International Journal of Mass Spectrometry最新文献

{"title":"Comparison of the results of the aberration approach for the calculation of electrostatic TOF mass analyzers with simulation in SIMION","authors":"Daniil D. Odintsov ,&nbsp;Sergey S. Poteshin","doi":"10.1016/j.ijms.2025.117526","DOIUrl":"10.1016/j.ijms.2025.117526","url":null,"abstract":"<div><div>In the last few years, high-resolution time-of-flight mass analyzers (TOF-MA) have been intensively developed. Their development requires tools that provide very accurate calculation of ion trajectories in electric fields, since an error on the scale of hundreds of picoseconds at millisecond flight times (10⁻¹⁰ %) already leads to noticeable distortions of the result. The main apparatus for calculating such systems is the aberration theory, but it has a limitation in the accuracy of calculations, since it is based on expansion in a series, and taking into account the next order of expansion significantly complicates the formulas. In this regard, using the example of calculating ion trajectories for TOF-MA with sector electrostatic fields, a comparison of the results, obtained using the aberration theory was carried out with the results of modeling in Simion. Results of the comparison indicate the possibility of applicability of the program for calculating multi-turn mass analyzers (MT-MA). Using the developed program, MT-MA with a resolution of 470,000 was calculated.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"519 ","pages":"Article 117526"},"PeriodicalIF":1.7,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145048038","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":"GC-MS unveils monosaccharide D-Allose in Terminalia arjuna bark extract acting against biofilm regulatory proteins (SrtA and SarA) of Staphylococcus aureus: A drug discovery approach","authors":"Shraavani Konatam,&nbsp;Dijendra Nath Roy","doi":"10.1016/j.ijms.2025.117527","DOIUrl":"10.1016/j.ijms.2025.117527","url":null,"abstract":"<div><div>The rising prevalence of biofilm-related infections and foodborne diseases, particularly those caused by <em>Staphylococcus aureus</em>, presents significant challenges to conventional treatment strategies due to the increasing phenomenon of antibiotic resistance caused by biofilm. In response, this study employed GC-MS analysis of the methanolic and n-hexane extracts of <em>Terminalia arjuna</em> bark, a traditional medicinal plant, and identified a diverse array of bioactive compounds. All 79 compounds identified from GC-MS data were examined to determine the best binding score with SrtA and SarA, two key proteins involved in the development of biofilms and the pathogenicity of <em>Staphylococcus aureus.</em> Among 79 compounds, D-Allose, a monosaccharide, demonstrated the best binding affinity with SrtA (−6.304 kcal/mol) by involving five hydrogen bonds and SarA (−5.101 kcal/mol) by involving three hydrogen bonds, compared to other compounds among 158 interactions. Molecular dynamics and simulations were performed for 100 ns to analyze the interaction parameters with SrtA and SarA. Corresponding MM-GBSA binding energy values were −33.66 kcal/mol (D-Allose with SrtA), −18.09 kcal/mol (D-Allose with SarA). The fact that D-Allose has zero violations of Lipinski's Rule of Five further exemplifies its suitability as a medication candidate. These interactions suggest that D-Allose may interfere with bacterial adhesion, quorum sensing, and the synthesis of the biofilm matrix by interacting with SrtA and SarA. To the best of our knowledge, this is the first study to elucidate the potential mechanism by which D-Allose exerts its antibiofilm activity. Future research on in vitro and <em>in vivo</em> studies should focus on experimental validation to establish D-Allose as a promising monosaccharide candidate for combating biofilm-related antibiotic-resistant <em>Staphylococcus aureus</em> infections.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"518 ","pages":"Article 117527"},"PeriodicalIF":1.7,"publicationDate":"2025-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145045098","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":"Two-dimensional tandem mass spectrometry in a linear quadrupole ion trap using consecutive product ion sweeps","authors":"Eric T. Dziekonski","doi":"10.1016/j.ijms.2025.117524","DOIUrl":"10.1016/j.ijms.2025.117524","url":null,"abstract":"<div><div>Two-dimensional tandem mass spectrometry (2D-MS/MS) is a powerful analysis technique which can quickly produce a map of all precursor-product ion relationships within a sample, from a single ion injection event, and is greatly suited to low-cost instrumentation like ion traps. The ability to record this type of information in an unsupervised and unbiased manner makes this technique highly amenable to artificial intelligence-based workflows which can statistically examine the datasets to perform structural elucidation, generate more confident peak assignments, and/or discover new chemistries. Previous implementations of the 2D-MS/MS scan function kept the RF voltage applied to the trap constant and scanned an auxiliary frequency to eject and detect the product ions. A direct consequence of this is that ions of higher precursor and product <em>m/z</em> would have a lower observed mass resolution and sensitivity, leading to more potential candidates for peak identification algorithms and higher uncertainty in the reported results. Herein, we describe a new approach to 2D-MS/MS analysis in a linear quadrupole ion trap which utilizes consecutive, traditional, RF amplitude ramps to resonantly eject ions from the trap near the boundary of the Mathieu stability diagram. Relative to its predecessors, the technique does require more time to acquire, however, it necessitates fewer instrument modifications and has more robust calibration procedures. More importantly though, its use produces higher sensitivity spectra with constant 2D peak resolutions (3 Da FWHM @ 125 kDa/s), which can be predicted based on the set product ion scan rate and resonant ejection point. Additional discussion is aimed at methods by which the scan might be improved, or optimized, for higher speed workflows utilizing sample arrays. This work paves the path towards isotopically resolved 2D-MS/MS spectra, which would greatly enhance the power of the technique.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"518 ","pages":"Article 117524"},"PeriodicalIF":1.7,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145026637","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 thermal perspective on MALDI ionization: A long journey from fundamental mechanisms to a practical solution for carbohydrate analysis","authors":"I-Chung Lu","doi":"10.1016/j.ijms.2025.117516","DOIUrl":"10.1016/j.ijms.2025.117516","url":null,"abstract":"<div><div>Matrix-assisted laser desorption/ionization (MALDI) is a vital analytical tool, but the fundamental ionization mechanism has long been debated. This perspective summarizes over a decade of research to introduce a comprehensive thermal framework, culminating in the quantitative thermally induced proton transfer (TIPT) model for MALDI. Validated by numerous experiments without fitting parameters, we identify that laser-induced temperature is the dominant factor in the primary ionization of protonated ions. The principle was subsequently applied to resolve the longstanding challenges of carbohydrate analysis. To overcome the characteristically low sensitivity of carbohydrates, the rapidly freeze-drying droplet (RFDD) sample preparation method was developed by preserving homogeneously distributed, preformed sodium adducts. RFDD increases ion intensity by over two orders of magnitude, eliminates the \"sweet spot\" effect, and enables reliable quantitative analysis. This journey from fundamental mechanistic inquiry to a practical, innovative technology powerfully illustrates how basic science drives analytical advancements.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"518 ","pages":"Article 117516"},"PeriodicalIF":1.7,"publicationDate":"2025-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144925849","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":"Extended m/z range of coaxial linear ion trap/time-of-flight mass spectrometry using dynamic electric field ejection","authors":"Yixue Cao ,&nbsp;Xuesong Zhang ,&nbsp;Jilong Wang ,&nbsp;Chenxin Wu ,&nbsp;Lei Hua ,&nbsp;Ping Chen ,&nbsp;Haiyang Li","doi":"10.1016/j.ijms.2025.117517","DOIUrl":"10.1016/j.ijms.2025.117517","url":null,"abstract":"<div><div>Linear ion trap/time-of-flight mass spectrometry (LIT/TOFMS) to perform ion accumulation in a separate LIT prior to mass analysis is a more generally accepted method to improve duty cycle. However, a long distance between the accumulation region and the TOF pusher led to time-of-flight dispersion of the injected ions with different <em>m/z</em>, thereby limiting the detectable mass range in a single scan. This paper studies the characteristic behaviors of ion ejection from a segmented LIT through SIMION simulation. A novel dynamic electric field ejection strategy is proposed to broaden the ejection mass range of LIT. By linearly scanning the voltages on the segmented LIT and the ion gate, the axial potential distribution is dynamically adjusted to gradually shift the ion accumulation region toward the TOF pusher. As a result, the ejection distance between the accumulation region and the TOF pusher was slowly shortened, reducing time dispersion among different <em>m/z</em> ions. The simulation results demonstrate that this method significantly improves mass range of the coaxial dual LIT/TOFMS, achieving near 100 % injection efficiency for <em>m/z</em> 130–2000 with a mass window ratio <em>(m/z)</em>_<em>max</em><em>/(m/z)</em>_<em>min</em> of 15. This technology provides a solution for broadening the mass range of LIT-based hybrid instruments.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"518 ","pages":"Article 117517"},"PeriodicalIF":1.7,"publicationDate":"2025-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145019351","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":"Next generation MasSpec pen technology: Innovations in instrumentation and medical device development for intraoperative use","authors":"Charles A. Wolfe ,&nbsp;Sydney Povilaitis ,&nbsp;Michael F. Keating ,&nbsp;Ashley E. Montgomery ,&nbsp;Bryan M. Burt ,&nbsp;Amir A. Jazaeri ,&nbsp;Livia S. Eberlin","doi":"10.1016/j.ijms.2025.117515","DOIUrl":"10.1016/j.ijms.2025.117515","url":null,"abstract":"<div><div>The chemical specificity and sensitivity of mass spectrometry techniques are being increasingly explored to enhance intraoperative decision making. Several mass spectrometry technologies have been developed to rapidly detect changes in tissue metabolism, generating “molecular fingerprints” that enable rapid tissue identification in surgical procedures. Among these, our team has developed the MasSpec Pen as a liquid-extraction based device integrated to an interface and mass spectrometer for direct and rapid molecular analysis of tissues <em>in vivo</em> and <em>ex vivo</em>. Since its first report and clinical testing in intraoperative studies, we have made several improvements to the MasSpec Pen technology to improve its analytical and procedural functionality for medical use. Here, we describe the latest advances in MasSpec Pen technology including the development of a new interface with a dual heated path vacuum chamber that improves solvent vaporization, data quality, and enables integration with different mass spectrometers. We also describe the development of new MasSpec Pen devices made with 3D printing technology for use in laparoscopy and bronchoscopy procedures. Examples of molecular data obtained with these systems are provided in the direct analysis of human tissues.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"518 ","pages":"Article 117515"},"PeriodicalIF":1.7,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144917638","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":"Pyrolysis and thermal extraction of polymeric materials with suction-driven, real-time ionization sources and rapid polarity switching, high resolution mass spectrometry","authors":"G. Asher Newsome ,&nbsp;Katja S. Diaz-Granados ,&nbsp;Karen Sam ,&nbsp;Joshua D. Caldwell ,&nbsp;Erin R. Birdsall","doi":"10.1016/j.ijms.2025.117514","DOIUrl":"10.1016/j.ijms.2025.117514","url":null,"abstract":"<div><div>Real-time sampling systems are assembled for analysis of pyrolyzed material using in-line ionization and high resolution mass spectrometry. Two commercial models of Pyroprobe pyrolyzer with either a wand-mounted coil or a drop-in sample chamber are reconfigured from the standard gas chromatograph interface. Either a flow cell containing a platinum coil or a drop-in pyrolysis chamber is connected to a heated transfer line that conducts pyrolysates directly to a photoionization or dielectric barrier discharge source. The ion source is mounted to the front of an Orbitrap system, drawing analyte through from the pyrolyzer using instrument vacuum and/or supplementary pumping. The mass spectrometer scans in rapidly-alternating polarity so that positive and negative mode analyses are acquired in a single run. Pyrolyzed samples of tens of micrograms of polymeric materials yielded robust and resolved signal, especially from halogenated ions in negative mode that otherwise did not produce enough electron impact ionization signal for identification. The photoionization source in particular was easily purged of lingering pyrolysate by temporarily increasing the supplemental flow rate, rapidly returning signal to baseline levels after an analytical run. Elimination of carryover allowed replicate analyses to be collected at a rate of every 2 min without an autosampler. Slow-ramp thermal extraction analyses was performed on the same system as flash pyrolysis without any change in hardware.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"518 ","pages":"Article 117514"},"PeriodicalIF":1.7,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144906909","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":"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}