or IM-MS) is a powerful analytical technique that combines the gas-phase separation capabilities of IM with the identification and quantification capabilities of MS. IM-MS can differentiate molecules with indistinguishable masses but different structures (e.g., isomers, isobars, molecular classes, and contaminant ions). The importance of this analytical technique is reflected by a staged increase in the number of applications for molecular characterization across a variety of fields, from different MS-based omics (proteomics, metabolomics, lipidomics, etc.) to the structural characterization of glycans, organic matter, proteins, and macromolecular complexes. With the increasing application of IM-MS there is a pressing need for effective and accessible computational tools. This article presents an overview of the most recent free and open-source software tools specifically tailored for the analysis and interpretation of data derived from IM-MS instrumentation. This review enumerates these tools and outlines their main algorithmic approaches, while highlighting representative applications across different fields. Finally, a discussion of current limitations and expectable improvements is presented.
    Keywords:  algorithm; collision-cross section; computational tool; data processing; ion mobility spectrometry-mass spectrometry; lipidomics; metabolomics; proteomics; software
    DOI:  https://doi.org/10.1002/pmic.202200436
  10. J Chromatogr B Analyt Technol Biomed Life Sci. 2024 Feb 28. pii: S1570-0232(24)00065-5. [Epub ahead of print]1236 124057
      This study developed and validated a new liquid chromatography-tandem mass spectrometry (LC-MS/MS) method to quantify omadacycline and its epimerization in stool to facilitate microbiome studies. Omadacycline was extracted in a methanol-water-ethylenediaminetetraacetic acid (ETDA) solvent containing deuterated omadacycline as internal standard, followed by dilution. In an optimal gradient elution mode, omadacycline and its C4 epimer were separated within 5 min on reversed-phase C18 column. The method showed a broad working range of 0.1-200 ng/ml with a limitation of detection (LOD) of 0.03 ng/ml, little fecal matrix effect, good intra-day and inter-day accuracy (90-101 %), precision (2-15 %), and recovery rate (99-105 %). The method was sufficiently sensitive to quantify omadacycline in human fecal samples (n = 82) collected during a 10-day therapy course and at follow-up (day 13 and day 30) that ranged from 1 to 4785 µg/g. Further analysis revealed that ∼9 % of omadacycline was epimerized in fecal matrix control while, on average, 37.4 % was epimerized in human fecal samples. This study developed and validated a novel, simple, sensitive, and accurate method utilizing LC-MS/MS to quantify omadacycline its epimerization in the human gut. This has important implications for future studies of omadacycline and other tetracycline-class antibiotics as part of gut microbiome studies.
    Keywords:  Chromatography; Epimer; Epimerization; Human gut microbiome; LC-MS/MS; Omadacycline
    DOI:  https://doi.org/10.1016/j.jchromb.2024.124057
  11. J Anal Toxicol. 2024 Mar 05. pii: bkae019. [Epub ahead of print]
      The antiviral drug acyclovir (ACV) may induce drug-induced neuropsychiatric symptoms as side effects. The detailed pathogenic mechanism remains unclear; however, it is hypothesized that 9-carboxymethoxymethylguanine (CMMG), a metabolite of ACV, is the causative compound. Therefore, the blood concentrations of ACV and CMMG should be analyzed in ACV toxicity studies. However, it is rare to find methods that can sufficiently separate the ACV and CMMG peaks during simultaneous analysis of both compounds. Therefore, we intended to develop a liquid chromatography tandem mass spectrometry method with improved peak separation of analytes. Samples were deproteinized using methanol/acetonitrile solution (6:4, v/v). Analytes were separated on an InertSustain® Amide column (3 μm, 2.1 × 150 mm). The mobile phase consisted of acetonitrile/10 mM ammonium formate (5:95, v/v) (A) and acetonitrile/10 mM ammonium formate (95:5, v/v, pH 5.0) (B) and samples were eluted in the gradient mode. The separation of analytes was satisfactory and the peak shapes were good. Linear regression models weighted 1/x2 were obtained in the range of 0.25-10 μg/mL. The range of quality control (QC) bias was between 3.6 and 19.8%, and the within-run and between-run precisions of QC were within 13.5%. Recovery ranged from 83.6 to 103.7%, but ion suppression was observed. Samples from a patient with ACV encephalopathy were analyzed using this method. The resulting blood ACV and CMMG concentrations were 8.2 and 8.5 μg/mL, respectively. This method, with sufficient separation of ACV and CMMG, proved useful for use in ACV toxicity studies.
    Keywords:  9-Carboxymethoxymethylguanine; Acyclovir; Acyclovir encephalopathy; Acyclovir-induced neurotoxicity; HILIC; LC-MS/MS; Toxicokinetics
    DOI:  https://doi.org/10.1093/jat/bkae019
  12. J Proteome Res. 2024 Mar 06.
      Targeted mass spectrometry (MS)-based absolute quantitative analysis has been increasingly used in biomarker discovery. The ability to accurately measure the masses by MS enabled the use of isotope-incorporated surrogates having virtually identical physiochemical properties with the target analytes as calibrators. Such a unique capacity allowed for accurate in-sample calibration. Current in-sample calibration uses multiple isotopologues or structural analogues for both the surrogate and the internal standard. Here, we simplified this common practice by using endogenous light peptides as the internal standards and used a mathematical deduction of "heavy matching light, HML" to directly quantify an endogenous analyte. This method provides all necessary assay performance parameters in the authentic matrix, including the lower limit of quantitation (LLOQ) and intercept of the calibration curve, by using only a single isotopologue of the analyte. This method can be applied to the quantitation of proteins, peptides, and small molecules. Using this method, we quantified the efficiency of heart tissue digestion and recovery using sodium deoxycholate as a detergent and two spiked exogenous proteins as mimics of heart proteins. The results demonstrated the robustness of the assay.
    Keywords:  absolute protein quantification; digestion and recovery efficiency; in-sample calibration; membrane proteins; parallel reaction monitoring (PRM); stable isotope dilution; surrogate analyte method; surrogate matrix method; targeted mass spectrometry
    DOI:  https://doi.org/10.1021/acs.jproteome.3c00848
  13. Anal Chim Acta. 2024 Apr 08. pii: S0003-2670(24)00146-6. [Epub ahead of print]1297 342345
      Mass spectrometry imaging (MSI) visualizes spatial distribution of molecules in a biological tissue. However, compared with traditional microscopy-based imaging, conventional MSI is limited to its spatial resolution, resulting in difficulties in identifying detailed tissue morphological characters, such as lesion boundary or nanoscale structures. On the other hand, expansion microscopy, a tissue expansion method widely used in optical imaging to improve morphological details, has great potential to solve insufficient spatial resolution in mass spectrometry imaging (MSI). However, expansion microscopy was not originally designed for MSI, resulting in problems while combining expansion microscopy and MSI such as expanded sample fragility, vacuum stability and molecule loss during sample preparation. In this research we developed a MALDI MSI compatible expansion protocol by adjusting sample preparation methods during tissue expansion, successfully combining expansion microscopy with MSI. After tissue expansion the expanded sample can be readily applied to MALDI MSI sample preparation and further data acquisition. The MALDI MSI compatible expansion protocol has great potential to be widely applied in MALDI MSI sample preparation to facilitate improvement of MSI spatial resolution.
    Keywords:  Expansion microscopy; Mass spectrometry imaging(MSI); Matrix-assisted laser desorption/ionization mass spectrometry imaging(MALDI MSI); Spatial resolution
    DOI:  https://doi.org/10.1016/j.aca.2024.342345
  14. Drug Metab Dispos. 2024 Mar 04. pii: DMD-AR-2023-001618. [Epub ahead of print]
      The determination of metabolic stability is critical for drug discovery programs, allowing for the optimization of chemical entities and compound prioritization. As such, it is common to perform high-volume in vitro metabolic stability experiments early in the lead optimization process to understand metabolic liabilities. Additional metabolite identification experiments are subsequently performed for a more comprehensive understanding of the metabolic clearance routes to aid medicinal chemists in the structural design of compounds. Collectively, these experiments require extensive sample preparation and a substantial amount of time and resources. To overcome the challenges, a high-throughput integrated assay for simultaneous hepatocyte metabolic stability assessment and metabolite profiling was developed. This assay platform consists of four parts: 1) an automated liquid-handling system for sample preparation and incubation; 2) a liquid chromatography and high-resolution mass spectrometry-based system to simultaneously monitor the parent compound depletion and metabolite formation; 3) an automated data analysis and report system for hepatic clearance assessment; and 4) a streamlined auto-batch processing for software-based metabolite profiling. The assay platform was evaluated using eight control compounds with various metabolic rates and biotransformation routes in hepatocytes across three species. Multiple sample preparation and data analysis steps were evaluated and validated for accuracy, repeatability, and metabolite coverage. The combined utility of an automated liquid-handling instrument, a high-resolution mass spectrometer, and multiple streamlined data processing software improves the process of these highly demanding screening assays, and allows for simultaneous determination of metabolic stability and metabolite profiles for more efficient lead optimization during early drug discovery. Significance Statement Metabolic stability assessment and metabolite profiling are pivotal in drug discovery to fully comprehend metabolic liabilities for chemical entity optimization and lead selection. The process of these assays can be repetitive, time-consuming, and resource demanding. Here, we developed an integrated hepatocyte stability assay that combines automation, HRMS and batch-processing softwares, to improve and combine the workflow of these assays. The integrated approach allows simultaneous metabolic stability assessment and metabolite profiling, significantly accelerating screening and lead optimization in a resource-effective manner.
    Keywords:  High performance liquid chromatography (HPLC); Mass spectrometry (MS); drug clearance; hepatocytes; high throughput screening; metabolite identification
    DOI:  https://doi.org/10.1124/dmd.123.001618
  15. Wei Sheng Yan Jiu. 2024 Jan;53(1): 102-108
      OBJECTIVE: To establish a method for determination of perchlorate and chlorate in drinks by ultra-performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS) based on isotopic internal standard method.METHODS: The perchlorate and chlorate residue in liquid drinks were extracted with methanol, in solid drinks with acetic acid solution, then centrifuged. The supernatant was cleaned-up with PSA/C18 cleanup tube. The separation of perchlorate and chlorate was carried out on a Acquity CSH fluorophenyl column(100 mm×2.1mm, 1.7 μm) and the detection was performed with tandem mass spectrometry with internal standard method for quantification.
    RESULTS: The peak area ratio of perchlorate and chlorate had a good linear relationship with their mass concentration within their respective linear ranges, with correlation coefficients(r) greater than 0.999. The limits of detection of perchlorate and chlorate were 0.2and 1 μg/L respectively and the limits of quantification were 0.5 and 3 μg/L respectively. The mean recoveries of two compounds were from 84.0% to 105.5% with relative standard deviations from 4.2% to 17.0% and 82.7% to 112.1% with relative standard deviations from 5.5% to 18.4%(n=6), respectively. The perchlorates in 11 kinds of beverage samples were 0.53-4.12 μg/L, chlorates were 3.27-61.86 μg/L.
    CONCLUSION: This method is simple, sensitive, accurate and reliable, which is suitable for the determination of perchlorate and chlorate in drinks.
    Keywords:  chlorate; drinks; isotopic internal standard method; perchlorate; ultra performance liquid chromatography tandem mass spectrometry
    DOI:  https://doi.org/10.19813/j.cnki.weishengyanjiu.2024.01.016
  16. J Pharm Biomed Anal. 2024 Feb 27. pii: S0731-7085(24)00114-6. [Epub ahead of print]243 116074
      Rapid diagnosis of diseases is one of the challenging areas in clinical research. From the analytical chemist's perspective, the main challenges are isolating the compounds from the bio-specimen and lengthy analysis times. In this regard, solid phase microextraction offers a platform to address the abovementioned challenges. Moreover, its sharp tip-thin film geometry, known as coated blade spray (CBS), can enhance the extraction and act as an ionization source in direct mass spectrometric analysis. In this study, a new CBS device specifically designed for polar analytes was prepared and optimized to determine urinary metabolites. For this purpose, polyacrylonitrile (PAN) was selected as a base polymer as it can be electrospun to form a nanofibrous structure, and it can be modified with weak ion exchange moieties to interact with polar analytes. Following the electrospinning of PAN, hydrolysis was optimized, and conditions leading to sufficient extraction enhancement without dissolving the polymer were obtained when probes were treated with 5.0 M of NaOH for 2.5 h. Using the coated blades prepared as explained, the evaluation of various extraction conditions showed that 5 min is sufficient for equilibrium extraction. In addition, the solution's ionic strength and pH significantly affect the extraction. Optimum sorption was obtained at no salt added and pH 7.0 conditions. The CBS-MS optimization showed that 10.0 µL of ACN/MeOH/H2O (40:40:20, v/v/v) with formic acid kept for 15 seconds on the blade before voltage application leads to the highest signal. The limits of quantification of the analytes are between 50 and 100 ng/mL.
    Keywords:  Biomarkers; Electrospinning; Mass spectrometry; Polar metabolites; Solid phase microextraction
    DOI:  https://doi.org/10.1016/j.jpba.2024.116074
  17. J Pharm Biomed Anal. 2024 Mar 03. pii: S0731-7085(24)00115-8. [Epub ahead of print]243 116075
      BACKGROUND: Drug testing commonly use urine as a specimen and immunoassays for screening. The need for supervised urine collection has led to an interest in alternative specimens and a need for using mass spectrometry methods already for screening. In addition, mass spectrometry methods allow for broad multipanel screening which of great value because of the increased number of substances that needs to be covered has increased over time. One alternative specimen of interest for drugs of abuse testing is dried blood spots (DBS) and this work aimed at developing multipanel screening methods based on selected reaction monitoring liquid chromatography - mass spectrometry for both urine and dried finger blood as specimens.MATERIALS AND METHODS: The urine method comprised 37 analytes and utilised salted out liquid/liquid extraction in 96-well format, respectively, and the blood method comprised 35 analytes, a 10 µL volumetric DBS device and a two-step solvent extraction procedure. In both cases stable isotope labelled internal standards were used for almost all analytes.
    RESULTS: The methods were validated according to forensic standard. The lowest reporting limits were generally set at 100 ng/mL for urine and 1 ng/mL for blood and the accuracy and imprecision were within limits of 15 and 20%. The methods were applied in a clinical study on patients receiving methadone maintenance treatment for opioid dependence. Methadone was detected in all urine and DBS samples, for urine sometimes below the commonly applied screening cutoff limit of 300 ng/mL. In 20 out of 99 cases no other drug was detected in any specimen. The most commonly other detected substances were pregabalin, amphetamine, alprazolam, zopiclone and THCCOOH. Findings in urine and DBS generally agreed well but more positives were detected in DBS.
    CONCLUSION: Multipanel methods using liquid chromatography - mass spectrometry suitable for clinical drug screening were successfully developed for urine and blood collected by finger-pricking and stored as DBS.
    Keywords:  Dried blood spots; Drugs of abuse; Liquid chromatography – mass spectrometry; Screening; Urine; Volumetric
    DOI:  https://doi.org/10.1016/j.jpba.2024.116075
  18. J Chromatogr B Analyt Technol Biomed Life Sci. 2024 Feb 27. pii: S1570-0232(24)00070-9. [Epub ahead of print]1236 124062
      BACKGROUND: Reduced and oxidized glutathione play an important role for the intracellular detoxification of reactive oxygen species. The iron-dependent formation of such reactive oxygen species in conjunction with the inhibition of the redox-balancing enzyme glutathione peroxidase 4 underlie an imbalance in the cellular redox state, thereby resulting in a non-apoptotic form of cell death, defined as ferroptosis, which is relevant in several pathologies.METHODS: Here we present a rapid ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) based method providing the accurate quantification of 12 glutathione pathway metabolites after in situ derivatization with N-Ethylmaleimide (NEM). The method was validated regards linearity, recovery and accuracy as well as precision. The assay includes glutathione and its oxidized form glutathione disulfide. Furthermore, the related precursors cysteine, cystine, glutamic acid, γ-glutamylcysteine and cysteinylglycine, biomarkers of protein crosslinking such as cystathionine and lanthionine, as well as metabolites of the transsulfuration pathway, methionine, homocysteine and serine are simultaneously determined.
    RESULTS: Twelve glutathione pathway metabolites were simultaneously analyzed in four different human cell line extracts within a total LC run time of 5.5 min. Interday coefficients of variation (1.7 % to 12.0 %), the mean observed accuracy (100.0 % ± 5.2 %), linear quantification ranges over three orders of magnitude for all analytes and sufficient metabolite stability after NEM-derivatization demonstrate method reliability. Immediate derivatization with NEM at cell harvesting prevents autooxidation of glutathione, ensures accurate results for the GSH/GSSG redox ratio and thereby allows interpretation of cellular redox state.
    CONCLUSION: The described UPLC-MS/MS method provides a sensitive and selective tool for a fast and simultaneous analysis of glutathione pathway metabolites, its direct precursors and related compounds. Assay performance characteristics demonstrate the suitability of the method for applications in different cell cultures. Therefore, by providing glutathione related functional metabolic readouts, the method enables investigations in mechanisms of ferroptosis and alterations in oxidative stress levels in several pathophysiologies.
    Keywords:  Ferroptosis; Glutathione; LC-MS/MS; NEM; Oxidative stress
    DOI:  https://doi.org/10.1016/j.jchromb.2024.124062
  19. ACS ES T Water. 2023 Oct 13. 3(10): 3293-3304
      The tire-derived contaminant N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine quinone (6-PPDQ) was recently identified as a potent toxin to coho salmon (Oncorhynchus kisutch). Studies investigating 6-PPDQ have employed solid-phase extraction (SPE) or liquid-liquid extraction (LLE) with liquid chromatography-mass spectrometry (LC-MS), providing excellent sensitivity and selectivity. However, cleanup and pre-enrichment steps (SPE/LLE) followed by chromatographic separation can be time- and cost-intensive, limiting sample throughput. The ubiquitous distribution of 6-PPDQ necessitates numerous measurements to identify hotspots for targeted mitigation. We recently developed condensed phase membrane introduction mass spectrometry (CP-MIMS) for rapid 6-PPDQ analysis (2.5 min/sample), with a simple workflow and low limit of detection (8 ng/L). Here, we describe improved quantitation using isotopically labeled internal standards and inclusion of a suite of PPDQ analogues. A low-cost autosampler and data processing software were developed from a three-dimensional (3D) printer and Matlab to fully realize the high-throughput capabilities of CP-MIMS. Cross-validation with a commercial LC-MS method for 10 surface waters provides excellent agreement (slope: 1.01; R2 = 0.992). We employ this analytical approach to probe fundamental questions regarding sample stability and sorption of 6-PPDQ under lab-controlled conditions. Further, the results for 192 surface water samples provide the first spatiotemporal characterization of PPDQs on Vancouver Island and the lower mainland of British Columbia.
    DOI:  https://doi.org/10.1021/acsestwater.3c00275
  20. Biomed Chromatogr. 2024 Mar 05. e5855
      Metabolite profiling has the potential to comprehensively bridge phenotypes and complex heterogeneous physiological and pathological states. We performed a metabolomics study using parallel liquid chromatography-mass spectrometry (LC-MS) combined with multivariate data analysis to screen for biomarkers of primary aldosteronism (PA) from a cohort of 111 PA patients and 218 primary hypertension (PH) patients. Hydrophilic interaction chromatography and reversed-phase liquid chromatography separations were employed to obtain a global plasma metabolome of endogenous metabolites. The satisfactory classification between PA and PH patients was obtained using the MVDA model. A total of 35 differential metabolites were screened out and identified. A diagnostic biomarker panel was established using the least absolute shrinkage and selection operator (LASSO) binary logistic regression model and receiver operating characteristic analysis. Joint analysis with clinical indicators, including plasma supine aldosterone level, plasma orthostatic aldosterone level, body mass index, and blood potassium, revealed that the combination of metabolite biomarker panel and plasma supine aldosterone has the best clinical diagnostic efficacy.
    Keywords:  LC-MS; diagnostic biomarker; metabolomics; plasma; primary aldosteronism
    DOI:  https://doi.org/10.1002/bmc.5855
  21. Sci Rep. 2024 Mar 08. 14(1): 5699
      Mass spectrometry-based lipidomics approaches offer valuable tools for the detection and quantification of various lipid species, including sphingolipids. The present study aimed to develop a new method to simultaneously detect various sphingolipid species that applies to diverse biological samples. We developed and validated a measurement system by employing a single-column liquid chromatography-mass spectrometry system utilizing a normal-phase separation mode with positive ionization. The measurement system provided precision with a coefficient of variant below 20% for sphingolipids in all types of samples, and we observed good linearity in diluted serum samples. This system can measure the following sphingolipids: sphingosine 1-phosphate (S1P), sphingosine (Sph), dihydroS1P (dhS1P), dihydroSph (dhSph), ceramide 1-phosphate (Cer1P), hexosylceramide (HexCer), lactosylceramide (LacCer), dh-ceramide, deoxy-ceramide, deoxy-dh-ceramide, and sphingomyelin (SM). By measuring these sphingolipids in cell lysates where S1P lyase expression level was modulated, we could observe significant and dynamic modulations of sphingolipids in a comprehensive manner. Our newly established and validated measurement system can simultaneously measure many kinds of sphingolipids in biological samples. It holds great promise as a valuable tool for laboratory testing applications to detect overall modulations of sphingolipids, which have been proposed to be involved in pathogenesis processes in a series of elegant basic research studies.
    Keywords:  Ceramide1-phosphate (Cer1P); Deoxy-ceramide; Deoxy-dh-ceramide; Hexosylceramide (HexCer); Lactosylceramide (LacCer); Sphingolipid; dh-ceramide
    DOI:  https://doi.org/10.1038/s41598-024-56321-w
  22. J Chromatogr A. 2024 Feb 24. pii: S0021-9673(24)00144-4. [Epub ahead of print]1720 464771
      During collagen biosynthesis, proline is post-translationally converted to hydroxyproline by specific enzymes. This amino acid, unique to collagen, plays a crucial role in stabilizing the collagen triple helix structure and could serve as an important biomarker for collagen content and quality analysis. Hydroxyproline has four isomers, depending on whether proline is hydroxylated at position 4 or 3 and on whether the cis- or trans- conformation is formed. Moreover, as extensive hydrolysis of collagen is required for its amino acid analysis, epimerization may also occur, although to a lesser extent, giving a total of eight possible isomers. The aim of the present study was to develop a reversed-phase high-performance liquid chromatography-UV-mass spectrometry (RPLC-UV-MS) method for the separation and quantification of all eight hydroxyproline isomers. After the chiral derivatization of the hydroxyproline isomers with Nα-(2,4-dinitro-5-fluorophenyl)-L-valinamide (L-FDVA), to enable their UV detection, the derivatized diastereoisomers were separated by testing different C18 column technologies and morphologies and optimizing operative conditions such as the mobile phase composition (solvent, additives), elution mode, flow rate and temperature. Baseline resolution of all eight isomers was achieved on a HALO® ES-C18 reversed-phase column (150×1.5 mm, 2.7 μm, 160 Å) using isocratic elution and MS-compatible mobile phase. The optimized method was validated for the quantification of hydroxyproline isomers and then applied to different collagen hydrolysates to gain insight and a deeper understanding of hydroxyproline abundances in different species (human, chicken) and sources (native, recombinant).
    Keywords:  Amino acid analysis; Collagen; Hydroxyproline isomers; Mass spectrometry; Recombinant collagen; Reverse phase chromatography
    DOI:  https://doi.org/10.1016/j.chroma.2024.464771
  23. Bioinformatics. 2024 Mar 05. pii: btae133. [Epub ahead of print]
      SUMMARY: Python is the most commonly used language for deep learning (DL). Existing Python packages for mass spectrometry imaging (MSI) data are not optimized for DL tasks. We therefore introduce pyM2aia, a Python package for MSI data analysis with a focus on memory-efficient handling, processing and convenient data-access for DL applications. pyM2aia provides interfaces to its parent application M2aia, which offers interactive capabilities for exploring and annotating MSI data in imzML format. pyM2aia utilizes the image input and output routines, data formats, and processing functions of M2aia, ensures data interchangeability, and enables the writing of readable and easy-to-maintain DL pipelines by providing batch generators for typical MSI data access strategies. We showcase the package in several examples, including imzML metadata parsing, signal processing, ion-image generation, and, in particular, DL model training and inference for spectrum-wise approaches, ion-image-based approaches, and approaches that use spectral and spatial information simultaneously.AVAILABILITY: Python package, code and examples are available at (https://m2aia.github.io/m2aia).
    SUPPLEMENTARY INFORMATION: Supplementary data are available at Bioinformatics online.
    DOI:  https://doi.org/10.1093/bioinformatics/btae133
  24. Drug Dev Ind Pharm. 2024 Mar 08. 1-13
      OBJECTIVE: To develop a sensitive and fast detection method via ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) to assess the concentration of ajuforrestin A, ajuforrestin B, ajugamacrin and 8-O-Acetylharpagide primarily derived from Ajuga plants in mice blood and their pharmacokinetics.METHODS: Single protein precipitation with high-proportioned acetonitrile is chosen for sample clean-up. The UPLC HSS T3 (2.1 mm × 100 mm, 1.8 µm) column with a mobile phase in gradient elution mode at the flow rate of 0.4 mL/min was used for sample separation. Acetonitrile was selected as the organic phase solution and water containing 0.1% formic acid was chosen as the aqueous solution. A tandem mass spectrometer containing an electrospray ionization (ESI) source in the positive ionization mode was used to detect four compounds via multiple reaction monitoring (MRM).
    RESULTS: The calibration curves (5-1000 ng/mL) of four compounds were linear with correlation coefficients > 0.997. The matrix effects, accuracy, precision, and recovery were all within permissible scope.
    CONCLUSIONS: In this approach, the corresponding pharmacokinetic parameters were successfully clarified in mouse for the first time, which provided a theoretical basis for the improvement of the standard of Ajuga plants and the safety of clinical medication. Furthermore, this method may provide the UPLC-MS/MS evidence for the differentiation of the main close relative varieties of genus Ajuga according to these plants contain different mixtures of the four marker compounds.
    Keywords:  8-O-acetylharpagide; UPLC-MS/MS; ajuforrestin A; ajuforrestin B; ajugamacrin; pharmacokinetics
    DOI:  https://doi.org/10.1080/03639045.2024.2328731
  25. Rapid Commun Mass Spectrom. 2024 May 15. 38(9): e9725
      RATIONALE: Mass spectrometry imaging (MSI) elevates the power of conventional mass spectrometry (MS) to multidimensional space, elucidating both chemical composition and localization. However, the field lacks any robust quality control (QC) and/or system suitability testing (SST) protocols to monitor inconsistencies during data acquisition, both of which are integral to ensure the validity of experimental results. To satisfy this demand in the community, we propose an adaptable QC/SST approach with five analyte options amendable to various ionization MSI platforms (e.g., desorption electrospray ionization, matrix-assisted laser desorption/ionization [MALDI], MALDI-2, and infrared matrix-assisted laser desorption electrospray ionization [IR-MALDESI]).METHODS: A novel QC mix was sprayed across glass slides to collect QC/SST regions-of-interest (ROIs). Data were collected under optimal conditions and on a compromised instrument to construct and refine the principal component analysis (PCA) model in R. Metrics, including mass measurement accuracy and spectral accuracy, were evaluated, yielding an individual suitability score for each compound. The average of these scores is utilized to inform if troubleshooting is necessary.
    RESULTS: The PCA-based SST model was applied to data collected when the instrument was compromised. The resultant SST scores were used to determine a statistically significant threshold, which was defined as 0.93 for IR-MALDESI-MSI analyses. This minimizes the type-I error rate, where the QC/SST would report the platform to be in working condition when cleaning is actually necessary. Further, data scored after a partial cleaning demonstrate the importance of QC and frequent full instrument cleaning.
    CONCLUSIONS: This study is the starting point for addressing an important issue and will undergo future development to improve the efficiency of the protocol. Ultimately, this work is the first of its kind and proposes this approach as a proof of concept to develop and implement universal QC/SST protocols for a variety of MSI platforms.
    DOI:  https://doi.org/10.1002/rcm.9725