International Journal of Mass Spectrometry最新文献

An adaptive EEMD-machine learning algorithm for multi-matrix drug concentration prediction using miniature mass spectrometry 微型质谱法多基质药物浓度预测的自适应eemd -机器学习算法

IF 1.6 3区化学

International Journal of Mass Spectrometry Pub Date : 2025-06-28 DOI: 10.1016/j.ijms.2025.117485

Binrui Xie , Yanbing Li , Nan Zhang , Chuangui Zhou , Jiexun Bu , Lun Wu , Jun Zhu , Wenzhuo Wang , Lei Liu , Ming Li

{"title":"An adaptive EEMD-machine learning algorithm for multi-matrix drug concentration prediction using miniature mass spectrometry","authors":"Binrui Xie , Yanbing Li , Nan Zhang , Chuangui Zhou , Jiexun Bu , Lun Wu , Jun Zhu , Wenzhuo Wang , Lei Liu , Ming Li","doi":"10.1016/j.ijms.2025.117485","DOIUrl":"10.1016/j.ijms.2025.117485","url":null,"abstract":"<div><div>In this study, an innovative approach combining Machine Learning (ML) with Ensemble Empirical Mode Decomposition (EEMD) was proposed to predict lamotrigine concentrations in actual samples, improving detection performance in complex matrices. EEMD decomposed the mass spectrometry data to extract Intrinsic Mode Functions (IMFs), enabling separation of noise from key signal features. Ridge Regression (RR) addressed multicollinearity among high-dimensional IMF features and enhanced model generalization via L2 regularization. ML was further applied to optimize the key EEMD parameter (ensemble number K),thereby improving both decomposition quality and prediction accuracy. Experimental validation showed that the method achieved over 90 % prediction accuracy in three types of blind samples (PBS, rabbit blood, and human matrix), with improved Relative Standard Deviation (RSD). These results confirm the method’s precision and robustness in diverse biological matrices. Compared to traditional techniques, the proposed approach delivers marked improvements in both accuracy and stability, can supporting more reliable drug concentration monitoring for clinical applications.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"516 ","pages":"Article 117485"},"PeriodicalIF":1.6,"publicationDate":"2025-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144523240","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}

引用次数: 0

All-ions laser induced dissociation (AI-LID) in the C-trap of a Q Exactive: Data independent identification and quantification directly from ultra-high resolution differential mass spectra Q萃取物c阱中全离子激光诱导离解（AI-LID）：直接从超高分辨率微分质谱数据独立鉴定和定量

IF 1.6 3区化学

International Journal of Mass Spectrometry Pub Date : 2025-06-18 DOI: 10.1016/j.ijms.2025.117484

Luke MacAleese , Xavier Dagany , Lény Garcia , Jérôme Lemoine , Philippe Dugourd , Marion Girod

{"title":"All-ions laser induced dissociation (AI-LID) in the C-trap of a Q Exactive: Data independent identification and quantification directly from ultra-high resolution differential mass spectra","authors":"Luke MacAleese , Xavier Dagany , Lény Garcia , Jérôme Lemoine , Philippe Dugourd , Marion Girod","doi":"10.1016/j.ijms.2025.117484","DOIUrl":"10.1016/j.ijms.2025.117484","url":null,"abstract":"<div><div>An analytical method is demonstrated which allows to follow a data independent, all ion fragmentation (AIF) acquisition procedure, but to fall back on a standard and generic data-dependent acquisition (DDA) analysis procedure for the data treatment: searching databases with individual precursor ions and fragments lists. This method is implemented with photo-activation (LID) in the visible range which allows extreme specificity and sensitivity, and is demonstrated on Cysteine-containing tryptic peptides grafted with a chromophore. This proof of concept relies on the efficient implementation of LID directly in the C-trap of a ThermoScientific QExactive mass spectrometer during ion accumulation, before full MS detection. Laser irradiation turned alternatively ON and OFF after each full MS allows to build differential mass spectra in which non-dissociating ions are cancelled out while fragmenting precursors and fragments show up with opposite signs, which enables to build precursor/fragments lists for database search. Protein identification was demonstrated with remarkably low false discovery rates. Relative quantification was also demonstrated by integration of precursor and fragment ion elution peaks after differential analysis and limits of quantifications were demonstrated down to 11 ng of proteins injected. This mixed approach takes the best of both worlds – the deep proteome coverage of DIA, with the exhaustive fragmentation of all precursor ions, and the reliability and ease of use of classical DDA database search, relieving the need for the initial constitution of a spectral library.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"515 ","pages":"Article 117484"},"PeriodicalIF":1.6,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144335901","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}

引用次数: 0

Structure selective fragment ions of epoxidized sphingolipids 环氧鞘脂结构选择性片段离子

IF 1.6 3区化学

International Journal of Mass Spectrometry Pub Date : 2025-06-16 DOI: 10.1016/j.ijms.2025.117483

Jing Yu , Sven Heiles

{"title":"Structure selective fragment ions of epoxidized sphingolipids","authors":"Jing Yu , Sven Heiles","doi":"10.1016/j.ijms.2025.117483","DOIUrl":"10.1016/j.ijms.2025.117483","url":null,"abstract":"<div><div>Sphingolipids are essential building blocks of most organisms. The structure of sphingolipids is tightly regulated and dysregulation during diseases can result in altered sphingolipid structures. In this manuscript, we explore the potential of sphingolipid epoxidation for the assignment and discrimination of sphingolipid structures. Employing shotgun tandem mass spectrometry, liquid chromatography tandem mass spectrometry, authentic sphingolipid standards, and density function theory, we demonstrate that epoxidation of shingoid bases (SPBs), ceramides, and sphingomyelins facilitates C=C bond (DB) position assignment. This includes DBs in the N-linked fatty acyl moiety and the sphingoid base. For SPBs with DBs at position 4, a major component for almost all sphingolipids, we furthermore demonstrate that the fragmentation pathway differs for this DB position compared to other DB-diagnostic fragment ions. We show that epoxidation of this DB position facilities intramolecular rearrangement and formation of distinct diagnostic fragment ions. To demonstrate the analytical capabilities and show that the 4 SPB DBs enable confident differentiation of ceramides and dihydroceramides, results for brain ceramide extract are presented. The identified fragmentation pathway for 4 SPB DB ions in combination with N-acyl assignment and DB position assignment allows to annotate 25 ceramide/dihydroceramide compounds in the brain ceramide extract out of which 23 are DB position isomers.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"515 ","pages":"Article 117483"},"PeriodicalIF":1.6,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144330782","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}

引用次数: 0

MALDI-TOF-MS unveils the distribution of oligosaccharides produced by hydrolysis of lichen polysaccharides through acidic and oxidative methods – a comparative study MALDI-TOF-MS揭示了通过酸性和氧化方法水解地衣多糖产生的低聚糖的分布-一项比较研究

IF 1.6 3区化学

International Journal of Mass Spectrometry Pub Date : 2025-06-06 DOI: 10.1016/j.ijms.2025.117473

Camille Guitteny , Simon Ollivier , Oznur Yeni , Mathis Ralaivao , Mathieu Fanuel , Joël Boustie , Isabelle Compagnon , Vincent Ferrières , Solenn Ferron , Hélène Rogniaux , David Ropartz , Laurent Legentil , Françoise Le Dévéhat

{"title":"MALDI-TOF-MS unveils the distribution of oligosaccharides produced by hydrolysis of lichen polysaccharides through acidic and oxidative methods – a comparative study","authors":"Camille Guitteny , Simon Ollivier , Oznur Yeni , Mathis Ralaivao , Mathieu Fanuel , Joël Boustie , Isabelle Compagnon , Vincent Ferrières , Solenn Ferron , Hélène Rogniaux , David Ropartz , Laurent Legentil , Françoise Le Dévéhat","doi":"10.1016/j.ijms.2025.117473","DOIUrl":"10.1016/j.ijms.2025.117473","url":null,"abstract":"<div><div>MALDI-TOF MS methods coupled with offline chromatographic data were used to compare the distribution of oligosaccharides generated from acidic or oxidative degradation (Fitdog) of high molecular weight polysaccharides (>10 kDa) obtained from two lichens <em>Lasallia pustulata</em> and <em>Cetraria islandica</em>. MALDI allowed to quickly compare the kinetics of degradation on both models (starting from non-purified polysaccharides) and to evaluate the dispersity of the resulting oligosaccharides. MALDI-MS confirmed on one hand that TFA hydrolysis gave neutral oligosaccharides easy to correlate with the chemical formula. On the other hand, more structural diversity was evidenced using the Fitdog protocol. Deep analysis of the MALDI data highlighted the formation of by-products corresponding to modified oligosaccharides (e.g., intracyclic cleavages).</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"515 ","pages":"Article 117473"},"PeriodicalIF":1.6,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144280201","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}

引用次数: 0

Structural analysis of echinocandins via high-performance liquid chromatography-quadrupole/time-of-flight-tandem mass spectrometry 高效液相色谱-四极杆/飞行时间串联质谱法分析棘白菌素的结构

IF 1.6 3区化学

International Journal of Mass Spectrometry Pub Date : 2025-06-05 DOI: 10.1016/j.ijms.2025.117475

Hanzhi Zhang , Xiakun Wang , Bin Xu , Zhenhua Tian , Yu Luo , Zhijun Tang , Wen Liu

{"title":"Structural analysis of echinocandins via high-performance liquid chromatography-quadrupole/time-of-flight-tandem mass spectrometry","authors":"Hanzhi Zhang , Xiakun Wang , Bin Xu , Zhenhua Tian , Yu Luo , Zhijun Tang , Wen Liu","doi":"10.1016/j.ijms.2025.117475","DOIUrl":"10.1016/j.ijms.2025.117475","url":null,"abstract":"<div><div>Herein, the structures of echinocandins were analyzed by high-performance liquid chromatography-quadrupole/time-of-flight-tandem mass spectrometry (HPLC-Q/TOF-MS/MS). The echinocandin components were separated by using a Diamonsil Plus C18 column (5 μm, 4.6 mm × 250 mm), with 0.1 % formic acid in water as mobile phase A and 0.1 % formic acid in acetonitrile as mobile phase B under gradient elution. A systematic strategy for the structural characterization of echinocandin B, which is the main component of echicandins, is presented based on the accurate molecular mass and diagnostic ions obtained from both adduct ions [M+H]<sup>+</sup> and [M+Na]<sup>+</sup> as precursor ions. In the three fragmentation pathways obtained from the precursor ion of [M+H]<sup>+</sup>, echinocandins and its fragment ions produced continuous dehydrated ions ([M-<em>n</em>H<sub>2</sub>O + H]<sup>+</sup>, <em>n</em> = 1, 2, 3, 4). The <em>N</em>-terminal fatty acyl (FA) connecting to the ornithine derivative transferred to the amino group of the proline derivative during fragmentation. Different characteristic ions, depending on the number of hydroxyls (0, 1, 2) on the ornithine derivative of different echinocandin analog. Moreover, the threonine residues underwent the neutral consecutive loss of acetaldehyde from the [M+Na]<sup>+</sup> precursor ion. The [M+H]<sup>+</sup> and [M+Na]<sup>+</sup> echinocandin precursor ions respectively lost 1-(4-hydroxyphenyl)ethane-1,2-diol and 2-hydroxy-2-(4-hydroxyphenyl)acetaldehyde from the homotyrosine residues to generate different fragmentation ions. Thirteen echinocandin analogs were identified, including echinocandin C, echinocandin D, and echinocandin B variants with different FA and amino acid compositions.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"515 ","pages":"Article 117475"},"PeriodicalIF":1.6,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144243010","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}

引用次数: 0

Structural ion mobility spectrometry: What can we really measure? 结构离子迁移率光谱法：我们真正能测量什么？

IF 1.6 3区化学

International Journal of Mass Spectrometry Pub Date : 2025-06-04 DOI: 10.1016/j.ijms.2025.117482

Thanh D. Do

引用次数: 0

Development of a high efficiency cavity ion source and its characterization using a quadrupole mass analyser 高效腔离子源的研制及其四极质谱分析仪表征

IF 1.6 3区化学

International Journal of Mass Spectrometry Pub Date : 2025-05-31 DOI: 10.1016/j.ijms.2025.117474

VarunK. Yadav , R.K. Bhatia , A. Singh , A.M. Kasbeker , M.M. Gulhane , E. Ravisankar , T.K. Saha

引用次数: 0

An in situ analysis of the components of HTS vapor using a home-made high-temperature time-of-flight mass spectrometer 利用自制的高温飞行时间质谱仪对高温高温蒸汽组分进行了原位分析

IF 1.6 3区化学

International Journal of Mass Spectrometry Pub Date : 2025-05-21 DOI: 10.1016/j.ijms.2025.117471

Zejie Fei, Min Ge, Yuan Qian, Hongtao Liu, Yuanyuan Tang

{"title":"An in situ analysis of the components of HTS vapor using a home-made high-temperature time-of-flight mass spectrometer","authors":"Zejie Fei, Min Ge, Yuan Qian, Hongtao Liu, Yuanyuan Tang","doi":"10.1016/j.ijms.2025.117471","DOIUrl":"10.1016/j.ijms.2025.117471","url":null,"abstract":"<div><div>The aim of this study was to propose the decomposition mechanism of heat transfer salt (HTS or Hitec salt) using a high-temperature furnace coupled with a time-of-flight mass spectrometer (TOF-MS). The decomposition process was systematically investigated in a vacuum environment at temperatures of 45 °C, 80 °C, 150 °C, 200 °C, 220 °C and 280 °C. The thermal decomposition of HTS initiated at and above 200 °C, which was slightly higher than its melting point of 142 °C. The main products resulting from the thermochemical reactions of nitrate/nitrite were NO and N<sub>2</sub> respectively, followed by N<sub>2</sub>O. These findings revealed an unconventional reaction pathways for HTS decompositions as it contradicted the common assumption that O<sub>2</sub> or NO<sub>2</sub> would be present during this process. These new evidences further support the existence of intermediate species, such as superoxide and peroxide ions, in the molten salts during the initial thermal-chemical reaction process involving nitrite/nitrate salts.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"514 ","pages":"Article 117471"},"PeriodicalIF":1.6,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144106834","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}

引用次数: 0

Chirality effects on the intrinsic acidity of isomeric tripeptides containing a D/L-Cysteine on the N-terminus: CAA and dCAA 手性对n端含D/ l -半胱氨酸的异构体三肽固有酸度的影响：CAA和dCAA

IF 1.6 3区化学

International Journal of Mass Spectrometry Pub Date : 2025-05-20 DOI: 10.1016/j.ijms.2025.117472

Shiyuan Wang, Zachary Buen, Kimberlyann R. Harvey, Yuntao Zhang, Jianhua Ren

{"title":"Chirality effects on the intrinsic acidity of isomeric tripeptides containing a D/L-Cysteine on the N-terminus: CAA and dCAA","authors":"Shiyuan Wang, Zachary Buen, Kimberlyann R. Harvey, Yuntao Zhang, Jianhua Ren","doi":"10.1016/j.ijms.2025.117472","DOIUrl":"10.1016/j.ijms.2025.117472","url":null,"abstract":"<div><div>Chirality effects on the intrinsic gas-phase acidity of oligopeptides have been studied using a pair of stereoisomeric tripeptides consisting of a D/L-cysteine (C) and two residues of alanine (A): CAA and <sup>d</sup>CAA, where the C-terminus is amidated. Mass spectrometry measurements through bracketing via collision-induced dissociation clearly show that CAA is a stronger gas-phase acid than <sup>d</sup>CAA. Quantitative values of the acidity were determined using the extended Cooks kinetic method. The resulting deprotonation enthalpy (<em>Δ</em><sub>acid</sub><em>H</em>) for CAA is 326.2 kcal/mol (1364.7 kJ/mol) and for <sup>d</sup>CAA it is 326.8 kcal/mol (1367.6 kJ/mol). The corresponding gas-phase acidity (<em>Δ</em><sub>acid</sub><em>G</em>) for CAA is 321.3 kcal/mol (1344.2 kJ/mol) and for <sup>d</sup>CAA it is 322.0 kcal/mol (1347.3 kJ/mol). Changing the N-terminal cysteine from the L-form to the D-form reduces the gas-phase acidity by about 0.6 kcal/mol (2.5 kJ/mol). Extensive conformational searches followed by quantum chemical calculations at the ωB97X-D/6-311+G(d,p) level of theory yielded a set of lowest energy conformations for each peptide species. Theoretical gas-phase acidities calculated using the Boltzmann averaged conformational contributions are in good agreement with the experimental data. The shift in the acidity is likely due to the conformational effect induced by D-cysteine, which increases the stability of the neutral <sup>d</sup>CAA, and hence reduces its acidity. A chirality change on a single amino acid can have a noticeable effect on the biochemical properties of peptides and proteins.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"514 ","pages":"Article 117472"},"PeriodicalIF":1.6,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144139461","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}

引用次数: 0

Impact of glucagon oxidation on fibril formation 胰高血糖素氧化对纤维形成的影响

IF 1.6 3区化学

International Journal of Mass Spectrometry Pub Date : 2025-05-14 DOI: 10.1016/j.ijms.2025.117468

Aleksandra Antevska , Gaoyuan Lu , Emmanuel Nkyaagye , Sarah S. Hirschbeck , Connor C. Long , Lingjun Li , Thanh D. Do

{"title":"Impact of glucagon oxidation on fibril formation","authors":"Aleksandra Antevska , Gaoyuan Lu , Emmanuel Nkyaagye , Sarah S. Hirschbeck , Connor C. Long , Lingjun Li , Thanh D. Do","doi":"10.1016/j.ijms.2025.117468","DOIUrl":"10.1016/j.ijms.2025.117468","url":null,"abstract":"<div><div>Glucagon structural dynamics is crucial for its function and pathology, yet its oligomerization and fibrillization mechanisms remain unclear. The early assembly of glucagon into fibrils is a critical process that can be perturbed by oxidation at key residues. In this study, we systematically tracked the oligomer formation of native glucagon up to the decamer level, revealing that glucagon undergoes oxidation at tryptophan and methionine—residues essential to its steric zipper structure. Our findings also indicate that oxidation exerts a dual effect on glucagon fibrillation. At low concentrations, oxidation partially unfolds glucagon's α-helix, facilitating hetero-oligomer formation between oxidized and native peptides, which promotes further oligomerization and unfolding. However, at high concentrations, oxidized glucagon fails to self-assemble into fibrils and appears more susceptible to degradation. Chromatographic analysis differentiates native and oxidized glucagon, highlighting increased polarity and multiple elution peaks indicative of diverse oxidative states, while mass spectrometry confirms site-specific modifications that influence structural transitions. These results emphasize the fine balance between oxidation and self-assembly, with implications for glucagon's therapeutic stability. An understanding of oxidation-induced aggregation dynamics is essential for developing stable glucagon formulations, underscoring the importance of controlling oxidative conditions to preserve their functionality and efficacy.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"514 ","pages":"Article 117468"},"PeriodicalIF":1.6,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144090129","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}

引用次数: 0