International Journal of Mass Spectrometry最新文献

{"title":"Revealing the unexpected: formal charge exchanges in collisional activation of cereulide ionized molecular species","authors":"Chenqin Cao ,&nbsp;Sophie Liuu ,&nbsp;Ekaterina Darii ,&nbsp;Amandine Hueber ,&nbsp;Yves Gimbert ,&nbsp;Annelaure Damont ,&nbsp;Olivier Firmesse ,&nbsp;François Fenaille ,&nbsp;Jean-Claude Tabet","doi":"10.1016/j.ijms.2025.117513","DOIUrl":"10.1016/j.ijms.2025.117513","url":null,"abstract":"<div><div>Under positive electrospray desorption/ionization mass spectrometry (ESI-MS) conditions, a bacterial cyclodepsipeptide toxin, cereulide [^(D)Ala-^(L)OVal-^(L)Val-^(D)OLeu]₃, is mainly desorbed as ammonium adduct and alkali-cationized species. In addition to the naturally occurring alkali cation (Li⁺/Na⁺/K⁺), Rb⁺ can be attached to the molecule after addition of its chlorine salt (RbCl) solution. Under non-resonant collision-induced dissociations (non-resonant CID) using a quadrupole time-of-flight (Qq/TOF) instrument, bare alkali cations were recently detected in non-resonant CID spectra. Investigation using energy-resolved mass spectrometry (ERMS) of cationized cereulide revealed coexistence of <strong><em>charge-solvated (CS)</em></strong> and <strong><em>protonated salt (PS)</em></strong> tautomers. Infusion of cereulide solution containing RbCl salt into the ion source led to the unexpected detection of ⁸⁵Rb⁺ and ⁸⁷Rb⁺ within their natural abundances when Rb-free species ([M + NH₄]⁺, [M+Na]⁺ or [M+K]⁺) were selected for subsequent fragmentation. To elucidate the origin of these unexpected cations, ERMS of the various ionized cereulide species was carried out using an Orbitrap-based instrument. Curiously, in addition to the unexpected Rb⁺ isotopique cations, Rb₂Cl⁺ isotopologues were abundantly detected in non-resonant CID spectra of [M + NH₄]⁺, [M+Na]⁺, and [M+K]⁺, but not of [M+⁸⁵Rb]⁺. Additional calculations and ERMS logarithmic plots made it possible to rule out a possible <em>endogenous</em> origin of the Rb₂Cl⁺ and Rb⁺ isotopologues. They are produced by ion/molecule reactions in the higher-energy collisional dissociation (HCD) cell between ionized cereulide (and b_(12-n) ions), relaxed by the buffer gas, and neutral RbCl isotopologue salts present in gas phase. The latter are likely generated either during preliminary studies of Rb_nCl_(n-1)⁺ cluster dissociation in smaller cluster ions and neutral RbCl loss, or from the HCD cell surface by collisions with the buffer gas. Consequently, Rb₂Cl⁺ isotopologues are not precursors of ⁸⁵Rb⁺ plus ⁸⁷Rb⁺.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"518 ","pages":"Article 117513"},"PeriodicalIF":1.7,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144925850","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":"Structure characterisation using thin-layer chromatography-MALDI MS and infrared ion spectroscopy","authors":"Jelle L. Schuurman ,&nbsp;Lara van Tetering ,&nbsp;Giel Berden ,&nbsp;Jos Oomens ,&nbsp;Jonathan Martens","doi":"10.1016/j.ijms.2025.117512","DOIUrl":"10.1016/j.ijms.2025.117512","url":null,"abstract":"<div><div>The integration of thin-layer chromatography (TLC) with matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) provides a fast workflow for the analysis of mixtures. Nevertheless, distinguishing isomers and the structural elucidation of unknown compounds remains challenging and resource intensive. Based on tandem mass spectrometry, infrared ion spectroscopy (IRIS) generates structurally diagnostic vibrational spectra for mass-selected ions confined within a mass spectrometer. By coupling IRIS to the TLC-MALDI-MS workflow, the IR spectra of molecules ionized directly from the TLC plate are obtained. In this study, we separated and identified three isomeric compounds in a mixture through sequential TLC separation, ionization, mass selection and characterization using IRIS. Furthermore, we demonstrate isomer-selective photofragmentation scans of the TLC plate along the axis of separation. This TLC-MALDI-IRIS approach represents a robust, sensitive, and versatile analytical method with broad applications in complex mixture analysis.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"518 ","pages":"Article 117512"},"PeriodicalIF":1.7,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144906908","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":"Concept for high-throughput mRNA sequence confirmation by atmospheric pressure MALDI technique applied to RNA digestion products","authors":"Kerstin Strupat,&nbsp;Frederik Busse-Patel,&nbsp;Ralf Hartmer","doi":"10.1016/j.ijms.2025.117510","DOIUrl":"10.1016/j.ijms.2025.117510","url":null,"abstract":"<div><div>Development and manufacturing of mRNA vaccines require frequent quality control measures to ensure product safety and efficacy. Mass Spectrometry in combination with Liquid Chromatography (LC-MS) is known as a powerful tool for sequence confirmation and assessment of post-transcriptional modifications. LC-MS methods, while accurate, suffer from long acquisition times, making them typically impractical for high-throughput applications.</div><div>This study introduces a novel approach for RNA oligonucleotide sequence confirmation using UV-MALDI at atmospheric pressure (AP-MALDI) coupled with high-resolution accurate mass (HRAM) Orbitrap™ mass analyzer technology. By using an Orbitrap detector, we achieve a mass accuracy below 2 ppm for the digestion products of a RNA digest, suitable for verifying oligonucleotide sequences from complex mixtures without prior separation. We employ RNase T1 owing its G-specific cleavage, an ammonium-activated cation exchange resin for purification, followed by AP-UV-MALDI MS analysis. The method is validated with a synthetic 119mer RNA oligonucleotide, confirming sequence identity through MS/MS in both positive and negative ion modes. The approach is further applied to <em>in silico</em> analysis of mRNA sequences from vaccine variants, showcasing its potential for high-throughput, rapid sequence confirmation, and variant differentiation in RNA, particularly relevant for mRNA vaccine development and quality control in biopharmaceutical manufacturing.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"518 ","pages":"Article 117510"},"PeriodicalIF":1.7,"publicationDate":"2025-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144891934","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":"Demonstration of a nested electrostatic linear ion trap for flexibility in selecting analyzer figures-of-merit","authors":"Jordan M. Fritz,&nbsp;Ian J. Carrick,&nbsp;Nicholas R. Ellin,&nbsp;Eric T. Dziekonski,&nbsp;Scott A. McLuckey","doi":"10.1016/j.ijms.2025.117511","DOIUrl":"10.1016/j.ijms.2025.117511","url":null,"abstract":"<div><div>An electrostatic linear ion trap (ELIT) is used to trap ions between two ion mirrors with image current detection by central detection electrode. Transformation of the time-domain signal to the frequency-domain via Fourier transform (FT) yields an ion frequency spectrum that can be converted to a mass-to-charge (<em>m/z</em>) scale. Injection of ions into an ELIT from an external ion source leads to a time-of-flight ion separation that ultimately determines the range of <em>m/z</em> over which ions can be collected from a given ion injection step. The <em>m/z</em> range is determined both by the length of the ELIT and by the distance of the ELIT entrance from the ion source. A longer ELIT leads to a wider <em>m/z</em> range while a shorter ELIT, under equivalent conditions, leads to higher resolving power due to increased ion frequencies. Hence, there is an inherent trade-off between the two important analyzer figures-of-merit: <em>m/z</em> range and resolving power, based on the length of the ELIT. In this work, we demonstrate a nested ELIT arrangement, referred to herein as an NELIT, that allows for the selection of one of two possible ELIT lengths within a single array of plates while employing a common detection electrode. While a range of ELIT lengths are possible, in principle, the geometry described herein leads to an effective length ratio of 2.40 for the two traps in the NELIT.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"518 ","pages":"Article 117511"},"PeriodicalIF":1.7,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144865957","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":"Photoionization of phosphorous trichloride clusters at gigawatt intense laser field","authors":"Soumitra Das,&nbsp;Pramod Sharma,&nbsp;Chiranjib Majumder","doi":"10.1016/j.ijms.2025.117509","DOIUrl":"10.1016/j.ijms.2025.117509","url":null,"abstract":"<div><div>Photoionization study of PCl₃ clusters has been carried out using time-of-flight mass spectrometry at selected wavelengths of UV (266, 355 nm) and Visible (532 nm) region employing nanosecond laser pulses of intensity ∼10⁹ W/cm². At these three laser wavelengths, dissociated fragments such as P⁺, Cl⁺, PCl⁺ and PCl₂⁺ are observed in the mass spectra. Formation of different fragments has been explained based on the multiphoton excitation at the respective wavelengths. Moreover, PCl₄⁺ ions are observed in 266 and 355 nm ionization of PCl₃ clusters. Generation of PCl₄⁺ is explained based on ion-molecule reaction within the ionized cluster. Using density functional theory (DFT), structure, ionization energy and absorption spectra of PCl₃ monomer and clusters have been calculated which helps to rationalize the experimental observation. Along with singly charged fragment ions, multiply charged atomic ions up to P⁵⁺ (I.E: 65.1 eV) and Cl⁴⁺ (I.E: 53.5 eV) are observed at 532 nm. Generation of multiply charged ions at such low laser intensity indicates efficient ionization of PCl₃ clusters. Formation of higher charge states can be explained based on “multiphoton ionization ignited-inverse bremsstrahlung heating–electron ionization”. Detailed study reveals that laser intensity, cluster size and ionization energy of the cluster constituents play an important role in governing the ionization dynamics under gigawatt laser intensity conditions. Thus, PCl₃ clusters exhibit diverse photochemical process as a function of laser wavelength at ∼10⁹ W/cm².</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"518 ","pages":"Article 117509"},"PeriodicalIF":1.7,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144865958","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":"Unimolecular decomposition of deprotonated glyphosate: Discerning cyclic versus linear dehydration products using ion mobility mass spectrometry","authors":"Olivia Rusli,&nbsp;Nicole Joy Rijs","doi":"10.1016/j.ijms.2025.117508","DOIUrl":"10.1016/j.ijms.2025.117508","url":null,"abstract":"<div><div>As observed previously by multistage electrospray ionisation mass spectrometry, collision induced dissociation (CID) of deprotonated glyphosate results in several fragmentation pathways. These include decarboxylation and dehydration, with the formation of characteristic fragments and isomeric product ions depending on the fragmentation mechanism. Herein, the potential of ion mobility – mass spectrometry (IM-MS) to separate the isomers of dehydrated glyphosate was investigated. Separation of the two isomers of dehydrated glyphosate was not observed with single-pass cyclic ion mobility experiments, nor by multi-pass experiments. However, using characteristic fragments the cyclic isomer appeared to be more stable the linear isomer. The CH₄O₃P⁻ fragment (<em>m/z</em> 95) of dehydrated glyphosate was observed for the first time here. This is suspected to be the product of an ion molecule reaction between the dehydrated glyphosate anion and background water molecules within the travelling wave ion mobility (TWIMS) cell. Hydrolysis of the dehydrated glyphosate ion resulted in methyl phosphonate anion and neutral glycine imine formation. A concerted mechanism is supported by ¹³C labelling and H/D exchange experiments.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"517 ","pages":"Article 117508"},"PeriodicalIF":1.7,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144858388","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":"Determination of 238Pu/239Pu isotope ratio under uranium interference by thermal ionization mass spectrometry","authors":"Peng-fei Zhang,&nbsp;Zhi-ming Li,&nbsp;Wen-liang Wang,&nbsp;Lei Feng,&nbsp;Jiang Xu,&nbsp;Man-chao Zhang,&nbsp;Rui-yang Xi,&nbsp;Xiao-pan Shen,&nbsp;Wei Wang","doi":"10.1016/j.ijms.2025.117496","DOIUrl":"10.1016/j.ijms.2025.117496","url":null,"abstract":"<div><div>A novel approach was developed for the precise analysis of the ²³⁸Pu/²³⁹Pu ratio in plutonium using thermal ionization mass spectrometry (TIMS). This methodology was based on the difference in thermal evaporation behavior between U and Pu during the total evaporation (TE) process. By incorporating the U interference indicator into the Pu solution, a linear model that related the <em>m/z</em> 238 a.m.u. intensity changes to the isotope ratios of ²³⁸Pu/²³⁹Pu and ²³⁸U/²³⁵U was established. The ratios of ²³⁸Pu/²³⁹Pu and ²³⁸U/²³⁵U was determined by fitting the experimental data using multiple linear regression analysis. This method had been applied to analyze laboratory isotopic standard samples Pu(SO₄)₂.4H₂O. Results showed that, even with extremely small sample size of ²³⁸Pu (picogram level), the relative standard deviation of ²³⁸Pu/²³⁹Pu ratio was less than 0.2 %. The approach was simple and would be an effective tool as a method for the characterization of ²³⁸Pu using TIMS.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"517 ","pages":"Article 117496"},"PeriodicalIF":1.7,"publicationDate":"2025-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144826472","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":"Hydrogenating atomic coinage metal cations (group 11) with H2 on charged He droplets (T<10 K) doped with metal Atoms: Early stages, ligation energies, core structures, group variations, and relativistic effects","authors":"O.V. Lushchikova ,&nbsp;M. Ončák ,&nbsp;J. Reichegger ,&nbsp;B. Felsner ,&nbsp;D.K. Böhme ,&nbsp;P. Scheier","doi":"10.1016/j.ijms.2025.117507","DOIUrl":"10.1016/j.ijms.2025.117507","url":null,"abstract":"<div><div>Experimental mass-spectrometric results are reported which demonstrate that ionized helium nanodroplets (at T &lt; 10 K) doped with the coinage metal atoms M = Cu, Ag or Au, and then exposed to molecular hydrogen, provide an abundance of singly and multiply hydrogenated coinage metal cations M⁺(H₂)_<em>n</em> and MH⁺(H₂)_<em>n</em> with <em>n</em> up to 25 and beyond. We explore here the information provided by observed distributions in the measured intensities of these ligated ions with <em>n</em> = 1–6 and use <em>ab initio</em> quantum chemical calculations to extract fundamental insights into variations in ligation energies and structures with increasing H₂ ligation and going down the Periodic Table (M⁺ = Cu⁺, Ag⁺ and Au⁺) with an eye on the role of relativistic contributions to the ligation energies expected with the increasing nuclear charge of M⁺. “Magic” numbers of H₂ additions with relatively high intensity are apparent among the first 5, especially the first 2, H₂ additions. Very substantial relativistic enhancements of <em>the third over the second-row</em> ligation energies were computed, especially for Au⁺: 83 % and 60 % respectively, for the first two H₂ ligands intimately bonded to Au⁺, and 19 % and 67 % respectively, for the addition of the first two H₂ ligands to AuH⁺. Relativistic enhancements for the addition of a third H₂ ligand and beyond were found to be essentially negligible.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"517 ","pages":"Article 117507"},"PeriodicalIF":1.7,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144840827","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":"Effect of rod asymmetry on field distortions and transmission characteristics in linear quadrupole mass filters","authors":"Sukanya Jana ,&nbsp;Santu Nath ,&nbsp;Pintu Mandal ,&nbsp;Nabanita Deb","doi":"10.1016/j.ijms.2025.117495","DOIUrl":"10.1016/j.ijms.2025.117495","url":null,"abstract":"<div><div>This article reports the appearance of the octupole and hexadecapole components in the radial potential, which are otherwise absent in a linear quadrupole mass filter of symmetric round-rod configuration, if a small structural asymmetry is introduced in one electrode. Using the commercial ion simulation package SIMION, it is shown that the weightage of the octupole and hexadecapole potential increases with an increase in the asymmetry factor. A consistent correlation is observed between the octupole and dodecapole components, and between the hexadecapole and icosapole components with asymmetry added to different rod-to-field radius ratios. The transmission characteristics of the mass filter are studied for different asymmetry factors and rod-to-field radius ratios. The variation in the resolution parameter, as derived from the transmission contour, exhibits a strong correlation with the combined weightage of the multipole fields.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"517 ","pages":"Article 117495"},"PeriodicalIF":1.7,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144827876","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":"Atmospheric pressure surface ionization mass spectrometry for oxidized SUS304 and nichrome: chromic acids (H2CrnO3n+1) as intermediate precursors for the formation of hexavalent chromium oxide negative ions HCrnO3n+1− and protonated oxide surface as solid acid","authors":"Kenzo Hiraoka ,&nbsp;Stephanie Rankin-Turner ,&nbsp;Dilshadbek T. Usmanov ,&nbsp;Satoshi Ninomiya","doi":"10.1016/j.ijms.2025.117506","DOIUrl":"10.1016/j.ijms.2025.117506","url":null,"abstract":"<div><div>Negative and positive ions generated from heated oxidized SUS304 and nichrome filaments were measured by atmospheric pressure surface ionization mass spectrometry. Both filaments produced hexavalent chromium-oxide negative ions of HCr_nO_3n+1⁻ (n = 1–4) and Cr_nO_3n^−• (n = 1–4) and positive ions of A₂HCr_nO_3n+1⁺ (n = 1–3) (A: Na and/or K). While negative ions were detected at temperatures above ∼1000 °C, positive ions were detected at much lower temperature above ∼800 °C. The precursors of negative ions were assumed to be chromic acid formed by the reaction, Cr_nO_3n + H₂O → H₂Cr_nO_3n+1 followed by electrolytic dissociation, H₂Cr_nO_3n+1 → H⁺ + HCr_nO_3n+1⁻ taking place on the solid surface. The proton H⁺ may be captured by the surface oxide instantly to form protonated metal oxide which acts a solid Brønsted acid for the protonation of gas-phase analytes. The formation of hexavalent chromium oxide ions from heated chromium alloys may be hazardous to health because they are carcinogenic at low concentrations due to their strong oxidizing properties.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"517 ","pages":"Article 117506"},"PeriodicalIF":1.7,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144827875","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}