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 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

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

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 in vivo and ex vivo. 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.

质谱技术的化学特异性和敏感性正在被越来越多地探索，以提高术中决策。已经开发了几种质谱技术来快速检测组织代谢的变化，产生“分子指纹”，使外科手术过程中的组织快速识别成为可能。其中，我们的团队开发了MasSpec Pen，作为一种基于液体萃取的设备，集成到接口和质谱仪上，用于体内和离体组织的直接和快速分子分析。自从首次报告和术中临床试验以来，我们对MasSpec Pen技术进行了几次改进，以提高其医疗用途的分析和程序功能。在这里，我们描述了MasSpec Pen技术的最新进展，包括开发了一个带有双加热路径真空室的新接口，该接口可以改善溶剂蒸发，数据质量，并能够与不同的质谱仪集成。我们还描述了用3D打印技术制造的用于腹腔镜和支气管镜检查程序的新型MasSpec Pen设备的开发。在人体组织的直接分析中提供了用这些系统获得的分子数据的例子。

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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 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

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

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 (m/z) 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 m/z over which ions can be collected from a given ion injection step. The m/z 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 m/z 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: m/z 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.

采用静电线性离子阱（ELIT）在两个离子镜之间捕获离子，并采用中心检测电极进行图像电流检测。通过傅里叶变换（FT）将时域信号转换为频域，可以得到离子频谱，该频谱可以转换为质量-电荷（m/z）尺度。从外部离子源向ELIT注入离子导致飞行时间离子分离，最终决定了从给定离子注入步骤中可以收集离子的m/z范围。m/z范围由ELIT的长度和ELIT入口到离子源的距离决定。较长的ELIT导致更宽的m/z范围，而较短的ELIT，在同等条件下，由于离子频率的增加，导致更高的分辨能力。因此，在两个重要的分析仪参数之间存在固有的权衡：m/z范围和分辨率，基于ELIT的长度。在这项工作中，我们展示了一个嵌套的ELIT安排，这里称为NELIT，它允许在单个板阵列中选择两种可能的ELIT长度之一，同时使用一个共同的检测电极。虽然ELIT的长度范围是可能的，但原则上，本文描述的几何形状导致NELIT中两个圈闭的有效长度比为2.40。

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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 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

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

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 m/z, 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 m/z ions. The simulation results demonstrate that this method significantly improves mass range of the coaxial dual LIT/TOFMS, achieving near 100 % injection efficiency for m/z 130–2000 with a mass window ratio (m/z)_max/(m/z)_min of 15. This technology provides a solution for broadening the mass range of LIT-based hybrid instruments.

线性离子阱/飞行时间质谱（LIT/TOFMS）在质量分析之前在单独的LIT中进行离子积累是一种更普遍接受的改善占空比的方法。然而，积累区和TOF推子之间的距离较长，导致注入的离子具有不同的m/z的飞行时间色散，从而限制了单次扫描可检测的质量范围。本文通过SIMION仿真研究了分段式LIT中离子喷射的特征行为。提出了一种新的动态电场抛射策略，以扩大抛射质量范围。通过线性扫描分段式LIT和离子栅上的电压，动态调整轴向电位分布，使离子积累区逐渐向TOF推子移动。累积区与TOF推子之间的弹射距离逐渐缩短，减少了不同m/z离子之间的时间色散。仿真结果表明，该方法显著提高了同轴双LIT/TOFMS的质量范围，在质量窗比（m/z）max/(m/z)min为15的情况下，m/z 130 ~ 2000的喷射效率接近100%。该技术为扩大基于lit的混合仪器的质量范围提供了一种解决方案。

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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 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

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

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 m/z 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.

二维串联质谱（2D-MS/MS）是一种功能强大的分析技术，可以从单个离子注入事件中快速生成样品中所有前体-产物离子关系图，非常适合离子阱等低成本仪器。以无监督和无偏见的方式记录这类信息的能力使该技术高度适用于基于人工智能的工作流程，可以对数据集进行统计检查，以执行结构解析，生成更自信的峰值分配，和/或发现新的化学物质。以前实现的2D-MS/MS扫描功能保持施加于陷阱的射频电压恒定，并扫描辅助频率以弹出和检测产物离子。这样做的一个直接后果是，前驱体和产物m/z较高的离子将具有较低的观察质量分辨率和灵敏度，从而导致更多的潜在候选峰识别算法和报告结果的更高不确定性。在此，我们描述了一种在线性四极离子阱中进行2D-MS/MS分析的新方法，该方法利用连续的传统RF振幅坡道从Mathieu稳定性图边界附近的阱中共振地射出离子。相对于其前身，该技术确实需要更多的时间来获得，但是，它需要更少的仪器修改和更稳健的校准程序。更重要的是，它的使用产生了更高的灵敏度光谱，具有恒定的二维峰值分辨率（3 Da FWHM @ 125 kDa/s），可以根据设定的产物离子扫描速率和谐振弹射点进行预测。另外的讨论是针对方法的扫描可能被改进，或优化，为更高的速度工作流程利用样本阵列。这项工作为同位素解析2D-MS/MS光谱铺平了道路，这将大大提高该技术的能力。

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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 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

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

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.

基于质谱（MS）的蛋白质组学经常面临冗余或信息不丰富的串联质谱的挑战。虽然数据独立采集（DIA）质谱提供了出色的再现性，但DIA中使用的宽隔离窗口不可避免地产生了大量无用的MS/MS光谱，并损害了肽分析的特异性。在这里，我们探索了在之前的数据依赖获取（DDA）调查运行中确定的有用肽上专门安排DIA的可能性。与传统的静态DIA方法相比，建立并优化了一种schedule -DIA方法，以减少占空比，提高蛋白质的鉴定和定量。我们将Scheduled-DIA方法应用于全局标记和接近标记蛋白质组学。溶酶体接近标记实验尤其受益于Scheduled-DIA方法，该方法增加了鉴定和定量关键溶酶体膜蛋白和溶酶体相互作用物的敏感性。综上所述，Scheduled-DIA是获取高质量蛋白质组学DIA数据的另一种有效策略。

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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 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

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

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.

采用常压表面电离质谱法测定了SUS304和镍铬丝加热氧化后产生的负离子和正离子。两种细丝均产生六价氧化铬负离子HCrnO3n+1−(n = 1 - 4)和CrnO3n−•（n = 1 - 4）和正离子A2HCrnO3n+1+ (n = 1 - 3) （A: Na和/或K）。负离子在温度高于~ 1000°C时被检测到，而正离子在温度低于~ 800°C时被检测到。负离子前体假定为铬酸，由反应形成，CrnO3n+ H2O→H2CrnO3n+1，然后电解解离，H2CrnO3n+1→H+ + HCrnO3n+1−发生在固体表面。质子H+可立即被表面氧化物捕获，形成质子化的金属氧化物，该金属氧化物在气相分析物的质子化过程中充当固体Brønsted酸。从加热的铬合金中形成六价氧化铬离子可能对健康有害，因为由于其强氧化性，它们在低浓度下具有致癌性。

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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 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

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

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.

获得准确和可重复的数据对于分析化学家来说至关重要，然而，样品存储和操作在获得高质量结果中起着重要作用。在质谱分析之前，自动进样器小瓶和小体积插入物用于样品制备和存储，然而，这些工具的实用性、设计和材料差异很大。在这里，我们评估了由玻璃和聚丙烯制成的小瓶和插入物在数据可重复性、样品损失和物理差异方面的差异，这些小瓶和插入物用于组合（小瓶/插入物）：玻璃/玻璃（GG）、玻璃/聚丙烯（GP）、聚丙烯/玻璃（PG）和聚丙烯/聚丙烯（PP）。六种全氟烷基和多氟烷基物质（PFAS）在40:60的甲醇：水和3mm醋酸铵中进行了32天的评估，以确定随着时间的推移峰面积的再现性，因为PFAS不会降解，因此变化很可能是由于粘附和蒸发。在第1天，6种PFAS的测量平均峰面积在任何组合之间均无统计学意义，但PP的可重复性最低(相对标准偏差>；10%)。然后将所有样品在- 20°C下重新封装并保存一个月，并重新分析以比较第1天至第32天之间的峰面积。所有组合在至少4种PFAS的峰面积上显示出10%的差异，并且观察到蒸发和粘附。而最大的影响，由于粘附发生在玻璃插入，玻璃小瓶显示最小的体积损失蒸发。因此，当粘附和蒸发一起考虑时，推荐GP组合用于PFAS分析，因为玻璃小瓶减少蒸发速率，聚丙烯插入物最大限度地减少粘附。

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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 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

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

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.

长期以来，气相破碎一直被用于获取离子结构信息，从而大大扩展了通过质谱法可以获得的信息。获得离子单分子反应的能量和熵的定量测量的实验方法对于提供离子碎裂的机制方面的见解是有价值的。这种测量对于大的多原子离子来说尤其具有挑战性。以已知方式改变离子温度的方法可用于确定Arrhenius或Eyring参数。然而，这种方法需要小心地改变真空系统的温度。离子阱碰撞激活提供了另一种改变离子温度的方法，前提是所使用的实验条件可以与有效离子温度联系起来。Tolmachev等人描述了这样一个模型，使用偶极直流电作为诱导受控射频加热的手段。我们使用质子化亮氨酸脑啡肽作为温度计离子对该模型进行了评估，并发现，经过一些调整，该模型可用于建立与DDC动力学测量相关的有效温度。在这项工作中，我们使用另一种单质子化的温度计离子，质子化的缓激肽来评估调整后的模型，并将该方法扩展到双质子化的缓激肽。后一种离子使我们能够确定如何在双电荷前驱体产生互补对的单电荷产物的情况下使用通道板探测器进行离子存活量测量。

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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 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

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

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 m/z 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.

提出了一种利用热电离质谱法（TIMS）精确分析钚中238Pu/239Pu比值的新方法。该方法是基于U和Pu在总蒸发（TE）过程中热蒸发行为的差异。通过将U干扰指示器加入到Pu溶液中，建立了m/z 238 a.m.u.强度变化与238Pu/239Pu和238U/235U同位素比值的线性模型。采用多元线性回归方法拟合实验数据，确定了238Pu/239Pu和238U/235U的配比。该方法已应用于实验室同位素标准样品Pu(SO4)2.4H2O的分析。结果表明，即使在极小的238Pu样本量（图级）下，238Pu/239Pu比值的相对标准偏差小于0.2%。该方法简单，可作为TIMS表征238Pu的有效工具。

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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 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

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

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 (m/z 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.

正如之前通过多级电喷雾电离质谱法观察到的那样，碰撞诱导解离（CID）脱质子草甘膦会导致几种分裂途径。这些过程包括脱羧和脱水，并根据断裂机制形成特征片段和异构体产物离子。本文研究了离子迁移率-质谱法（IM-MS）分离脱水草甘膦异构体的潜力。脱水草甘膦的两种异构体在单次循环离子迁移实验和多次循环实验中均未被分离。然而，使用特征片段，环状异构体似乎比线性异构体更稳定。本文首次观察到脱水草甘膦的CH4O3P−片段（m/z 95）。这被怀疑是在行波离子迁移（TWIMS）细胞中脱水草甘膦阴离子和本底水分子之间的离子分子反应的产物。脱水草甘膦离子水解生成膦酸甲酯阴离子和中性甘氨酸亚胺。13C标记和H/D交换实验支持了一个协调的机制。

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引用次数: 0