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

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 : 2025-08-15 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

Photoionization of phosphorous trichloride clusters at gigawatt intense laser field 千兆瓦强激光场下三氯化磷团簇的光电离

IF 1.7 3区化学 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

International Journal of Mass Spectrometry

Pub Date : 2025-08-12 DOI: 10.1016/j.ijms.2025.117509

Soumitra Das, Pramod Sharma, Chiranjib Majumder

Photoionization study of PCl₃ clusters has been carried out using time-of-flight mass spectrometry at selected wavelengths of UV (266, 355 nm) and Visible (532 nm) region employing nanosecond laser pulses of intensity ∼10⁹ W/cm². At these three laser wavelengths, dissociated fragments such as P⁺, Cl⁺, PCl⁺ and PCl₂⁺ are observed in the mass spectra. Formation of different fragments has been explained based on the multiphoton excitation at the respective wavelengths. Moreover, PCl₄⁺ ions are observed in 266 and 355 nm ionization of PCl₃ clusters. Generation of PCl₄⁺ is explained based on ion-molecule reaction within the ionized cluster. Using density functional theory (DFT), structure, ionization energy and absorption spectra of PCl₃ monomer and clusters have been calculated which helps to rationalize the experimental observation. Along with singly charged fragment ions, multiply charged atomic ions up to P⁵⁺ (I.E: 65.1 eV) and Cl⁴⁺ (I.E: 53.5 eV) are observed at 532 nm. Generation of multiply charged ions at such low laser intensity indicates efficient ionization of PCl₃ clusters. Formation of higher charge states can be explained based on “multiphoton ionization ignited-inverse bremsstrahlung heating–electron ionization”. Detailed study reveals that laser intensity, cluster size and ionization energy of the cluster constituents play an important role in governing the ionization dynamics under gigawatt laser intensity conditions. Thus, PCl₃ clusters exhibit diverse photochemical process as a function of laser wavelength at ∼10⁹ W/cm².

利用飞行时间质谱技术，利用强度为~ 109 W/cm2的纳秒激光脉冲，在选定波长的紫外（266,355nm）和可见光（532nm）区域对PCl3簇进行了光电离研究。在这三个激光波长下，在质谱中观察到P+、Cl+、PCl+和PCl2+等解离碎片。基于各自波长的多光子激发，解释了不同碎片的形成。此外，PCl3簇在266 nm和355nm电离处均有PCl4+离子的存在。PCl4+的产生是基于电离团簇内的离子-分子反应。利用密度泛函理论（DFT）计算了PCl3单体和团簇的结构、电离能和吸收光谱，有助于实验观测的合理化。除了带单电荷的碎片离子外，在532 nm处还观察到P5+（即：65.1 eV）和Cl4+（即：53.5 eV）的多电荷原子离子。在如此低的激光强度下产生多重带电离子表明PCl3团簇的有效电离。高电荷态的形成可以用“多光子电离点燃-逆轫致加热-电子电离”来解释。详细研究表明，激光强度、团簇大小和团簇组分的电离能对吉瓦激光强度条件下的电离动力学起着重要的控制作用。因此，PCl3团簇表现出不同的光化学过程，作为激光波长在~ 109 W/cm2下的函数。

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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 : 2025-08-12 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

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 : 2025-08-09 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

Hydrogenating atomic coinage metal cations (group 11) with H2 on charged He droplets (T<10 K) doped with metal Atoms: Early stages, ligation energies, core structures, group variations, and relativistic effects 在掺杂金属原子的带电He液滴（T<10 K）上用H2加氢原子造金属阳离子（11族）：早期阶段、连接能、核心结构、基团变化和相对论效应

IF 1.7 3区化学 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

International Journal of Mass Spectrometry

Pub Date : 2025-08-08 DOI: 10.1016/j.ijms.2025.117507

O.V. Lushchikova , M. Ončák , J. Reichegger , B. Felsner , D.K. Böhme , P. Scheier

Experimental mass-spectrometric results are reported which demonstrate that ionized helium nanodroplets (at T < 10 K) doped with the coinage metal atoms M = Cu, Ag or Au, and then exposed to molecular hydrogen, provide an abundance of singly and multiply hydrogenated coinage metal cations M⁺(H₂)_n and MH⁺(H₂)_n with n up to 25 and beyond. We explore here the information provided by observed distributions in the measured intensities of these ligated ions with n = 1–6 and use ab initio quantum chemical calculations to extract fundamental insights into variations in ligation energies and structures with increasing H₂ ligation and going down the Periodic Table (M⁺ = Cu⁺, Ag⁺ and Au⁺) with an eye on the role of relativistic contributions to the ligation energies expected with the increasing nuclear charge of M⁺. “Magic” numbers of H₂ additions with relatively high intensity are apparent among the first 5, especially the first 2, H₂ additions. Very substantial relativistic enhancements of the third over the second-row ligation energies were computed, especially for Au⁺: 83 % and 60 % respectively, for the first two H₂ ligands intimately bonded to Au⁺, and 19 % and 67 % respectively, for the addition of the first two H₂ ligands to AuH⁺. Relativistic enhancements for the addition of a third H₂ ligand and beyond were found to be essentially negligible.

实验质谱结果表明，电离氦纳米液滴(在T <；10 K)掺杂铸币金属原子M = Cu， Ag或Au，然后暴露于分子氢中，可以提供丰富的单氢化和多重氢化铸币金属阳离子M+(H2)n和MH+(H2)n，其中n高达25甚至更高。在这里，我们探索了这些n = 1-6的连接离子在测量强度中的观测分布所提供的信息，并使用从头算量子化学计算来提取连接能和结构随H2连接增加和元素周期表（M+ = Cu+， Ag+和Au+）的变化的基本见解，并着眼于相对论对随着M+核电荷增加而预期的连接能的贡献。H2加成强度较高的“魔术”数在前5个加成中较为明显，尤其是前2个加成。与第二行连接能相比，第三行连接能有非常大的相对论性增强，特别是对于Au+：前两个H2配体与Au+紧密结合，分别为83%和60%，前两个H2配体与AuH+结合，分别为19%和67%。发现添加第三个H2配体及其他配体的相对论增强基本上可以忽略不计。

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引用次数: 0

Effect of rod asymmetry on field distortions and transmission characteristics in linear quadrupole mass filters 棒不对称对线性四极质量滤波器场畸变和传输特性的影响

IF 1.7 3区化学 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

International Journal of Mass Spectrometry

Pub Date : 2025-08-07 DOI: 10.1016/j.ijms.2025.117495

Sukanya Jana , Santu Nath , Pintu Mandal , Nabanita Deb

This article reports the appearance of the octupole and hexadecapole components in the radial potential, which are otherwise absent in a linear quadrupole mass filter of symmetric round-rod configuration, if a small structural asymmetry is introduced in one electrode. Using the commercial ion simulation package SIMION, it is shown that the weightage of the octupole and hexadecapole potential increases with an increase in the asymmetry factor. A consistent correlation is observed between the octupole and dodecapole components, and between the hexadecapole and icosapole components with asymmetry added to different rod-to-field radius ratios. The transmission characteristics of the mass filter are studied for different asymmetry factors and rod-to-field radius ratios. The variation in the resolution parameter, as derived from the transmission contour, exhibits a strong correlation with the combined weightage of the multipole fields.

本文报道了径向电位中八极和六极分量的出现，如果在一个电极中引入小的结构不对称，则在对称圆棒配置的线性四极质量滤波器中不存在八极和六极分量。利用商业离子模拟软件SIMION，研究了八极和十六极电势的权重随不对称系数的增加而增加。在不同的棒场半径比下，八极子和十二极子分量以及六极子和二十极子分量之间存在一致的相关性。研究了不同不对称系数和棒场半径比下质量滤波器的传输特性。从传输轮廓线得出的分辨率参数的变化与多极场的组合权重有很强的相关性。

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 : 2025-08-06 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

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 : 2025-08-05 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

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 : 2025-08-05 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 : 2025-08-05 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