International Journal of Mass Spectrometry最新文献_第5页

Next generation MasSpec pen technology: Innovations in instrumentation and medical device development for intraoperative use 下一代MasSpec笔技术：手术中使用的仪器和医疗设备开发的创新

IF 1.7 3区化学

International Journal of Mass Spectrometry Pub Date : 2025-12-01 Epub Date: 2025-08-26 DOI: 10.1016/j.ijms.2025.117515

Charles A. Wolfe , Sydney Povilaitis , Michael F. Keating , Ashley E. Montgomery , Bryan M. Burt , Amir A. Jazaeri , Livia S. Eberlin

{"title":"Next generation MasSpec pen technology: Innovations in instrumentation and medical device development for intraoperative use","authors":"Charles A. Wolfe , Sydney Povilaitis , Michael F. Keating , Ashley E. Montgomery , Bryan M. Burt , Amir A. Jazaeri , 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":"2025-12-01","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}

引用次数: 0

Demonstration of a nested electrostatic linear ion trap for flexibility in selecting analyzer figures-of-merit 演示了一个嵌套静电线性离子阱，以灵活地选择分析仪的性能值

IF 1.7 3区化学

International Journal of Mass Spectrometry Pub Date : 2025-12-01 Epub Date: 2025-08-15 DOI: 10.1016/j.ijms.2025.117511

Jordan M. Fritz, Ian J. Carrick, Nicholas R. Ellin, Eric T. Dziekonski, Scott A. McLuckey

{"title":"Demonstration of a nested electrostatic linear ion trap for flexibility in selecting analyzer figures-of-merit","authors":"Jordan M. Fritz, Ian J. Carrick, Nicholas R. Ellin, Eric T. Dziekonski, 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":"2025-12-01","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}

引用次数: 0

Extended m/z range of coaxial linear ion trap/time-of-flight mass spectrometry using dynamic electric field ejection 使用动态电场喷射的同轴线性离子阱/飞行时间质谱扩展m/z范围

IF 1.7 3区化学

International Journal of Mass Spectrometry Pub Date : 2025-12-01 Epub Date: 2025-08-30 DOI: 10.1016/j.ijms.2025.117517

Yixue Cao , Xuesong Zhang , Jilong Wang , Chenxin Wu , Lei Hua , Ping Chen , Haiyang Li

{"title":"Extended m/z range of coaxial linear ion trap/time-of-flight mass spectrometry using dynamic electric field ejection","authors":"Yixue Cao , Xuesong Zhang , Jilong Wang , Chenxin Wu , Lei Hua , Ping Chen , 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><sub><em>max</em></sub><em>/(m/z)</em><sub><em>min</em></sub> 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":"2025-12-01","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}

引用次数: 0

Two-dimensional tandem mass spectrometry in a linear quadrupole ion trap using consecutive product ion sweeps 二维串联质谱法在线性四极离子阱使用连续产品离子扫描

IF 1.7 3区化学

International Journal of Mass Spectrometry Pub Date : 2025-12-01 Epub Date: 2025-09-05 DOI: 10.1016/j.ijms.2025.117524

Eric T. Dziekonski

{"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":"2025-12-01","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}

引用次数: 0

Scheduled data-independent acquisition mass spectrometry for global proteomics and proximity labeling 计划数据独立采集质谱法用于全球蛋白质组学和接近标记

IF 1.7 3区化学

International Journal of Mass Spectrometry Pub Date : 2025-11-01 Epub Date: 2025-08-05 DOI: 10.1016/j.ijms.2025.117497

Jiawei Ni , Ashley M. Frankenfield , Ling Hao

{"title":"Scheduled data-independent acquisition mass spectrometry for global proteomics and proximity labeling","authors":"Jiawei Ni , Ashley M. Frankenfield , Ling Hao","doi":"10.1016/j.ijms.2025.117497","DOIUrl":"10.1016/j.ijms.2025.117497","url":null,"abstract":"<div><div>Mass spectrometry (MS)-based proteomics often faces challenges with redundant or uninformative tandem MS/MS spectra. Although data-independent acquisition (DIA) MS offers excellent reproducibility, the wide isolation windows used in DIA inevitably generate numerous MS/MS spectra that are not useful and compromise the specificity of peptide analysis. Here, we explored the possibility of scheduling DIA exclusively on useful peptides identified in a preceding data-dependent acquisition (DDA) survey run. We established and optimized a Scheduled-DIA method to reduce duty cycle and improve protein identification and quantification compared to the traditional static DIA method. We applied the Scheduled-DIA method to both global and proximity labeling proteomics. Lysosomal proximity labeling experiments particularly benefited from the Scheduled-DIA method, which increased sensitivity for identifying and quantifying key lysosomal membrane proteins and lysosomal interactors. To summarize, Scheduled-DIA is an alternative and useful strategy for acquiring high-quality DIA data for proteomics.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"517 ","pages":"Article 117497"},"PeriodicalIF":1.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144772618","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

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 大气压表面电离质谱法测定氧化的SUS304和镍铬：铬酸（H2CrnO3n+1）作为中间前驱体，形成六价氧化铬负离子HCrnO3n+1−和质子化的氧化物表面作为固体酸

IF 1.7 3区化学

International Journal of Mass Spectrometry Pub Date : 2025-11-01 Epub Date: 2025-08-06 DOI: 10.1016/j.ijms.2025.117506

Kenzo Hiraoka , Stephanie Rankin-Turner , Dilshadbek T. Usmanov , Satoshi Ninomiya

{"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 , Stephanie Rankin-Turner , Dilshadbek T. Usmanov , 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<sub>n</sub>O<sub>3n+1</sub><sup>−</sup> (n = 1–4) and Cr<sub>n</sub>O<sub>3n</sub><sup>−•</sup> (n = 1–4) and positive ions of A<sub>2</sub>HCr<sub>n</sub>O<sub>3n+1</sub><sup>+</sup> (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<sub>n</sub>O<sub>3n</sub> + H<sub>2</sub>O → H<sub>2</sub>Cr<sub>n</sub>O<sub>3n+1</sub> followed by electrolytic dissociation, H<sub>2</sub>Cr<sub>n</sub>O<sub>3n+1</sub> → H<sup>+</sup> + HCr<sub>n</sub>O<sub>3n+1</sub><sup>−</sup> taking place on the solid surface. The proton H<sup>+</sup> 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":"2025-11-01","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}

引用次数: 0

Selecting the correct autosampler vial and insert to improve reproducibility and accuracy in mass spectrometry analyses 选择正确的自动进样器小瓶和插入物，以提高质谱分析的再现性和准确性

IF 1.7 3区化学

International Journal of Mass Spectrometry Pub Date : 2025-11-01 Epub Date: 2025-08-05 DOI: 10.1016/j.ijms.2025.117499

Ashlee T. Falls, Erin S. Baker

{"title":"Selecting the correct autosampler vial and insert to improve reproducibility and accuracy in mass spectrometry analyses","authors":"Ashlee T. Falls, Erin S. Baker","doi":"10.1016/j.ijms.2025.117499","DOIUrl":"10.1016/j.ijms.2025.117499","url":null,"abstract":"<div><div>Acquiring accurate and reproducible data is crucial for analytical chemists, however, sample storage and manipulation play a large role in achieving high-quality results. Autosampler vials and small-volume inserts are used for sample preparation and storage prior to mass spectrometry analyses, however, the utility, design, and material of these vary greatly. Here, we assessed differences in data reproducibility, sample loss, and physical differences among vials and inserts made of glass and polypropylene for combinations (vial/insert): glass/glass (GG), glass/polypropylene (GP), polypropylene/glass (PG), and polypropylene/polypropylene (PP). Six per- and polyfluoroalkyl substances (PFAS) were evaluated in 40:60 methanol:water with 3 mM ammonium acetate for 32 days to determine peak area reproducibility over time since PFAS do not degrade, therefore changes would most likely be due to adhesion and evaporation. On Day 1, the measured average peaks areas for the 6 PFAS were not statistically significant between any combinations, however, PP was the least reproducible (relative standard deviation > 10 %). All samples were then recapped and stored for one month at −20 °C and reanalyzed to compare the peak areas between Day 1 to Day 32. All combinations showed >10 % differences in peak area for at least 4 PFAS and both evaporation and adhesion were observed. While the greatest effects due to adhesion occurred in the glass inserts, the glass vials showed the least volume loss to evaporation. Thus, when adhesion and evaporation are considered together, the GP combination is recommended for PFAS analyses as the glass vial reduces evaporation rates, and the polypropylene insert minimizes adhesion.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"517 ","pages":"Article 117499"},"PeriodicalIF":1.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144780429","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

Arrhenius parameters of singly- and doubly-protonated bradykinin measured via dipolar DC kinetics on a quadrupole/time-of-flight platform 在四极杆/飞行时间平台上通过偶极直流动力学测量单质子化和双质子化缓激肽的Arrhenius参数

IF 1.7 3区化学

International Journal of Mass Spectrometry Pub Date : 2025-11-01 Epub Date: 2025-08-05 DOI: 10.1016/j.ijms.2025.117498

Samantha A. Mehnert, Katherine J. Lee, Seth A. Horn, Scott A. McLuckey

{"title":"Arrhenius parameters of singly- and doubly-protonated bradykinin measured via dipolar DC kinetics on a quadrupole/time-of-flight platform","authors":"Samantha A. Mehnert, Katherine J. Lee, Seth A. Horn, Scott A. McLuckey","doi":"10.1016/j.ijms.2025.117498","DOIUrl":"10.1016/j.ijms.2025.117498","url":null,"abstract":"<div><div>Gas-phase fragmentation has long been used to obtain ion structure information, thereby significantly expanding the information that can be obtained via mass spectrometry. Experimental approaches for obtaining quantitative measures of the energies and entropies of unimolecular reactions of ions can be valuable for providing insights into mechanistic aspects of ion fragmentation. Such measurements can be particularly challenging for large polyatomic ions. Approaches that vary the temperatures of ions in a known way can be used to determine Arrhenius or Eyring parameters. However, such approaches require careful variation of the temperature of the vacuum system. Ion trap collisional activation provides another approach to varying ion temperatures provided the experimental conditions used can be connected with an effective ion temperature. Tolmachev et al. have described such a model using dipolar DC as a means for inducing controlled rf-heating. We have evaluated this model using the well-studied protonated leucine enkephalin as a thermometer ion and found that, with a few adjustments, the model is useful in establishing effective temperatures to associate with DDC kinetics measurements. In this work, we evaluate the adjusted model using another singly-protonated thermometer ion, protonated bradykinin, and extended the approach to doubly-protonated bradykinin. The latter ion allowed us to determine how to conduct ion survivor measurements using a channelplate detector under the scenario of a doubly-charged precursor giving rise to complementary pairs of singly charged products.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"517 ","pages":"Article 117498"},"PeriodicalIF":1.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144780430","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

Determination of 238Pu/239Pu isotope ratio under uranium interference by thermal ionization mass spectrometry 热电离质谱法测定铀干扰下238Pu/239Pu同位素比值

IF 1.7 3区化学

International Journal of Mass Spectrometry Pub Date : 2025-11-01 Epub Date: 2025-08-09 DOI: 10.1016/j.ijms.2025.117496

Peng-fei Zhang, Zhi-ming Li, Wen-liang Wang, Lei Feng, Jiang Xu, Man-chao Zhang, Rui-yang Xi, Xiao-pan Shen, Wei Wang

{"title":"Determination of 238Pu/239Pu isotope ratio under uranium interference by thermal ionization mass spectrometry","authors":"Peng-fei Zhang, Zhi-ming Li, Wen-liang Wang, Lei Feng, Jiang Xu, Man-chao Zhang, Rui-yang Xi, Xiao-pan Shen, 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 <sup>238</sup>Pu/<sup>239</sup>Pu 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 <sup>238</sup>Pu/<sup>239</sup>Pu and <sup>238</sup>U/<sup>235</sup>U was established. The ratios of <sup>238</sup>Pu/<sup>239</sup>Pu and <sup>238</sup>U/<sup>235</sup>U was determined by fitting the experimental data using multiple linear regression analysis. This method had been applied to analyze laboratory isotopic standard samples Pu(SO<sub>4</sub>)<sub>2</sub>.4H<sub>2</sub>O. Results showed that, even with extremely small sample size of <sup>238</sup>Pu (picogram level), the relative standard deviation of <sup>238</sup>Pu/<sup>239</sup>Pu ratio was less than 0.2 %. The approach was simple and would be an effective tool as a method for the characterization of <sup>238</sup>Pu using TIMS.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"517 ","pages":"Article 117496"},"PeriodicalIF":1.7,"publicationDate":"2025-11-01","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}

引用次数: 0

Unimolecular decomposition of deprotonated glyphosate: Discerning cyclic versus linear dehydration products using ion mobility mass spectrometry 去质子化草甘膦的单分子分解：使用离子迁移率质谱法识别循环与线性脱水产物

IF 1.7 3区化学

International Journal of Mass Spectrometry Pub Date : 2025-11-01 Epub Date: 2025-08-12 DOI: 10.1016/j.ijms.2025.117508

Olivia Rusli, Nicole Joy Rijs

{"title":"Unimolecular decomposition of deprotonated glyphosate: Discerning cyclic versus linear dehydration products using ion mobility mass spectrometry","authors":"Olivia Rusli, 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 CH<sub>4</sub>O<sub>3</sub>P<sup>−</sup> 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 <sup>13</sup>C 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":"2025-11-01","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}

引用次数: 0