International Journal of Mass Spectrometry最新文献

英文中文

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 : 2025-11-01 Epub 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 : 2025-11-01 Epub 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

Experimental studies on low-pressure air dielectric barrier discharge plasma for ionization source 低压空气介质阻挡放电等离子体电离源实验研究

IF 1.6 3区化学 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

International Journal of Mass Spectrometry

Pub Date : 2025-10-01 Epub Date: 2025-07-08 DOI: 10.1016/j.ijms.2025.117493

Chenxin Ye , Xinyao Wang , Junliang Zhang , Boping Li , Jiancheng Yu

This study experimentally investigates the properties of low-pressure dielectric barrier discharge (DBD) plasma. A ring-ring DBD configuration was employed. Spectroscopic and electrical measurements were conducted at varying gas pressures to characterize the plasma properties. The results revealed that the luminous region of the plasma expands and exhibits maximum luminescence near 600 Pa, with a subsequent contraction and intensity diminution at lower pressures. Analysis of emission spectra identified nitrogen's second positive system (SPS) and first negative system (FNS) as the primary contributors. The highest density of excited molecule

N_{2} (C^{3} Π_{u})

and excited ion

N_{2}^{+} (B^{2} Σ_{u}^{+})

are at 660 Pa and 100 Pa, respectively. Mass spectrometry measurements indicate that the excited state

N_{2} (C^{3} Π_{u})

has the ability to undergo Penning ionization. This study provides the variation of excited molecules and ions with pressure in low-pressure dielectric barrier discharge, which can be used for the optimization of ionization source and the analysis of mass spectrometry data.

实验研究了低压介质阻挡放电（DBD）等离子体的特性。采用环环DBD配置。光谱和电学测量在不同的气体压力下进行，以表征等离子体的特性。结果表明，等离子体的发光区域在600 Pa附近扩展并显示出最大的发光，随后在较低的压力下收缩和强度降低。发射光谱分析表明，氮的第二正系统（SPS）和第一负系统（FNS）是主要贡献者。受激分子N2（C3Πu）和受激离子N2+（B2Σu+）的最高密度分别为660 Pa和100 Pa。质谱测量表明激发态N2（C3Πu）具有经历潘宁电离的能力。本研究提供了低压介质阻挡放电中受激分子和离子随压力的变化规律，可用于电离源的优化和质谱数据的分析。

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引用次数: 0

An adaptive EEMD-machine learning algorithm for multi-matrix drug concentration prediction using miniature mass spectrometry 微型质谱法多基质药物浓度预测的自适应eemd -机器学习算法

IF 1.6 3区化学 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

International Journal of Mass Spectrometry

Pub Date : 2025-10-01 Epub Date: 2025-06-28 DOI: 10.1016/j.ijms.2025.117485

Binrui Xie , Yanbing Li , Nan Zhang , Chuangui Zhou , Jiexun Bu , Lun Wu , Jun Zhu , Wenzhuo Wang , Lei Liu , Ming Li

In this study, an innovative approach combining Machine Learning (ML) with Ensemble Empirical Mode Decomposition (EEMD) was proposed to predict lamotrigine concentrations in actual samples, improving detection performance in complex matrices. EEMD decomposed the mass spectrometry data to extract Intrinsic Mode Functions (IMFs), enabling separation of noise from key signal features. Ridge Regression (RR) addressed multicollinearity among high-dimensional IMF features and enhanced model generalization via L2 regularization. ML was further applied to optimize the key EEMD parameter (ensemble number K),thereby improving both decomposition quality and prediction accuracy. Experimental validation showed that the method achieved over 90 % prediction accuracy in three types of blind samples (PBS, rabbit blood, and human matrix), with improved Relative Standard Deviation (RSD). These results confirm the method’s precision and robustness in diverse biological matrices. Compared to traditional techniques, the proposed approach delivers marked improvements in both accuracy and stability, can supporting more reliable drug concentration monitoring for clinical applications.

在这项研究中，提出了一种结合机器学习（ML）和集成经验模式分解（EEMD）的创新方法来预测实际样品中的拉莫三嗪浓度，提高了复杂矩阵中的检测性能。EEMD对质谱数据进行分解，提取本征模态函数（IMFs），实现了噪声与关键信号特征的分离。Ridge回归（RR）解决了高维IMF特征之间的多重共线性问题，并通过L2正则化增强了模型的泛化。进一步应用ML对EEMD关键参数（集合数K）进行优化，提高了分解质量和预测精度。实验验证表明，该方法对3种盲样（PBS、兔血和人基质）的预测准确率达到90%以上，相对标准偏差（RSD）有所提高。这些结果证实了该方法在不同生物基质中的精确性和鲁棒性。与传统技术相比，该方法在准确性和稳定性方面都有显著提高，可以为临床应用提供更可靠的药物浓度监测。

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引用次数: 0

Mass spectrometry of laser reduced graphene oxide in vacuum 真空中激光还原氧化石墨烯的质谱分析

IF 1.6 3区化学 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

International Journal of Mass Spectrometry

Pub Date : 2025-10-01 Epub Date: 2025-07-18 DOI: 10.1016/j.ijms.2025.117494

L. Torrisi , A. Torrisi , M. Cutroneo

Graphene oxide (GO) foils were irradiated in high vacuum using an ns pulsed laser operating at 1064 nm and different fluences. Laser irradiation generates plasma and promotes the emission of carbon atoms and molecules, functional groups of oxygen, and absorbed gases, generating a surface GO reduction. The emitted particles have been monitored through a high-sensitivity mass quadrupole spectrometer operating between 1 amu and 300 amu.

The produced laser irradiation was investigated using low fluences, as well as the generated plasma.

The pristine and laser-irradiated GO were analyzed using different analysis techniques: Optical spectroscopy, time-of-flight measurements and mass spectrometry. The results obtained in previous experiments using other types of analyses were also cited.

Results demonstrated that under laser-irradiation graphene oxide loses different functional groups of oxygen becoming richer in sp² hybridized carbon content, enhancing its carbon content, and becoming more electrically conductive.

在高真空条件下，利用波长为1064 nm的脉冲激光辐照氧化石墨烯（GO）薄膜。激光照射产生等离子体，促进碳原子和分子、氧官能团和吸收气体的发射，产生表面氧化石墨烯还原。发射的粒子通过高灵敏度的质量四极谱计进行监测，工作在1amu和300amu之间。研究了低影响下产生的激光辐照，以及产生的等离子体。使用不同的分析技术对原始氧化石墨烯和激光辐照氧化石墨烯进行了分析：光谱学、飞行时间测量和质谱分析。还引用了以前使用其他类型分析获得的实验结果。结果表明，在激光照射下，氧化石墨烯失去了不同官能团的氧，sp2杂化碳含量增加，碳含量提高，导电性能增强。

引用次数: 0

All-ions laser induced dissociation (AI-LID) in the C-trap of a Q Exactive: Data independent identification and quantification directly from ultra-high resolution differential mass spectra Q萃取物c阱中全离子激光诱导离解（AI-LID）：直接从超高分辨率微分质谱数据独立鉴定和定量

IF 1.6 3区化学 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

International Journal of Mass Spectrometry

Pub Date : 2025-09-01 Epub Date: 2025-06-18 DOI: 10.1016/j.ijms.2025.117484

Luke MacAleese , Xavier Dagany , Lény Garcia , Jérôme Lemoine , Philippe Dugourd , Marion Girod

An analytical method is demonstrated which allows to follow a data independent, all ion fragmentation (AIF) acquisition procedure, but to fall back on a standard and generic data-dependent acquisition (DDA) analysis procedure for the data treatment: searching databases with individual precursor ions and fragments lists. This method is implemented with photo-activation (LID) in the visible range which allows extreme specificity and sensitivity, and is demonstrated on Cysteine-containing tryptic peptides grafted with a chromophore. This proof of concept relies on the efficient implementation of LID directly in the C-trap of a ThermoScientific QExactive mass spectrometer during ion accumulation, before full MS detection. Laser irradiation turned alternatively ON and OFF after each full MS allows to build differential mass spectra in which non-dissociating ions are cancelled out while fragmenting precursors and fragments show up with opposite signs, which enables to build precursor/fragments lists for database search. Protein identification was demonstrated with remarkably low false discovery rates. Relative quantification was also demonstrated by integration of precursor and fragment ion elution peaks after differential analysis and limits of quantifications were demonstrated down to 11 ng of proteins injected. This mixed approach takes the best of both worlds – the deep proteome coverage of DIA, with the exhaustive fragmentation of all precursor ions, and the reliability and ease of use of classical DDA database search, relieving the need for the initial constitution of a spectral library.

本文演示了一种分析方法，该方法允许遵循数据独立的、所有离子碎片（AIF）获取过程，但对于数据处理，可以退回到标准的、通用的数据依赖获取（DDA）分析过程：用单个前体离子和碎片列表搜索数据库。该方法在可见光范围内使用光激活（LID）实现，具有极高的特异性和敏感性，并在接枝带有发色团的含半胱氨酸的色氨酸肽上得到了证明。这一概念证明依赖于在离子积累过程中，在全质谱检测之前，在ThermoScientific QExactive质谱仪的c阱中直接有效地实施LID。激光照射在每次全质谱后交替打开和关闭，可以建立微分质谱，其中非解离离子被抵消，而碎片前体和片段显示相反的符号，这使得建立前体/片段列表用于数据库搜索。蛋白质鉴定被证明具有非常低的错误发现率。通过差异分析后前体和片段离子洗脱峰的整合，也证明了相对定量，并证明了定量的限制低至11 ng注射的蛋白质。这种混合方法充分利用了两个方面的优点：DIA的蛋白质组覆盖范围广，所有前体离子的详尽碎片化，以及经典DDA数据库搜索的可靠性和易用性，减轻了谱库初始构建的需要。

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引用次数: 0

Development of a high efficiency cavity ion source and its characterization using a quadrupole mass analyser 高效腔离子源的研制及其四极质谱分析仪表征

IF 1.6 3区化学 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

International Journal of Mass Spectrometry

Pub Date : 2025-09-01 Epub Date: 2025-05-31 DOI: 10.1016/j.ijms.2025.117474

VarunK. Yadav , R.K. Bhatia , A. Singh , A.M. Kasbeker , M.M. Gulhane , E. Ravisankar , T.K. Saha

The present work deals with the design and development of an efficient cavity ion source (CIS). The design optimization of CIS was carried out on the basis of experimental studies using an indigenous quadrupole mass analyser (QMA). Subsequently, the optimally designed CIS was characterized for the quantitative and qualitative detection of various rare earth and actinide elements. Sensitivity measurement was carried out using total evaporation technique. Same set of studies were also conducted on a conventional thermal ion source (TIS) to compare the performance of the CIS with conventional TIS. The CIS showed an improvement in respective sensitivity by a factor of about 7 and 4 times for Uranium and Strontium as compared to conventional TIS. The improved sensitivity of CIS is attributed to the multiple interactions of the analyte species with the inner surface of the high temperature cavity tube thereby increasing its ionization probability.

本文研究了一种高效腔离子源（CIS）的设计与研制。在国产四极杆质量分析仪（QMA）实验研究的基础上，对CIS进行了优化设计。随后，对优化设计的CIS进行了表征，用于各种稀土和锕系元素的定量和定性检测。采用全蒸发法进行灵敏度测定。同样的一组研究也在传统热离子源（TIS）上进行，以比较CIS与传统TIS的性能。与传统TIS相比，CIS对铀和锶的灵敏度分别提高了约7倍和4倍。CIS灵敏度的提高是由于被分析物与高温腔管内表面的多重相互作用，从而增加了其电离概率。

引用次数: 0

MALDI-TOF-MS unveils the distribution of oligosaccharides produced by hydrolysis of lichen polysaccharides through acidic and oxidative methods – a comparative study MALDI-TOF-MS揭示了通过酸性和氧化方法水解地衣多糖产生的低聚糖的分布-一项比较研究

IF 1.6 3区化学 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

International Journal of Mass Spectrometry

Pub Date : 2025-09-01 Epub Date: 2025-06-06 DOI: 10.1016/j.ijms.2025.117473

Camille Guitteny , Simon Ollivier , Oznur Yeni , Mathis Ralaivao , Mathieu Fanuel , Joël Boustie , Isabelle Compagnon , Vincent Ferrières , Solenn Ferron , Hélène Rogniaux , David Ropartz , Laurent Legentil , Françoise Le Dévéhat

MALDI-TOF MS methods coupled with offline chromatographic data were used to compare the distribution of oligosaccharides generated from acidic or oxidative degradation (Fitdog) of high molecular weight polysaccharides (>10 kDa) obtained from two lichens Lasallia pustulata and Cetraria islandica. MALDI allowed to quickly compare the kinetics of degradation on both models (starting from non-purified polysaccharides) and to evaluate the dispersity of the resulting oligosaccharides. MALDI-MS confirmed on one hand that TFA hydrolysis gave neutral oligosaccharides easy to correlate with the chemical formula. On the other hand, more structural diversity was evidenced using the Fitdog protocol. Deep analysis of the MALDI data highlighted the formation of by-products corresponding to modified oligosaccharides (e.g., intracyclic cleavages).

采用MALDI-TOF质谱法结合离线色谱数据，比较了从两种地衣中获得的高分子量（>10 kDa） Lasallia pustulata和Cetraria islandica中酸性或氧化降解（Fitdog）产生的低聚糖的分布。MALDI可以快速比较两种模型（从未纯化的多糖开始）的降解动力学，并评估所得低聚糖的分散性。MALDI-MS一方面证实了TFA水解得到的中性低聚糖易于与化学式相关联。另一方面，使用Fitdog协议证明了更多的结构多样性。对MALDI数据的深入分析强调了与改性低聚糖（例如，环内裂解）相对应的副产物的形成。

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引用次数: 0

Structural ion mobility spectrometry: What can we really measure? 结构离子迁移率光谱法：我们真正能测量什么？

IF 1.6 3区化学 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

International Journal of Mass Spectrometry

Pub Date : 2025-09-01 Epub Date: 2025-06-04 DOI: 10.1016/j.ijms.2025.117482

Thanh D. Do

Advancing our understanding of biomolecular systems requires technologies that can unravel their intricate dynamics and structures. Mass spectrometry (MS) has emerged as a versatile technique for characterizing complex systems, yet its findings are most impactful when paired with structural methods such as NMR, X-ray crystallography, and microscopy. This Perspective examines how ion mobility-mass spectrometry (IM-MS) serves as a key connector between dynamic molecular behavior and high-resolution structural insights. Examples from recent research in our laboratory illustrate how IM-MS enhances the study of flexible peptides, transient protein assemblies, and metabolite aggregation. These studies highlight the method's ability to reveal properties inaccessible to single techniques. By integrating multiple approaches, researchers gain a more comprehensive view of biomolecular complexity, demonstrating the power of combining analytical methods to tackle open questions in structural biology. This approach reflects the collaborative and iterative nature of science, where diverse perspectives converge to deepen our understanding of the molecular world.

推进我们对生物分子系统的理解需要能够解开其复杂动力学和结构的技术。质谱（MS）已成为表征复杂系统的一种通用技术，但其发现在与核磁共振、x射线晶体学和显微镜等结构方法相结合时最具影响力。本展望探讨了离子迁移-质谱（IM-MS）如何作为动态分子行为和高分辨率结构洞察之间的关键连接器。我们实验室最近研究的例子说明了IM-MS如何增强对柔性肽、瞬态蛋白质组装和代谢物聚集的研究。这些研究突出了该方法揭示单一技术无法获得的特性的能力。通过整合多种方法，研究人员获得了对生物分子复杂性的更全面的看法，展示了结合分析方法解决结构生物学中开放性问题的力量。这种方法反映了科学的协作性和迭代性，不同的观点汇聚在一起，加深了我们对分子世界的理解。

引用次数: 0

Structure selective fragment ions of epoxidized sphingolipids 环氧鞘脂结构选择性片段离子

IF 1.6 3区化学 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

International Journal of Mass Spectrometry

Pub Date : 2025-09-01 Epub Date: 2025-06-16 DOI: 10.1016/j.ijms.2025.117483

Jing Yu , Sven Heiles

Sphingolipids are essential building blocks of most organisms. The structure of sphingolipids is tightly regulated and dysregulation during diseases can result in altered sphingolipid structures. In this manuscript, we explore the potential of sphingolipid epoxidation for the assignment and discrimination of sphingolipid structures. Employing shotgun tandem mass spectrometry, liquid chromatography tandem mass spectrometry, authentic sphingolipid standards, and density function theory, we demonstrate that epoxidation of shingoid bases (SPBs), ceramides, and sphingomyelins facilitates C=C bond (DB) position assignment. This includes DBs in the N-linked fatty acyl moiety and the sphingoid base. For SPBs with DBs at position 4, a major component for almost all sphingolipids, we furthermore demonstrate that the fragmentation pathway differs for this DB position compared to other DB-diagnostic fragment ions. We show that epoxidation of this DB position facilities intramolecular rearrangement and formation of distinct diagnostic fragment ions. To demonstrate the analytical capabilities and show that the 4 SPB DBs enable confident differentiation of ceramides and dihydroceramides, results for brain ceramide extract are presented. The identified fragmentation pathway for 4 SPB DB ions in combination with N-acyl assignment and DB position assignment allows to annotate 25 ceramide/dihydroceramide compounds in the brain ceramide extract out of which 23 are DB position isomers.

鞘脂是大多数生物体必不可少的组成部分。鞘脂结构受到严格调控，疾病期间的失调可导致鞘脂结构改变。在这篇论文中，我们探讨了鞘脂环氧化对鞘脂结构的分配和辨别的潜力。利用霰弹枪串联质谱法、液相色谱串联质谱法、真实鞘脂标准和密度函数理论，我们证明了鞘鞘碱（SPBs）、神经酰胺和鞘磷脂的环氧化有助于C=C键（DB）的位置分配。这包括在n -连接的脂肪酰基部分和鞘碱的db。对于位于4号位置（几乎所有鞘脂的主要成分）的spb，我们进一步证明了与其他DB诊断片段离子相比，该DB位置的碎片路径不同。我们发现这个DB位置的环氧化有助于分子内重排和形成不同的诊断片段离子。为了证明分析能力，并表明4个SPB db能够自信地区分神经酰胺和二氢神经酰胺，给出了脑神经酰胺提取物的结果。结合n -酰基分配和DB位置分配，确定了4个SPB - DB离子的碎片化途径，允许在脑神经酰胺提取物中注释25个神经酰胺/二氢神经酰胺化合物，其中23个是DB位置异构体。

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