Journal of Mass Spectrometry最新文献

{"title":"Advanced Ganglioside Characterization in Epileptic Human Hippocampus by Travelling Waves Ion Mobility Tandem Mass Spectrometry","authors":"Maria-Roxana Biricioiu,&nbsp;Kristina Mlinac-Jerković,&nbsp;Katarina Ilic,&nbsp;Tomislav Sajko,&nbsp;Raluca Ica,&nbsp;Mirela Sarbu,&nbsp;David E. Clemmer,&nbsp;Svjetlana Kalanj-Bognar,&nbsp;Alina D. Zamfir","doi":"10.1002/jms.5190","DOIUrl":"https://doi.org/10.1002/jms.5190","url":null,"abstract":"<div>\u0000 \u0000 <p>In this study, we present the first comprehensive application of ion mobility mass spectrometry (IMS MS) combined with collision-induced dissociation (CID MS/MS) to the comparative analysis of the gangliosidome in human hippocampal tissue affected by temporal lobe epilepsy and corresponding healthy controls. Using nanoESI IMS MS, we profiled complex ganglioside mixtures extracted from the human hippocampus affected by temporal lobe epilepsy and the normal hippocampus. A total of 217 ions corresponding to 192 distinct ganglioside species were identified in the epileptic tissue, compared with 156 ions assigned to 137 species in the healthy hippocampus. The majority of these species were polysialylated and exhibited extensive structural diversity in both glycan and ceramide moieties, with important modifications including fucosylation, <i>O</i>-acetylation, GalNAc, and CH₃COO⁻ attachments. The gangliosidome associated with epilepsy was found characterized by a higher overall degree of sialylation than previously known, with the exclusive presence of highly sialylated GP, GS, and GO species reported here for the first time in relation to this disease. CID MS/MS experiments enabled the structural elucidation of several biologically relevant species, including <i>O</i>-Ac–GD1b (d18:1/20:2) and GT1b (d18:1/23:0), demonstrating the method's capacity to resolve complex structures and identify specific ganglioside isomers. Significant differences in the expression and modification patterns between pathological and control samples suggest disease-associated remodeling of membrane components. This study not only reveals novel molecular features of epilepsy-related ganglioside alterations but also establishes IMS CID MS/MS as a powerful analytical platform for advancing glycosphingolipidomics and exploring biomolecular signatures in neurological disorders.</p>\u0000 </div>","PeriodicalId":16178,"journal":{"name":"Journal of Mass Spectrometry","volume":"60 11","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145242856","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Application of Gas-Phase Electrophoresis (nES GEMMA Instrumentation) in Molecular Weight Determination","authors":"Victor U. Weiss,&nbsp;Wladyslaw W. Szymanski,&nbsp;Martina Marchetti-Deschmann","doi":"10.1002/jms.5183","DOIUrl":"https://doi.org/10.1002/jms.5183","url":null,"abstract":"<p>Gas-phase electrophoresis by means of a nano-Electrospray Gas-phase Electrophoretic Mobility Molecular Analyzer (nES GEMMA, also known as e.g., nES DMA, MacroIMS, or LiquiScan ES) separates singly charged, aerosolized (bio-)nanoparticles at ambient pressure in the gas phase according to the particle electrophoretic mobility (EM) diameter, i.e., an equivalent size related to spherical analytes. Corresponding size spectra in the range of a few to several hundred nanometers in terms of an EM diameter relate particle number concentrations to particle size values. Already shortly after the introduction of the instrument to the community of analytical chemists, its ability to yield particle molecular weight (MW) values based on measured EM diameters applying a corresponding correlation function was described. This first calibration function was solely based on protein monomers, dimers, and larger aggregates. In the following years, it became evident that this correlation function was well suited to calculate MW of globular proteins based on their EM diameters. For other substance classes, significant deviations were observed which ultimately led to the definition of further calibration functions. This manuscript reviews these developments and provides an overview of some key applications of gas-phase electrophoresis using the nES GEMMA system for MW determination of (bio-)nanoparticles from initial experiments in the year 1996 to the current day (2025).</p>","PeriodicalId":16178,"journal":{"name":"Journal of Mass Spectrometry","volume":"60 11","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/epdf/10.1002/jms.5183","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145243051","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Simplified Analysis of Native Steroid Esters in Dried Blood Spots by LC–MS3","authors":"Andreas Thomas,&nbsp;Jasmin Thelen,&nbsp;Panagiotis Sakellariou,&nbsp;Mario Thevis","doi":"10.1002/jms.5188","DOIUrl":"https://doi.org/10.1002/jms.5188","url":null,"abstract":"<p>Steroidal esters (e.g., testosterone, nandrolone and boldenone esters) belong to the substance class prohibited in professional sport that is particularly frequently abused due to its considerable performance-enhancing effects. Thus, a high number of adverse analytical findings in doping controls is reported every year. Unfortunately, the analysis of steroids that are not exclusively of exogenous nature and, in particular, their differentiation from endogenously produced steroids is very time-consuming and resource-intensive (necessitating isotope-ratio mass spectrometric analysis). The direct detection of the applied (unequivocally exogenous) steroidal esters in blood or dried blood spots (DBS) can offer a much simpler approach. In the present project, the analysis of 17 underivatized steroidal esters (composed of testosterone, nandrolone and boldenone species) is reported, employing liquid chromatography-(low-resolution)-MSⁿ. The results show that all included esters can be selectively and sensitively detected in MS³ mode at sub-ng/mL levels in DBS. The detection limits for most analytes extracted from a single spot were below 0.1 ng/mL, and recovery rates were determined at 40%–80%. The overall procedure was controlled using four different stable isotope-labelled internal standards. Notably, the obtained results are largely independent from the sampling device, and the method works for cellulose-based DMPK cards as well as polymer-based TASSO devices. Proof-of-concept and applicability of the method to authentic samples were demonstrated by analysing post-administration samples collected after an oral administration of 80 mg of testosterone undecanoate.</p>","PeriodicalId":16178,"journal":{"name":"Journal of Mass Spectrometry","volume":"60 11","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/epdf/10.1002/jms.5188","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145243053","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Correction to \"Enhancing Herbal Formulation Analysis: The Role of Flash Chromatography and TLC-MS in Purification and Quality Control\".","authors":"","doi":"10.1002/jms.5182","DOIUrl":"https://doi.org/10.1002/jms.5182","url":null,"abstract":"","PeriodicalId":16178,"journal":{"name":"Journal of Mass Spectrometry","volume":"60 10","pages":"e5182"},"PeriodicalIF":2.0,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145238813","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Strategy to Achieve Sub-Parts-per-Million Mass Measurement Accuracy of N-Linked Glycans Using Infrared Matrix-Assisted Laser Desorption Electrospray Ionization","authors":"Adeleke A. Adepoju,&nbsp;Tana V. Palomino,&nbsp;Alexandria L. Sohn,&nbsp;David C. Muddiman","doi":"10.1002/jms.5184","DOIUrl":"10.1002/jms.5184","url":null,"abstract":"<p>Mass calibration techniques are vital in achieving high mass measurement accuracy (MMA) of large biomolecules. Variable ion populations that shift the axial frequencies due to space charge effects have been a significant challenge in achieving sub-parts-per-million (sub-ppm) MMA of glycans on a high-resolution accurate mass (HRAM) orbitrap instrument without the activation of automatic gain control. As the role of glycans is critical to our understanding of diverse biological processes, accurate identification of glycans using sub-ppm MMA is critical for biological interpretations. Hence, this study aims to achieve sub-ppm MMA of glycans by exploring the impact of different ion accumulation times, data collection modes, in addition to custom calibration strategies and external mass correction to optimize accurate mass measurements. Using infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI), direct analysis was performed on <i>N</i>-linked glycans cleaved from bovine fetuin in negative polarity, where 17 <i>N</i>-linked glycans were detected and annotated. Our results indicate the significance of implementing a custom calibration external lock mass and other techniques, including the effect of external mass correction in achieving sub-ppm MMA of large biomolecules. Implementing such approaches in mass spectrometry imaging (MSI) of biological tissue will enhance the confidence of glycan annotation and enable more accurate biological conclusions.</p>","PeriodicalId":16178,"journal":{"name":"Journal of Mass Spectrometry","volume":"60 10","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12481009/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145191718","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Influence of Filters, Solid to Fluid Ratios and Matrices on the Bioaccessibility of Potentially Toxic Elements in Airborne PM","authors":"Jawad Ali Hussein Alpofead,&nbsp;Christine M. Davidson","doi":"10.1002/jms.5185","DOIUrl":"10.1002/jms.5185","url":null,"abstract":"<div>\u0000 \u0000 <p>Determination of bioaccessibility of potentially toxic elements in inhaled airborne particulate matter has brought the attention of researchers. In this study, the effect of filters and solid-to-fluid ratios on the bioaccessible fraction of elements in airborne particulate matter determined by the simplified bioaccessibility extraction test was investigated. A matrix-matched and a non-matrix-matched set of calibration standards for inductively coupled plasma mass spectrometry was also examined. Nine elements: As, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn were determined. Results obtained illustrated that matrix matching was necessary for preparing As calibration standards. Results also indicated that the ratio adopted in the miniaturized version of the simplified bioaccessibility extraction test (0.1 g:10 mL) is the best choice when all elements tested are to be measured, compared to other ratios investigated in this study. However, all ratios can be applied with no significant difference for Cd, Cu and Ni. Results from filters' effect demonstrated that the relative percent difference between the bioaccessible fraction of elements in soil only and in soil loaded on filters was less than 20% for all elements except for Cd, Ni and Zn. Discrepancies observed for Zn were due to the variability in its amount used to produce filters.</p>\u0000 </div>","PeriodicalId":16178,"journal":{"name":"Journal of Mass Spectrometry","volume":"60 10","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145191755","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mass Spectrometric Assessment of the Reactivity and Target Sites of 3-Aminopropanal and 3-Aminopropanal-Released Acrolein in Peptides and Proteins","authors":"Michaela Rašková,&nbsp;Vlastimil Dorčák,&nbsp;Jan Vacek,&nbsp;Marek Šebela","doi":"10.1002/jms.5181","DOIUrl":"https://doi.org/10.1002/jms.5181","url":null,"abstract":"<p>Living cells are frequently exposed to aldehydes, as these compounds are produced during metabolism, found in natural dietary sources, and present as contaminants, drugs, and pollutants. For instance, acrolein is well-known as a toxic pollutant, but is also produced in the metabolism of polyamines, threonine, and polyunsaturated fatty acids. Another aldehyde, 3-aminopropanal, is a byproduct of polyamine oxidation, and its cytotoxicity has been implicated in various diseases, especially those involving oxidative stress and cellular damage. 3-Aminopropanal can readily convert to acrolein through ammonia elimination. Our objective was to compare the reactivity of these two compounds toward biomolecules. Amino acids such as cysteine and lysine, along with model peptides and proteins, were reacted with an excess of each compound. The reacted molecules were analyzed by MALDI-TOF mass spectrometry to assess the extent of modification by examining the difference in molecular mass. Modified peptides, including those obtained by enzymatic digestion of the reacted model proteins, were subjected to tandem mass spectrometry to identify modification sites and determine the structure of the modified amino acids. The most characteristic modifications were Michael addition to cysteine and Schiff base formation with lysine, consistent with known acrolein-induced protein modifications. Compared to acrolein, 3-aminopropanal exhibited substantially reduced reactivity, though it generally targeted the same sites. These results represent the first experimental characterization of 3-aminopropanal-induced protein modifications at the molecular level, and support the notion that 3-aminopropanal is converted to acrolein, which acts as the modifying agent.</p>","PeriodicalId":16178,"journal":{"name":"Journal of Mass Spectrometry","volume":"60 10","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/epdf/10.1002/jms.5181","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145146823","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Deciphering the Pharmacodynamic Basis of Biyan Qingdu Granules: Integrated key Pharmacodynamic Components Identification, Multi-Tissue Distribution, and Metabolic Profiling","authors":"Na Zhang,&nbsp;Xiang Fan,&nbsp;Fengyi Lv,&nbsp;Peng Li,&nbsp;Guanghui Xu,&nbsp;Min Zhao","doi":"10.1002/jms.5179","DOIUrl":"10.1002/jms.5179","url":null,"abstract":"<div>\u0000 \u0000 <p>Biyan Qingdu Granules (BYQD) is a traditional Chinese medicine (TCM) formulation used to treat symptoms associated with increased secretion during nasopharyngeal carcinoma (NPC) radiotherapy. However, a comprehensive investigation into its pharmacodynamic material basis has not been conducted. This study presents a method that integrates UHPLC-HRMS and UHPLC–MS/HRMS with network pharmacology to investigate the pharmacodynamic components, multi-tissue distribution and biotransformation processes of BYQD. This study systematically identified 20 pharmacodynamic constituents in plasma following BYQD administration and characterized their distribution patterns across six tissues (heart, liver, spleen, lung, kidney, and nasopharynx). Through integrated network pharmacology and molecular docking validation, four critical bioactive components were prioritized: quercetin, jaceosidin, α-allocryptopine, and magnoflorine. Furthermore, we established the first comprehensive multi-tissue metabolic atlas for BYQD, identifying 40 phase I/II metabolites with tissue-specific metabolic signatures. These findings delineate the in vivo process of BYQD components, unravel their pharmacodynamic material basis.</p>\u0000 </div>","PeriodicalId":16178,"journal":{"name":"Journal of Mass Spectrometry","volume":"60 10","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145137789","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Stress Degradation Study of Bosutinib and Structural Elucidation of Its Degradation Impurities by Using LC-Q-TOF-MS/MS and NMR","authors":"Sowmya Chaganti,&nbsp;Usha Chauhan,&nbsp;Dharipally Harini,&nbsp;H M Chandra Mouli,&nbsp;Bhukya Vijay Nayak,&nbsp;Gananadhamu Samanthula","doi":"10.1002/jms.5180","DOIUrl":"10.1002/jms.5180","url":null,"abstract":"<div>\u0000 \u0000 <p>Bosutinib monohydrate (BST) is an anticancer medicine used to treat Philadelphia chromosome-positive (Ph+) chronic myeloid leukemia. The present research focuses on the separation and structural elucidation of degradation impurities of BST using reversed-phase chromatography, mass spectrometry, and nuclear magnetic resonance spectroscopy methods. As per the International Council for Harmonisation (ICH) Q1A and Q1B guidelines, the stress degradation experiments on BST were carried out. The separation of degradation impurities was accomplished on an RP-HPLC using Agilent ZORBAX Eclipse plus C18 column (4.6 × 250 mm, 5 μm) on a gradient program with a flow rate of 1 mL/min, and 0.1% formic acid in water (%A) and acetonitrile (%B) as the mobile phases. Eight degradation impurities were detected in basic hydrolysis, oxidative conditions (H₂O₂), and photolytic (UV light and visible light) conditions. Structural elucidation of degradation impurities was performed by LC-Q-TOF-MS/MS. The obtained experimental masses were used to propose the fragmentation patterns and structures of BST and its degradation impurities. The data obtained from the mass spectrometry were used to propose the mechanism for the formation of the degradation impurities. The DI B-6 was isolated and NMR studies were performed for the confirmation of its structure. Zeneth was used to anticipate the in silico degradation profile of BST. The structures of seven degradation impurities matched with the in silico predictions of Zeneth. DEREK Nexus and SARAH Nexus were the in silico tools used to predict toxicity and mutagenicity. Thus, the outcomes attained from this study could be relevant for regular analysis and stability testing of BST in quality control laboratories.</p>\u0000 </div>","PeriodicalId":16178,"journal":{"name":"Journal of Mass Spectrometry","volume":"60 10","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145111301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Analysis of Acyl Solamines in Tuber Periderm of Cultivated and Wild Potatoes Using Liquid Chromatography Coupled With Electrospray Ionization Quadrupole Time-of-Flight Mass Spectrometry","authors":"Christoph Böttcher,&nbsp;Karin Gorzolka,&nbsp;Paul Himmighofen,&nbsp;Torsten Meiners","doi":"10.1002/jms.5177","DOIUrl":"10.1002/jms.5177","url":null,"abstract":"<p>Acyl solamines are a poorly investigated class of alkaloids found in several solanaceous plants. A general screening approach on the basis of all-ion fragmentation is proposed for this compound class using reversed-phase ultra-high performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight mass spectrometry. When applied to tuber periderm extracts of <i>Solanum tuberosum</i>, <i>Solanum pinnatisectum</i>, and <i>Solanum cardiophyllum</i>, this approach resulted in the annotation of over 20 acyl solamines including short- and medium-chain fatty acyl solamines, hydroxycinnamoyl solamines, and other aromatic acyl solamines. In addition, minor derivatives with <i>N</i>-oxidized solamine moieties (acyl solamine-<i>N</i>-oxides and di-<i>N</i>-oxides) and <i>N</i>-demethylated solamine moieties (acyl nor- and dinor-solamines) were detected. The annotated compounds formed singly and doubly protonated molecules under positive ion electrospray conditions. Upon collision-induced dissociation (CID), protonated acyl solamines and derivatives with modified solamine moieties produced informative and readily interpretable product ion spectra. This enabled the structural characterization of the solamine head group and, in some cases, of the acyl moiety. To localize the positions of the carbon–carbon double bonds, major unsaturated medium-chain fatty acyl solamines were isolated in small quantities from <i>S. tuberosum</i> tuber periderm and derivatized with meta-chloroperbenzoic acid. Analysis of the CID mass spectra obtained from the protonated oxidation products provided valuable information for the further structural characterization of these compounds.</p>","PeriodicalId":16178,"journal":{"name":"Journal of Mass Spectrometry","volume":"60 10","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/epdf/10.1002/jms.5177","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145111128","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}