International Journal of Mass Spectrometry最新文献

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Feedback control for electrospray ionization based on the shape of the liquid meniscus at the ESI emitter 基于ESI发射器液体半月板形状的电喷雾电离反馈控制
IF 1.7 3区 化学
International Journal of Mass Spectrometry Pub Date : 2026-02-01 Epub Date: 2025-12-27 DOI: 10.1016/j.ijms.2025.117567
Xiangting Chen , Qiangqiang Xie , Satoshi Ninomiya , Lee Chuin Chen
{"title":"Feedback control for electrospray ionization based on the shape of the liquid meniscus at the ESI emitter","authors":"Xiangting Chen ,&nbsp;Qiangqiang Xie ,&nbsp;Satoshi Ninomiya ,&nbsp;Lee Chuin Chen","doi":"10.1016/j.ijms.2025.117567","DOIUrl":"10.1016/j.ijms.2025.117567","url":null,"abstract":"<div><div>Stable electrospray ionization is crucial for ensuring consistent ion generation in mass spectrometry. Previously, a feedback control system based on spray current and Taylor cone angle was developed to automatically adjust the emitter voltage (Anal. Chem. 2023, 95, 28, 10744–10751). However, the system was susceptible to false signals caused by electrical noise, leakage, and discharge, and was not easy to implement in commercial ion sources. Here, we report a robust feedback system that relies solely on the optical image of the liquid meniscus condition at the emitter tip. A set of geometric parameters, including meniscus area, rectangularity, diameter-to-length ratio, and the degree of apex blurring, is extracted in real time from CCD images to identify the spraying mode and determine the required emitter voltage adjustment. The system maintains the Taylor cone shape within a target range, thereby preserving steady cone-jet operation under variations in flow rate, surface tension, and solvent composition. The feedback system was evaluated under both atmospheric and high-pressure ESI conditions. Under high-pressure operation, the system successfully stabilized the cone-jet mode even for pure water. The feedback-stabilized electrospray minimizes ion signal fluctuation caused by spray instability and may contribute to more reproducible ESI-MS analyses that reflect the true condition of the analyte in solution.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"520 ","pages":"Article 117567"},"PeriodicalIF":1.7,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880441","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
Improving long-term Δ47 repeatability of the Thermo Scientific 253 Plus 10 kV IRMS using a prototype Peltier-based cooling system 使用基于peltier的原型冷却系统,提高Thermo Scientific 253 Plus 10 kV IRMS的长期Δ47可重复性
IF 1.7 3区 化学
International Journal of Mass Spectrometry Pub Date : 2026-02-01 Epub Date: 2025-12-24 DOI: 10.1016/j.ijms.2025.117565
László Rinyu , Andrea Czébely , Diána Kiss , Sándor Kele , Sándor Czellár , József Molnár , Marianna Túri
{"title":"Improving long-term Δ47 repeatability of the Thermo Scientific 253 Plus 10 kV IRMS using a prototype Peltier-based cooling system","authors":"László Rinyu ,&nbsp;Andrea Czébely ,&nbsp;Diána Kiss ,&nbsp;Sándor Kele ,&nbsp;Sándor Czellár ,&nbsp;József Molnár ,&nbsp;Marianna Túri","doi":"10.1016/j.ijms.2025.117565","DOIUrl":"10.1016/j.ijms.2025.117565","url":null,"abstract":"<div><div>Clumped isotope thermometry is a robust technique for reconstructing carbonate formation temperatures; however its analytical precision is highly dependent on instrumental stability. In this study, we address the challenge of achieving long-term Δ<sub>47</sub> repeatability using a Thermo Scientific™ 253 Plus 10 kV isotope ratio mass spectrometer (IRMS) coupled to a Kiel IV automated carbonate preparation device. The IRMS is equipped with 10<sup>13</sup> Ω resistors on high-gain Faraday cups. To minimize the impact of daily laboratory temperature fluctuations, we developed and implemented a prototype Peltier-based cooling system for the amplifier housing.</div><div>The combined approach reduced long-term Δ<sub>47</sub> standard deviation from 40 to 45 ppm (occasionally reaching up to 60 ppm under extreme conditions) to around 32 ppm. Validation was performed using international carbonate standards and natural travertine samples with known formation temperatures (10–95 °C), and results were bench-marked against previously published data. These improvements demonstrate a practical pathway towards achieving high-precision clumped isotope measurements under variable environmental conditions, and they provide a reproducible methodology for laboratories operating similar instrumentation in comparable settings.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"520 ","pages":"Article 117565"},"PeriodicalIF":1.7,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837276","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
A framework for high-mass ion transmission in a hybrid SLIM-QTOF system 混合SLIM-QTOF系统中高质量离子传输的框架
IF 1.7 3区 化学
International Journal of Mass Spectrometry Pub Date : 2026-02-01 Epub Date: 2025-12-24 DOI: 10.1016/j.ijms.2025.117566
Justin Mak, Amin Famili, Christopher M. Crittenden
{"title":"A framework for high-mass ion transmission in a hybrid SLIM-QTOF system","authors":"Justin Mak,&nbsp;Amin Famili,&nbsp;Christopher M. Crittenden","doi":"10.1016/j.ijms.2025.117566","DOIUrl":"10.1016/j.ijms.2025.117566","url":null,"abstract":"<div><div>Structures for Lossless Ion Manipulation (SLIM) for high resolution ion mobility (HRIM) mass spectrometry has greatly enhanced resolution of isomers and compounds that challenge chromatography. However, in the current commercial setup consisting of a MOBIE SLIM coupled to an Agilent 6545XT, the upper limit of sensitive ion transmission is near <em>m/z</em> 4000.</div><div>We therefore aimed to overcome the truncated mass range because detecting large peptides, intact proteins, nucleic acids, and native complexes, as well as their aggregates, at lower charge states (higher <em>m/z</em>) increases spectral clarity of precursor ions, simplifies deconvolution, and can enrich sequencing coverage. Believing this was a solvable issue stemming from currently uncharacterized ion behavior, we investigated gas setup and DC potentials. Using cesium iodide and trastuzumab emtansine, our studies identified the importance of (1) increasing collision cell pressure, (2) reducing ion funnel source pressure, (3) placing the primary accelerating potential immediately before the ion trap (Trap Desolvation Delta), and (4) optimizing voltages in the Ion Beam Compressor. We also found that argon gas marginally increased signal intensities, suggesting that new hardware and electronics would be needed to further extend high-mass transmission. Taken together, our findings revise the current working theory of ion transmission in hybrid SLIM-MS systems—the primary accelerating potential must be applied immediately prior to the ion trap that accumulates ions for mobility separation instead of after the mobility separation—and serve as a more accurate user guide for higher <em>m/z</em> transmission.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"520 ","pages":"Article 117566"},"PeriodicalIF":1.7,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837270","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
Identification of transformation products by high resolution mass spectrometry wide scope screening, and risk assessment for atrazine, carbamazepine, and sulfamethoxazole aqueous solution, resulting from UV-C/chlorination 紫外- c /氯化反应对阿特拉津、卡马西平和磺胺甲恶唑水溶液转化产物的高分辨率质谱大范围筛选鉴定及风险评估
IF 1.7 3区 化学
International Journal of Mass Spectrometry Pub Date : 2026-02-01 Epub Date: 2025-12-05 DOI: 10.1016/j.ijms.2025.117555
Vitor M. Nilson , Nicole H. Lazzari , Suzan C. Zilli , Mariana R. Gama , Cristane S. Schwalm , Salatiel W. da Silva , Livia Streit , Tânia M. Pizzolato
{"title":"Identification of transformation products by high resolution mass spectrometry wide scope screening, and risk assessment for atrazine, carbamazepine, and sulfamethoxazole aqueous solution, resulting from UV-C/chlorination","authors":"Vitor M. Nilson ,&nbsp;Nicole H. Lazzari ,&nbsp;Suzan C. Zilli ,&nbsp;Mariana R. Gama ,&nbsp;Cristane S. Schwalm ,&nbsp;Salatiel W. da Silva ,&nbsp;Livia Streit ,&nbsp;Tânia M. Pizzolato","doi":"10.1016/j.ijms.2025.117555","DOIUrl":"10.1016/j.ijms.2025.117555","url":null,"abstract":"<div><div>Contaminants of environmental concern are compounds frequently detected in surface and groundwater due to anthropogenic activity. Among these compounds are atrazine (ATZ, a pesticide), carbamazepine (CBZ, an antiepileptic), and sulfamethoxazole (SMX, an antibiotic). These compounds are frequently detected in both raw and treated water samples, with concentrations ranging from ng L<sup>−1</sup> to μg L<sup>−1</sup>. The degradation of these contaminants can lead to incomplete mineralization, potentially forming sub-products known as transformation products. Both parent compounds and by-products may be of toxicological concern. In the present study, samples resulting from the degradation of ATZ, CBZ, and SMX by combined UV-C irradiation and chlorination were analyzed to investigate the formation of transformation products and their associated toxicity. ATZ and SMX underwent nearly complete degradation (&gt;99 %), whereas CBZ showed limited degradation (28 %). A total of 24 transformation products were identified using ultra-high performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UHPLC-QTOF-MS) and a suspect screening approach. <em>In silico</em> quantitative structure–activity relationship analysis was performed to assess the potential risks of the compounds. Developmental toxicity, ready biodegradability, carcinogenicity, and mutagenicity were predicted using VEGA software. The results show that, while CBZ itself is not mutagenic, all transformation products except CBZ-255 are predicted as mutagenic with high reliability. CBZ transformation products are carcinogenic and toxicants with moderate to high reliability, and non-readily biodegradable with moderate to low reliability. All ATZ transformation products were found to be carcinogenic with moderate to low reliability, and toxicant with low reliability.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"520 ","pages":"Article 117555"},"PeriodicalIF":1.7,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748584","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
Optimising the choice of normalisation method for use in machine-learning classification of human blood plasma ambient ionisation mass spectra 优化归一化方法的选择,用于人类血浆环境电离质谱的机器学习分类
IF 1.7 3区 化学
International Journal of Mass Spectrometry Pub Date : 2026-02-01 Epub Date: 2025-12-03 DOI: 10.1016/j.ijms.2025.117553
Annabel S.J. Eardley-Brunt , Liwen Song , Oxford Acute Myocardial Infarction Study , Oxford Abdominal Aortic Aneurysm Study , Claire Vallance
{"title":"Optimising the choice of normalisation method for use in machine-learning classification of human blood plasma ambient ionisation mass spectra","authors":"Annabel S.J. Eardley-Brunt ,&nbsp;Liwen Song ,&nbsp;Oxford Acute Myocardial Infarction Study ,&nbsp;Oxford Abdominal Aortic Aneurysm Study ,&nbsp;Claire Vallance","doi":"10.1016/j.ijms.2025.117553","DOIUrl":"10.1016/j.ijms.2025.117553","url":null,"abstract":"<div><div>Construction of large mass spectrometric data sets usually involves some combination of normalisation, scaling, and transformation of individual mass spectra in order to correct for technical (and sometimes biological) variation. Many different approaches to data normalisation have been reported, and there is no particular consensus on the best approach. The present study systematically evaluates a set of 24 normalisation, scaling, and transformation methods, and their 420 possible combinations, in the context of atmospheric solids analysis probe (ASAP) mass spectra of human blood plasma. The plasma samples came from two separate cohorts of patients, enrolled respectively in the Oxford Acute Myocardial Infarction (OxAMI) and Oxford Abdominal Aortic Aneurysm (OxAAA) clinical studies. Within each cohort, patients are classified according to a number of different clinical variables. We have investigated the effect of normalisation, scaling, and transformation method on subsequent clustering of the data into the classes of interest, and on machine-learning based classification of the data into the categories of interest. The choice of method was found to have a substantial effect on data clustering, measured via the clustering ratio <span><math><msub><mrow><mi>C</mi></mrow><mrow><mi>R</mi></mrow></msub></math></span>, but a much smaller effect on machine-learning based classification, quantified via Cohen’s <span><math><mi>κ</mi></math></span> statistic. New intensity-histogram-based normalisation methods were found to have the greatest effect on clustering, while mean, median, vector, and AUC normalisation yielded the best machine-learning classification performance across multiple algorithms. High clustering ratios do not necessarily correlate with improved supervised classification outcomes, underscoring the need to consider subsequent data analysis methodology carefully when optimising data preprocessing pipelines.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"520 ","pages":"Article 117553"},"PeriodicalIF":1.7,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145692375","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
The IJMS Young Scientist Feature: a special article collection featuring perspectives and critical insights from early career mass spectrometrists around the globe IJMS青年科学家专题:一个特别的文章集合,展示了来自全球早期职业质谱学家的观点和关键见解
IF 1.7 3区 化学
International Journal of Mass Spectrometry Pub Date : 2026-02-01 Epub Date: 2025-12-26 DOI: 10.1016/j.ijms.2025.117568
Julia Laskin, Zheng Ouyang, Isabelle Fournier, Stephen Blanksby
{"title":"The IJMS Young Scientist Feature: a special article collection featuring perspectives and critical insights from early career mass spectrometrists around the globe","authors":"Julia Laskin,&nbsp;Zheng Ouyang,&nbsp;Isabelle Fournier,&nbsp;Stephen Blanksby","doi":"10.1016/j.ijms.2025.117568","DOIUrl":"10.1016/j.ijms.2025.117568","url":null,"abstract":"","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"520 ","pages":"Article 117568"},"PeriodicalIF":1.7,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880442","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
Overcoming the limitations of explosives analysis by GC-MS with cold EI 克服冷EI气相色谱-质谱分析爆炸物的局限性
IF 1.7 3区 化学
International Journal of Mass Spectrometry Pub Date : 2026-02-01 Epub Date: 2025-12-12 DOI: 10.1016/j.ijms.2025.117564
Benny Neumark , Aviv Amirav
{"title":"Overcoming the limitations of explosives analysis by GC-MS with cold EI","authors":"Benny Neumark ,&nbsp;Aviv Amirav","doi":"10.1016/j.ijms.2025.117564","DOIUrl":"10.1016/j.ijms.2025.117564","url":null,"abstract":"<div><div>Explosives present significant challenges for chemical analysis. Traditional methods like High-Pressure Liquid Chromatography (HPLC) with UV/Vis detection often lack sufficient sensitivity and selectivity for complex matrices. HPLC coupled with Mass Spectrometry (MS) is also limited, as many explosives do not ionize efficiently with electrospray or atmospheric pressure chemical ionization. Gas Chromatography (GC) methods using Electron Capture Detection (ECD) or Mass Spectrometry (MS) with standard Electron Ionization (EI) also fall short. GC-MS with standard EI struggles due to thermal degradation at the injector and the hot metallic surface of the ion source and limited sensitivity. While GC-ECD can achieve lower detection limits, it lacks the selectivity of MS and poses safety risks due to its radioactive source.</div><div>GC-MS with Cold Electron Ionization (Cold EI) offers a superior solution. Cold EI incorporates a supersonic molecular beam (SMB) interface, allowing contact-free ionization of vibrationally cold molecules. This enhances molecular ions, improves sensitivity, reduces noise, and expands the range of compounds amenable for GC-MS analysis. The result is faster, more selective, and sensitive analysis that is ideal for the full range of organic explosives.</div><div>This study demonstrates the effectiveness of GC-MS with Cold EI for trace explosives analysis in soil. Using 17 explosive compounds listed in EPA Method 8095, we performed a complete method validation. The method's limits of detection were below 10 ng/g for all explosives, well below EPA thresholds for GC-ECD. GC-MS with Cold EI thus represents a significant advancement in mass spectrometry for forensic and environmental chemical analysis.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"520 ","pages":"Article 117564"},"PeriodicalIF":1.7,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145797438","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
Development of a laser desorption ionization – ion mobility – mass spectrometry method to accelerate the cyclic peptides stereochemistry determination workflow 建立了一种激光解吸电离-离子迁移-质谱法,以加快环多肽立体化学的测定工作流程
IF 1.7 3区 化学
International Journal of Mass Spectrometry Pub Date : 2026-01-01 Epub Date: 2025-09-23 DOI: 10.1016/j.ijms.2025.117533
Jia-Xuan Yan, Wendy Zhong
{"title":"Development of a laser desorption ionization – ion mobility – mass spectrometry method to accelerate the cyclic peptides stereochemistry determination workflow","authors":"Jia-Xuan Yan,&nbsp;Wendy Zhong","doi":"10.1016/j.ijms.2025.117533","DOIUrl":"10.1016/j.ijms.2025.117533","url":null,"abstract":"<div><div>Cyclic peptides are a class of compounds with significant therapeutic potential. The increase in number of stereocenters resulting in exponential surge of stereoisomers poses an immense challenge on the stereochemical analysis of these molecules. Current stereochemistry control strategies for synthetic peptides requires chiral LC method development using synthetic markers. However, the synthesis of all possible stereoisomers as well as chiral LC method development to separate all of them is extremely costly and time consuming. Alternatively, cyclic peptides can be hydrolyzed into single amino acids (AA), further derivatized by chiral reagents for LC-MS analysis, and compared to AA standards subjected to identical derivatization protocols. This LC-MS based methodologies could determine chirality for all possible stereoisomers within short time (less than 1hr) avoiding the need to synthesize large number of cyclic peptide stereoisomers. While examining literature reported LC-MS methodologies, we sought opportunities to further reduce the analysis time required for comprehensive determinations of the stereochemistry of cyclic peptides via advanced MS platforms. Here-in we report a new laser desorption/ionization-ion mobility-mass spectrometry (LDI-IM-MS) method for the rapid determination of amino acid stereochemistry in cyclic peptides. Chiral derivatization reagents, <span>l</span>-FDLA (Nα-(2,4-dinitro-5-fluorophenyl)-<span>l</span>-leucinamide) and <span>d</span>-FDLA were used to derivatize the amino acids into diastereomer pairs. The diastereomers were differentiated using LDI-IM-MS on a Bruker timsTOF flex platform, with key ion mobility parameters optimized and experimental CCS (collision cross section) values calculated. Enhanced sample preparation workflow including solid phase extraction (SPE) and CuCl<sub>2</sub> doping exhibited better ion mobility differentiation for selected samples. This approach was successfully applied to the analysis of polymyxin B, a natural product cyclic peptide, providing comprehensive stereochemical determination of all constituent amino acids within 1 min. The new workflow not only accelerates the stereochemical analysis of cyclic peptides but also holds promise for broader applications in pharmaceuticals including chiral quality control and monitoring of peptide stability.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"519 ","pages":"Article 117533"},"PeriodicalIF":1.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145156068","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
Identification of aromatic aldehyde and keto functionalities in protonated polyfunctional analytes via gas-phase ion-molecule reactions followed by collision-activated dissociation in a linear quadrupole ion trap mass spectrometer 在线性四极离子阱质谱仪中通过气相离子分子反应和碰撞激活解离鉴定质子化多功能化分析物中的芳香醛和酮类官能团
IF 1.7 3区 化学
International Journal of Mass Spectrometry Pub Date : 2026-01-01 Epub Date: 2025-10-31 DOI: 10.1016/j.ijms.2025.117546
Jaskiran Kaur , Ruth O. Anyaeche , Landon Wence , Yue Fu , Kawthar Z. Alzarieni , Hilkka Kenttämaa
{"title":"Identification of aromatic aldehyde and keto functionalities in protonated polyfunctional analytes via gas-phase ion-molecule reactions followed by collision-activated dissociation in a linear quadrupole ion trap mass spectrometer","authors":"Jaskiran Kaur ,&nbsp;Ruth O. Anyaeche ,&nbsp;Landon Wence ,&nbsp;Yue Fu ,&nbsp;Kawthar Z. Alzarieni ,&nbsp;Hilkka Kenttämaa","doi":"10.1016/j.ijms.2025.117546","DOIUrl":"10.1016/j.ijms.2025.117546","url":null,"abstract":"<div><div>The levels of potentially mutagenic impurities and metabolites, such as aldehydes and ketones, are highly regulated in active pharmaceutical ingredients and must be below a critical safety threshold. Therefore, the ability to detect and identify previously known as well as unknown aldehydes and ketones in drug products is of utmost importance. However, traditional tandem mass spectrometry methods based on collision-activated dissociation (CAD) usually fail in this task as isomeric protonated analytes often fragment in an identical manner, and CAD can cause isomerization of the ions. In this study, selective gas-phase ion-molecule reactions of trimethoxymethylsilane (TMMS) with protonated oxygen-containing analytes were combined with diagnostic CAD to reliably detect all mono- and polyfunctional analytes with aromatic aldehyde and ketone functionalities in a mixture. Various aliphatic and aromatic oxygen-containing analytes, <em>e.g.,</em> aldehydes, ketones, carboxylic acids, esters, alcohols, phenols, and amides, were protonated in a linear quadrupole ion trap mass spectrometer, transferred from the ion source into the ion trap, isolated, and allowed to react with TMMS. All protonated analytes produced a stable TMMS adduct and/or an adduct that had lost a methanol molecule. CAD of the latter product ion produced diagnostic fragment ions that correspond to the elimination of a formaldehyde molecule, an ion formally corresponding to the elimination of an oxygen atom from the original protonated analyte, and an ion with mass-to-charge ratio one unit less than the MW of the protonated analyte. These three fragment ions are diagnostic for protonated mono- and polyfunctional analytes with aromatic aldehyde and ketone functionalities, with the exception of pyrrole-2-carboxaldehyde and 2-quinolinecarboxaldehyde. Quantum chemical calculations were employed to delineate the likely mechanisms for the formation of the relevant product ions upon ion-molecule reactions and for the diagnostic fragmentation of specific product ions. This analysis does not require model compounds as the ion-molecule reactions are highly predictable, as opposed to CAD reactions.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"519 ","pages":"Article 117546"},"PeriodicalIF":1.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517064","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
Reactive nano-electrospray ionization for in-situ oxidation of aldehydes for direct mass spectrometry analysis 反应性纳米电喷雾电离用于直接质谱分析醛的原位氧化
IF 1.7 3区 化学
International Journal of Mass Spectrometry Pub Date : 2026-01-01 Epub Date: 2025-11-17 DOI: 10.1016/j.ijms.2025.117552
Kavyasree Chintalapudi, Jonathan N. Chilaka, Abraham K. Badu-Tawiah
{"title":"Reactive nano-electrospray ionization for in-situ oxidation of aldehydes for direct mass spectrometry analysis","authors":"Kavyasree Chintalapudi,&nbsp;Jonathan N. Chilaka,&nbsp;Abraham K. Badu-Tawiah","doi":"10.1016/j.ijms.2025.117552","DOIUrl":"10.1016/j.ijms.2025.117552","url":null,"abstract":"<div><div>A reactive nano-electrospray ionization (<strong>nESI</strong>) platform is introduced that is capable of electro-catalytic reaction screening when fitted with non-inert Ir electrode. We hypothesized that the application of electrical potential to the Ir electrode in the presence of water (i.e., anodic discharge) will cause the generation of a transient active species MO<sub>x</sub> (•OH) at the electrode surface, which can dissociate further to provide a more reactive and hydrated oxide form MO<sub>x</sub> (OH)<sub>y</sub>. The electro-catalytic activity of the resultant nascent oxide was investigated by analyzing aldehydes in negative-ion mode mass spectrometry (<strong>MS</strong>) and detecting the corresponding carboxylic acids. Surface effect on oxidizing the C=O bond was confirmed by comparing with MS signal from non-electrical sonic spray and non-contact nESI experiments. Electronic effects were also investigated via the analysis of seven para-substituted benzaldehydes and results subjected to Hammett analysis, which confirmed electron donating groups to undergo anodic oxidation at a faster rate than electron withdrawing groups. These results have significance in analytical measurements and reaction screening via in-situ synthesized oxides.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"519 ","pages":"Article 117552"},"PeriodicalIF":1.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145614852","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
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