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Mass Spectrometry-Based Proteomics to Understand Immune Thrombocytopenic Purpura: A Review 基于质谱的蛋白质组学研究免疫性血小板减少性紫癜:综述。
IF 1.7 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2026-01-20 DOI: 10.1002/rcm.70022
Syed Kashif Raza, Ayesha Iqbal

Background

Immune thrombocytopenic purpura (ITP) is an autoimmune bleeding disorder with substantial variability in bleeding manifestations and a generally low risk of fatal outcomes. Diagnosis is based on exclusion and is supported by thrombocytopenia in peripheral blood and characteristic megakaryocytic findings in bone marrow examination. In many adults, treatment remains suboptimal, and morbidity may result from both bleeding and the adverse effects of immunosuppressive therapies.

Rationale

Identifying the underlying disease process is essential for improving diagnostic precision, developing targeted therapies, and enhancing patient outcomes.

Objective

This review summarizes mass spectrometry-based proteomics studies investigating the pathogenesis of ITP and their diagnostic, prognostic, and therapeutic implications.

Conclusion

Despite significant clinical heterogeneity, proteomic research in ITP remains limited, underscoring the need for comprehensive molecular studies to better elucidate disease mechanisms.

背景:免疫性血小板减少性紫癜(ITP)是一种自身免疫性出血性疾病,出血表现有很大的变异性,通常死亡风险较低。诊断是基于排除和支持外周血血小板减少和特征性巨核细胞的骨髓检查结果。在许多成年人中,治疗仍然不够理想,并且发病率可能由出血和免疫抑制治疗的不良反应引起。基本原理:确定潜在的疾病过程对于提高诊断精度、开发靶向治疗和提高患者预后至关重要。目的:本文综述了基于质谱的蛋白质组学研究ITP的发病机制及其诊断、预后和治疗意义。结论:尽管存在显著的临床异质性,但ITP的蛋白质组学研究仍然有限,强调需要进行全面的分子研究以更好地阐明疾病机制。
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引用次数: 0
Pyrene-Conjugated, 2-Pyridinecarboxaldehyde Derivatives as N-Terminus-Specific Tags for MALDI- and LALDI-MS 吡啶共轭2-吡啶甲酸衍生物作为MALDI-和LALDI-MS的n端特异性标签
IF 1.7 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2026-01-20 DOI: 10.1002/rcm.70034
Mujia Jenny Li, Murat Kucukdisli, Florian Braun, David W. Will, Nadine Meier, Bettina Wehrle, Larissa Chiara Meyer, Melanie Christine Föll, Oliver Schilling

Background

Proteolytic processing is a fundamental post-translational modification. Liquid chromatography–tandem mass spectrometry (LC–MS/MS) workflows are powerful for degradomic analyses but inherently sacrifice spatial information, a critical aspect for investigating biological systems such as aberrant extracellular matrix remodeling and alterations of the tumor microenvironment. Matrix-assisted laser desorption/ionization (MALDI) offers potential for fast spatial profiling, but MALDI imaging of tryptic peptides is still challenged by spectral crowding and restricted abilities for MALDI MS/MS identification.

Methods

To address these limitations, we developed pyrene-conjugated 2-pyridinecarboxaldehyde (pyr-2PCA) tags for selective N-terminal labeling and enhanced detection sensitivity. The 2PCA reagent exclusively modifies N-terminal α-amines, not lysine ε-amines, as could be confirmed in MALDI-MS, with concentration-dependent side reactions minimized by dilution. A distinct reporter ion produced by 2PCA-labeled peptides in prm-PASEF (MALDI MS/MS) serves as a unique marker for successful labeling.

Results

The covalent conjugation of 2PCA with a pyrene structure results in the pyr-2PCA tag that enables matrix-free, label-assisted laser desorption ionization mass spectrometry (LALDI-MS) measurements of peptides. We demonstrate that labeling with a pyrene-coupled 2PCA tag (pyr-2PCA) prior to tryptic digestion results in the selective detection of N-terminal peptides in LALDI, with no significant off-target labeling.

Conclusions

This study presents the first presentation and characterization of this novel pyr-2PCA tag, thereby laying the groundwork and demonstrating its future potential for MALDI/LALDI-based in situ spatial N-terminomics to study proteolytic processes.

蛋白水解是一种基本的翻译后修饰。液相色谱-串联质谱(LC-MS /MS)工作流程对于降解分析功能强大,但固有地牺牲了空间信息,这是研究生物系统(如异常细胞外基质重塑和肿瘤微环境改变)的关键方面。基质辅助激光解吸/电离(MALDI)技术提供了快速空间分析的潜力,但MALDI成像仍然受到光谱拥挤和MALDI MS/MS鉴定能力的限制。方法针对这些局限性,我们开发了芘偶联的2-吡啶甲酸(pyr-2PCA)标签,用于选择性n端标记和提高检测灵敏度。正如MALDI-MS所证实的那样,2PCA试剂只修饰n端α-胺,而不是赖氨酸ε-胺,稀释后的浓度依赖性副反应最小化。在prm-PASEF (MALDI MS/MS)中,由2pca标记的肽产生的独特报告离子作为成功标记的独特标记。结果2PCA与芘共价偶联得到pyr-2PCA标签,该标签可用于多肽的无基质、标签辅助激光解吸电离质谱(LALDI-MS)测量。我们证明,在胰蛋白酶消化之前用芘偶联2PCA标记(pyr-2PCA)可以选择性地检测LALDI中的n端肽,而没有明显的脱靶标记。本研究首次提出并表征了这种新型pyr-2PCA标签,从而为基于MALDI/ laldi的原位空间n端组学研究蛋白质水解过程奠定了基础,并展示了其未来的潜力。
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引用次数: 0
Recursive Attention–Based Prediction of Theoretical MS/MS Spectra From Peptide Sequences 基于递归注意的多肽序列理论质谱/质谱预测
IF 1.7 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2026-01-20 DOI: 10.1002/rcm.70032
Di Dong, Changjiu He, Tao Cui, Yudong Lu, Xuebing Qin

Rationale

In tandem mass spectrometry (MS/MS)–based proteomics, precise prediction of peptide spectra is key to improving peptide identification accuracy and the overall reliability of proteomic studies. However, existing theoretical MS/MS prediction methods are limited by their focus on predicting only b and y backbone fragment ions and their inability to effectively capture the complex long-range dependencies among distant residues within peptide sequences.

Methods

To address these issues, we propose DeepMultiIon, a novel prediction framework based on a mathematically grounded recursive attention mechanism, designed to enhance MS/MS spectral fitting and improve peptide detection sensitivity. By combining local chunking with recursive attention, the model enables deep modeling of long-range residue interactions and the corresponding fragment intensity dependencies. In addition to conventional b and y backbone fragment ions, DeepMultiIon further extends its predictive coverage to a ions and precursor ions, while also encompassing their neutral loss ions (–H2O, –NH3) and isotopic peaks, offering comprehensive coverage of all major spectral peak types.

Results

Performance is evaluated using Pearson correlation coefficient (PCC) and entropy similarity (ES), with comparisons against b/y-only models such as Prosit, pDeep, and AlphaPeptDeep. Experimental results show that DeepMultiIon achieves notable improvements, with average increases of 0.18 in PCC and 0.22 in ES.

Conclusions

These findings demonstrate that incorporating recursive attention and multi-ion prediction significantly improve both the peak coverage and accuracy of theoretical MS/MS spectrum prediction, thereby enhancing peptide-spectrum fitting and contributing to improved peptide detection sensitivity, making DeepMultiIon a powerful tool for advanced proteomics analysis.

在基于串联质谱(MS/MS)的蛋白质组学中,精确预测肽谱是提高蛋白质组学研究的准确性和整体可靠性的关键。然而,现有的理论MS/MS预测方法仅限于预测b和y骨干片段离子,并且无法有效捕获肽序列中远端残基之间复杂的远程依赖关系。为了解决这些问题,我们提出了一种基于数学基础递归注意机制的新型预测框架DeepMultiIon,旨在增强质谱/质谱拟合并提高肽检测灵敏度。通过将局部分块与递归注意相结合,该模型能够对远程残留相互作用和相应的片段强度依赖进行深度建模。除了传统的b和y骨架碎片离子外,DeepMultiIon进一步将其预测范围扩展到a离子和前体离子,同时还包括它们的中性损失离子(-H2O, -NH3)和同位素峰,从而全面覆盖所有主要的光谱峰类型。使用Pearson相关系数(PCC)和熵相似度(ES)对性能进行评估,并与b/y-only模型(如Prosit, pDeep和AlphaPeptDeep)进行比较。实验结果表明,DeepMultiIon取得了显著的改进,PCC平均提高0.18,ES平均提高0.22。结论结合递归注意和多离子预测,可显著提高理论MS/MS谱预测的峰覆盖率和准确性,从而增强肽谱拟合,提高肽检测灵敏度,使DeepMultiIon成为高级蛋白质组学分析的有力工具。
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引用次数: 0
Clumped Isotope Temperature Reconstruction Using Stalagmite Drip Cups 用石笋滴杯重建块状同位素温度。
IF 1.7 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2026-01-20 DOI: 10.1002/rcm.70027
Stuart Umbo, Maria Box, Aviva Intveld, Jack Longman, Sevasti Modestou, Stacy A. Carolin, Daniel H. James, Alfredo Martínez-García, Carlos Peraza Lope, Mark Brenner, David Hodell, Sebastian F. M. Breitenbach

Rationale

Application of clumped isotope palaeothermometry to speleothems (carbonate cave deposits, e.g., stalagmites and flowstones) has been restricted largely to subaqueous samples because of kinetic fractionation processes that occur during subaerial speleothem formation, which lead to erroneously high inferred temperatures. Speleothems are spatially near-ubiquitous terrestrial archives that can be dated accurately over million-year timescales. Thus, wider application of the clumped isotope technique in speleothems could dramatically increase our understanding of terrestrial thermal history. In this study, we assessed the potential of speleothem drip cups (concave depressions at a stalagmite apex in which dripwater accumulates to create a subaqueous environment) to yield reliable palaeotemperature inferences.

Methods

We sampled along two isochronous layers that extend across both sides of a pronounced drip cup in stalagmite MAYA 22-7 from Cenote Ch'en Mul, Yucatán, Mexico, which was dated to 1650 ce ± 23 years. We measured bulk stable (δ18O and δ13C) and clumped (Δ47) isotope values at increasing distances from the drip cup centre to test for kinetic fractionation effects.

Results

Lower δ18O, δ13C, and higher Δ47 values were obtained from the drip cup's central subaqueous zone compared with the subaerial flanks, demonstrating reduced isotope fractionation in the subaqueous zone. Average clumped isotope temperatures (TΔ47) inferred from subaqueous drip cup samples are 1°C–2°C higher than modern cave temperatures and 3°C–7°C warmer than estimated formation paleotemperatures derived from nearby regional reconstructions and TEX86 analysis of our sample. This suggests a persistent degree of clumped isotope kinetic effects.

Conclusions

Despite persistent kinetic effects, lower inferred temperatures from subaqueous drip cup samples suggest closer to equilibrium precipitation compared with subaerial samples. We propose that drip cup carbonates have the potential to yield reliable palaeotemperatures and describe a widely applicable test for clumped isotope kinetic effects in speleothem drip cups by sampling across isochronous layers.

理论基础:块状同位素古温学在洞穴(碳酸盐洞穴矿床,如石笋和流石)中的应用主要局限于水下样品,因为在陆上洞穴形成过程中发生的动力学分馏过程导致错误的高推断温度。洞穴化石是空间上几乎无处不在的陆地档案,可以精确地追溯到百万年的时间尺度。因此,在洞穴中更广泛地应用团块同位素技术可以极大地增加我们对陆地热历史的理解。在这项研究中,我们评估了石笋滴杯(石笋顶端的凹凹处,水滴积聚在其中形成水下环境)的潜力,以产生可靠的古温度推断。方法:我们沿着两个等时层取样,这两个等时层延伸到一个明显的滴漏杯的两侧,来自墨西哥Yucatán的Cenote chen Mul的玛雅22-7石笋,其年代为1650 ce±23年。我们测量了体积稳定同位素(δ18O和δ13C)和团块同位素(Δ47)值,以增加距离滴杯中心,以测试动力学分馏效应。结果:滴水杯中部水下区δ18O、δ13C值较低,Δ47值较高,表明水下区同位素分馏减少。从地下滴杯样品推断出的平均团块同位素温度(TΔ47)比现代洞穴温度高1°C-2°C,比附近区域重建和TEX86样品分析得出的地层古温度高3°C-7°C。这表明存在一定程度的团块同位素动力学效应。结论:尽管存在持续的动力学效应,从水下滴杯样品推断的较低温度表明与地面样品相比更接近平衡降水。我们提出,滴漏杯碳酸盐有可能产生可靠的古温度,并描述了一种广泛适用的测试,通过在等时层取样,在洞穴中滴漏杯中进行块状同位素动力学效应。
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引用次数: 0
Chamber-by-Chamber Measurements of Planktonic Foraminiferal Mg, Sr, and Na to Ca Ratios With Femtosecond LA-ICP-MS 用飞秒LA-ICP-MS逐室测量浮游有孔虫Mg、Sr和Na / Ca比值。
IF 1.7 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2026-01-19 DOI: 10.1002/rcm.70026
Toshihiro Yoshimura, Qing Chang, Naohiko Ohkouchi, Yoshiyuki Ishitani, Dana Ulanova, Hirotoshi Endo, Junichiro Kuroda, Yurika Ujiié

Rationale

Distribution patterns of foraminifera are controlled by environmental parameters such as temperature, salinity, and nutrient concentrations in each water mass. Since trace elements to Ca ratios of marine microfossil calcite test of foraminifera record environmental and ecological habitat information, we used femtosecond (fs) LA-ICP-MS to obtain accurate chamber-by-chamber Mg/Ca, Sr/Ca, and Na/Ca of four foraminifera species to clarify the impact of foraminiferal depth migration on paleoceanographic reconstruction. The Mg/Ca and Sr/Ca ratios were measured with precision better than 5%, fulfilling the accuracy typically required for paleoceanographic reconstructions. We also examined the differences in element ratios due to the pretreatment cleaning methods for extracting accurate paleoceanographic information.

Methods

The fsLA-ICP-MS has the advantage of less matrix and instrumental element fractionation effects on elements with high condensation temperatures. We also applied the use of multiple carbonate standard materials for concentration standardization.

Results

The fsLA-ICP-MS analysis was optimized using a spot size of 30 μm or larger with a laser repetition frequency of 5 to 15 Hz in a circular analytical trajectory. A comparison between ultrasonic and oxidative cleaning protocols revealed that oxidative test cleaning with perchloric acid and hydrogen peroxide achieved higher reproducibility and more efficient impurity removal compared to ultrasonic cleaning with ultrapure water and methanol. Repeated analysis on the same chambers of two species, O. universa and P. obliquiloculata, yielded mean relative standard deviations for Mg/Ca and Sr/Ca of < 5%.

Conclusions

A quantitative method was rapidly developed for determination of Mg, Sr, and Na to ratios of biogenic carbonates of foraminifera. T. sacculifer showed no chamber-by-chamber Mg/Ca variation in calcifying temperature, but average test Mg/Ca temperature decreased by 1.4°C with the addition of the final sac-like chamber and final calcite layer. G. menardii showed a ~7°C difference among chambers suggesting upward migration in the shallow part of the thermocline.

理论基础:有孔虫的分布模式受环境参数控制,如温度、盐度和每个水体中的营养物质浓度。由于有孔虫海洋微化石方解石测试中微量元素与钙的比值记录了环境和生态栖息地信息,我们利用飞秒(fs) LA-ICP-MS精确获取了4种有孔虫的逐室Mg/Ca、Sr/Ca和Na/Ca,以阐明有孔虫深度迁移对古海洋重建的影响。Mg/Ca和Sr/Ca的测量精度均在5%以上,满足了古海洋重建的精度要求。我们还研究了提取准确古海洋学信息的预处理清洗方法所导致的元素比例差异。方法:fsLA-ICP-MS对高冷凝温度的元素具有基质和仪器元素分馏效应小的优点。我们还采用了多种碳酸盐标准材料进行浓度标准化。结果:fsLA-ICP-MS分析的光斑尺寸为30 μm或更大,激光重复频率为5 ~ 15 Hz,分析轨迹为圆形。超声波和氧化清洗方案的比较表明,与超纯水和甲醇的超声波清洗相比,高氯酸和过氧化氢的氧化试验清洗具有更高的再现性和更有效的杂质去除。结论:建立了有孔虫生物源碳酸盐中Mg、Sr、Na比值的定量测定方法,可快速测定有孔虫生物源碳酸盐中Mg、Sr、Na比值。不同室间的钙化温度Mg/Ca没有变化,但随着最终囊状室和最终方解石层的加入,平均试验Mg/Ca温度降低了1.4℃。G. menardii在各室间的差异为~7℃,表明在温跃层的浅部向上迁移。
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引用次数: 0
Microwave Plasma Torch Desorption Ionization Mass Spectrometry for Chemical Constituents of Pinellia ternata (Thunb.) Ten. ex Breitenb. 微波等离子体火炬解吸电离质谱法分析半夏化学成分十个。Breitenb交货。
IF 1.7 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2026-01-15 DOI: 10.1002/rcm.70033
Jiarui Gao

Rationale

Pinellia ternata (Thunb.) Ten. ex Breitenb. is a perennial herb that has a long history of use in traditional Chinese therapy due to its diverse pharmacological activities including antiemetic, antitussive, and anti-tumor activities. Characterization and quality control of P. ternata will be challenging due to its highly complex and diverse chemical composition.

Methods

In this study, we utilized microwave plasma torch desorption ionization mass spectrometry (MPT-MS) for the first time to investigate P. ternata for the purpose of direct in situ analysis of individual samples. Chemical analysis of P. ternata was performed without pretreatment, while accurately identifying classes of chemical constituents, including alkaloids, organic acids, phenolic compounds, and fatty acids. Meanwhile, tandem MPT-MS was used to verification Compounds got in MPT-MS.

Results

Results yielded reproducible and unique chemical fingerprints that reflected the overall chemical composition of P. ternata. Forty-one compounds were detected, including alkaloids, organic acids, phenolic compounds, and fatty acids.

Conclusion

MPT-MS facilitates rapid and direct characterization and quality assessment of this medicinal herb promoting better safety and reliability for clinical uses.

原理:半夏十个。Breitenb交货。是一种多年生草本植物,由于其多种药理活性,包括止吐,止咳和抗肿瘤活性,在传统中医治疗中有着悠久的历史。由于其化学成分的高度复杂和多样化,表征和质量控制将具有挑战性。方法首次利用微波等离子体火炬解吸电离质谱技术(MPT-MS)对拟南芥进行原位分析。在不进行预处理的情况下,对其化学成分进行了准确的分类,包括生物碱、有机酸、酚类化合物和脂肪酸。同时,采用串联MPT-MS对得到的化合物进行验证。结果所得到的指纹图谱重现性好,具有唯一性,能较好地反映药材的化学成分。共检测到41种化合物,包括生物碱、有机酸、酚类化合物和脂肪酸。结论MPT-MS能快速、直接地对该药材进行表征和质量评价,提高了其临床应用的安全性和可靠性。
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引用次数: 0
Gas-Phase F-Atom Migration Reactions of Perfluoroalkyl and Polyfluoroalkyl Sulfonic/Sulfinic Anions 全氟烷基和多氟烷基磺酸/亚磺酸阴离子的气相f原子迁移反应
IF 1.7 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2026-01-15 DOI: 10.1002/rcm.70035
Qingqin Liu, Xiaobao Lv, Chaojun Li, Ping Xing, Lin Ling, Hao-Yang Wang

Rationale

Many perfluoroalkyl and polyfluoroalkyl sulfonic/sulfinic acids and their derivatives are classified as perfluoroalkyl and polyfluoroalkyl substances (PFASs). The use of mass spectrometry techniques to analyze these compounds has attracted considerable research attention.

Methods

In this article, we employed high-resolution electrospray ionization tandem mass spectrometry (HR-ESI-MS/MS) and all-ion fragmentation (AIF) in negative ion mode to investigate gas-phase F-atom migration reactions of various perfluoroalkyl and polyfluoroalkyl sulfonic/sulfinic anions, particularly those yielding FSO3 or FSO2.

Results

HR-ESI-MS/MS of CF3SO3 yielded an unexpected product ion FSO3, representing a distinct pathway of gas-phase F-atom migration from C-atom to S-atom accompanied by the loss of CF2. Similarly, HR-ESI-MS/MS of CF3SO2 produced a dominant product ion FSO2 also via CF2 elimination. Complementary ESI-MS/MS and AIF experiments on these anions confirmed that FSO2 and/or FSO3 are their characteristic fragmentation ions.

Conclusion

Theoretical calculations of gas-phase reactions CF3SO3 → FSO3 + CF2 and CF3SO2 → FSO2 + CF2 were performed to investigate the possible F-atom migration mechanisms. These results show that FSO3 at m/z 99 and/or FSO2 at m/z 83 could serve as diagnostic ions for structural elucidation of perfluoroalkyl and polyfluoroalkyl sulfonic/sulfinic acids and their derivatives in non-target PFASs analyses by using mass spectrometry.

许多全氟烷基和多氟烷基磺酸/亚磺酸及其衍生物被归类为全氟烷基和多氟烷基物质(PFASs)。使用质谱技术分析这些化合物已经引起了相当大的研究关注。方法采用高分辨率电喷雾电离串联质谱法(HR-ESI-MS/MS)和负离子模式下的全离子碎片化(AIF)研究了各种全氟烷基和多氟烷基磺酸/亚磺酸阴离子的气相f原子迁移反应,特别是产生FSO3 -或FSO2 -的阴离子。结果CF3SO3−的HR-ESI-MS/MS得到了一个意想不到的产物离子FSO3−,代表了气相f原子从c原子迁移到s原子的独特途径,同时伴有CF2的损失。同样,HR-ESI-MS/MS的CF3SO2−也通过CF2消除产生优势产物离子FSO2−。对这些阴离子进行ESI-MS/MS和AIF互补实验,证实FSO2 -和/或FSO3 -是它们的特征破碎离子。结论对CF3SO3−→FSO3−+ CF2和CF3SO2−→FSO2−+ CF2的气相反应进行了理论计算,探讨了可能的f原子迁移机制。这些结果表明,FSO3 - at m/ z99和/或FSO2 - at m/ z83可以作为诊断离子,用于非靶PFASs分析中的全氟烷基和多氟烷基磺酸/亚磺酸及其衍生物的结构解析。
{"title":"Gas-Phase F-Atom Migration Reactions of Perfluoroalkyl and Polyfluoroalkyl Sulfonic/Sulfinic Anions","authors":"Qingqin Liu,&nbsp;Xiaobao Lv,&nbsp;Chaojun Li,&nbsp;Ping Xing,&nbsp;Lin Ling,&nbsp;Hao-Yang Wang","doi":"10.1002/rcm.70035","DOIUrl":"https://doi.org/10.1002/rcm.70035","url":null,"abstract":"<div>\u0000 \u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>Many perfluoroalkyl and polyfluoroalkyl sulfonic/sulfinic acids and their derivatives are classified as perfluoroalkyl and polyfluoroalkyl substances (PFASs). The use of mass spectrometry techniques to analyze these compounds has attracted considerable research attention.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>In this article, we employed high-resolution electrospray ionization tandem mass spectrometry (HR-ESI-MS/MS) and all-ion fragmentation (AIF) in negative ion mode to investigate gas-phase F-atom migration reactions of various perfluoroalkyl and polyfluoroalkyl sulfonic/sulfinic anions, particularly those yielding FSO<sub>3</sub><sup>−</sup> or FSO<sub>2</sub><sup>−</sup>.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>HR-ESI-MS/MS of CF<sub>3</sub>SO<sub>3</sub><sup>−</sup> yielded an unexpected product ion FSO<sub>3</sub><sup>−</sup>, representing a distinct pathway of gas-phase F-atom migration from C-atom to S-atom accompanied by the loss of CF<sub>2</sub>. Similarly, HR-ESI-MS/MS of CF<sub>3</sub>SO<sub>2</sub><sup>−</sup> produced a dominant product ion FSO<sub>2</sub><sup>−</sup> also via CF<sub>2</sub> elimination. Complementary ESI-MS/MS and AIF experiments on these anions confirmed that FSO<sub>2</sub><sup>−</sup> and/or FSO<sub>3</sub><sup>−</sup> are their characteristic fragmentation ions.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusion</h3>\u0000 \u0000 <p>Theoretical calculations of gas-phase reactions CF<sub>3</sub>SO<sub>3</sub><sup>−</sup> → FSO<sub>3</sub><sup>−</sup> + CF<sub>2</sub> and CF<sub>3</sub>SO<sub>2</sub><sup>−</sup> → FSO<sub>2</sub><sup>−</sup> + CF<sub>2</sub> were performed to investigate the possible F-atom migration mechanisms. These results show that FSO<sub>3</sub><sup>−</sup> at <i>m/z</i> 99 and/or FSO<sub>2</sub><sup>−</sup> at <i>m/z</i> 83 could serve as diagnostic ions for structural elucidation of perfluoroalkyl and polyfluoroalkyl sulfonic/sulfinic acids and their derivatives in non-target PFASs analyses by using mass spectrometry.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"40 7","pages":""},"PeriodicalIF":1.7,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145987047","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
Nitrogen Isotope Analysis of Aliphatic and Aromatic Amines by GC-C-IRMS and the Application for Tracing Atmospheric Organic Amine Sources GC-C-IRMS法分析脂肪族胺和芳香胺的氮同位素及在大气有机胺源追踪中的应用
IF 1.7 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2026-01-15 DOI: 10.1002/rcm.70028
Heizeng Chen, Zicong Wang, Meicheng Wen, Jukun Xiong, Qinhao Lin, Guiying Li, Taicheng An

Rationale

Compounds-specific stable isotope analysis (CSIA) is an advanced tool for assessing the sources and fates of organic amines in environments. The use of gas chromatography–combustion–isotope ratio mass spectrometry (GC-C-IRMS) remains constrained by the thermal stability, high polarity, and the typically low environmental concentrations of organic amines.

Methods

The development of suitable derivatization strategies for polar organic amines can broaden the applicability of GC-C-IRMS. To establish a nitrogen stable isotope analytical method for polar organic amines in the atmosphere, derivatization with isobutyl chloroformate (IBCF) reagent was adopted. Method performance was evaluated using six aliphatic amines and three aromatic amines.

Results

The derivatization method demonstrated good reproducibility, high linearity, and no detectable isotopic fractionation. Accurate and precise nitrogen stable isotope measurements were achieved using the IBCF derivatization reagent. Deviations of δ15N values from reference measurements obtained by elemental analyzer–isotope ratio mass spectrometry (EA-IRMS) were small (< 0.3‰) and within the typical uncertainty of GC-C-IRMS (< 0.6‰). Method detection limits (MDLs) for the nine organic amines ranged from 2.06 to 4.12 nmol N injected on column.

Conclusions

The applicability of the developed method was demonstrated through analysis of atmospheric methylamine (MA). The measured δ15N values of MA varied significantly across sources, ranging from −11.6‰ to −9.1‰ for vehicular exhaust, −20.2‰ to −15.7‰ for coastal samples, and −26.7‰ to −22.2‰ for municipal solid waste sanitary sources, indicating that δ15N values effectively distinguish MA sources.

化合物特异性稳定同位素分析(CSIA)是一种评估环境中有机胺来源和去向的先进工具。气相色谱-燃烧-同位素比值质谱(GC-C-IRMS)的使用仍然受到热稳定性、高极性和典型的低环境浓度有机胺的限制。方法开发适合极性有机胺的衍生化策略,扩大GC-C-IRMS的适用性。为了建立大气中极性有机胺的氮稳定同位素分析方法,采用氯甲酸异丁酯(IBCF)试剂衍生化。用6种脂肪胺和3种芳香胺评价了方法的性能。结果衍生化方法重现性好,线性度高,无同位素分离。使用IBCF衍生化试剂,实现了精确的氮稳定同位素测量。元素分析仪-同位素比质谱法(EA-IRMS)的δ15N值与参考测量值的偏差很小(0.3‰),在GC-C-IRMS的典型不确定度(0.6‰)内。方法9种有机胺的检出限(MDLs)为2.06 ~ 4.12 nmol N。结论通过对大气中甲胺(MA)的分析,验证了该方法的适用性。实测MA δ15N值在不同源间差异显著,汽车尾气δ15N值为- 11.6‰~ - 9.1‰,沿海样品δ15N值为- 20.2‰~ - 15.7‰,城市生活垃圾卫生源δ15N值为- 26.7‰~ - 22.2‰,表明δ15N值能有效区分MA源。
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引用次数: 0
Identification and Quantification of Structurally Related Peptide Impurity in Linaclotide by Liquid Chromatography–High Resolution Mass Spectrometry 液相色谱-高分辨质谱法鉴定和定量利那洛肽中结构相关肽杂质
IF 1.7 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2026-01-15 DOI: 10.1002/rcm.70030
Jinlan Cheng, Tianji Zhang, Xinling Cui, Peize Wu, Ming Li, Wenrui Hu, Xueting Dai, Xuesong Feng

Rationale

Linaclotide is an important peptide drug used to treat irritable bowel syndrome with constipation (IBS-C). However, structurally related impurities in peptide drugs can be generated during synthesis, storage, or transport, which compromise the quality and safety. Therefore, developing a highly sensitive analytical method for impurity detection is of great significance.

Methods

A liquid chromatography–high resolution mass spectrometry (LC-HRMS) method was developed. Linaclotide samples were directly analyzed using an Orbitrap mass spectrometer with an electrospray ionization (ESI) source operated in positive ion mode. Tandem mass spectrometry with collision-induced dissociation was utilized. The method leveraged high mass accuracy to identify and quantify structurally related peptide impurities in linaclotide samples from different manufacturers.

Results

The method was applied to characterize the peptide impurities in linaclotide study materials. In manufacturer A's material, [Des-Tyr14]-linaclotide was found at 0.453 mg/g. The same impurity was found in manufacturer B's material at 0.768 mg/g, as well as another impurity [endo-Ala9]-linaclotide at 0.555 mg/g.

Conclusions

The developed LC-HRMS method successfully addresses the challenge of determining structurally related peptide impurities in linaclotide. Its ability to characterize specific impurities provides a valuable complement to existing quality control strategies for peptide therapeutics.

利那洛肽是治疗肠易激综合征伴便秘(IBS-C)的重要肽类药物。然而,多肽药物在合成、储存或运输过程中会产生结构相关杂质,影响其质量和安全性。因此,开发一种高灵敏度的杂质检测分析方法具有重要意义。方法建立液相色谱-高分辨质谱联用方法。采用正离子模式电喷雾电离(ESI)源的Orbitrap质谱仪对利那氯肽样品进行直接分析。采用碰撞诱导解离串联质谱法。该方法利用高质量精度来鉴定和定量来自不同厂家的利那氯肽样品中结构相关的肽杂质。结果该方法可用于利那洛肽研究材料中多肽杂质的表征。在制造商A的材料中,[Des-Tyr14]-linaclotide的含量为0.453 mg/g。在B厂家的原料中也发现了同样的杂质,含量为0.768 mg/g,另一种杂质[endo-Ala9]-linaclotide含量为0.555 mg/g。结论建立的LC-HRMS方法成功地解决了利那洛肽结构相关肽杂质测定的难题。它表征特定杂质的能力为现有的肽治疗质量控制策略提供了有价值的补充。
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引用次数: 0
GC–MS of Some Haemanthamine- and Crinine-Type Amaryllidaceae Alkaloids 部分海毒属和海毒属香堇科生物碱的GC-MS分析
IF 1.7 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2026-01-15 DOI: 10.1002/rcm.70019
Strahil Berkov, Rumen Denev, David Kok, Jean Paulo de Andrade, Boriana Sidjimova, Luciana R. Tallini, Laura Torras-Claveria, Ahmed Hussein, Jaume Bastida

Rationale

The search for novel natural compounds and the identification of known ones is a challenge for the scientists working in different fields of plant science. Due to its accessibility, GC–MS is the most frequently applied method for analysis of extracts and fractions from plants of the subfamily Amaryllidoideae (Amaryllidaceae s.s.), known as a source of molecules with potent anti-acetylcholinesterase, anti-tumour, and antiprotozoal activities.

Methods

Thirty-four standard alkaloids with haemanthamine- and crinine-type scaffolds were subjected to electron impact gas chromatography–mass spectrometry (GC–MS) to determine their fragmentation patterns. Additionally, underivatised and silylated alkaloid fractions from several Amaryllidoideae plants were also analysed by GC–MS.

Results

Most of the compounds showed excellent separation and specific MS fragmentation allowing rapid structural determination. The degree of saturation of ring C and the substituents at C3, C6, and C11 impact the fragmentation of these molecules. GC–MS allowed differentiation of the epimers at C3. Silylation of compounds with hydroxyl groups at C6 and C11 improved the resolution, especially of C6-OH epimers. Analyses of alkaloid fractions from different Amaryllidaceae plants resulted in the tentative identification of five new alkaloids on the basis of their fragmentation pattern and comparison of their mass spectra with those of standard compounds.

Conclusions

GC–MS can be effectively employed for the discovery of novel bioactive compounds and the identification of known ones, as well as for chemotaxonomic and chemoecological studies, among other applications, within the Amaryllidoideae subfamily.

对从事植物科学不同领域的科学家来说,寻找新的天然化合物和鉴定已知化合物是一个挑战。由于其可及性,气相色谱-质谱是最常用的分析方法,用于分析从Amaryllidoideae亚科(amarylliidaceae s.s.)植物中提取的提取物和组分。Amaryllidoideae亚科是一种具有抗乙酰胆碱酯酶、抗肿瘤和抗原虫活性的分子来源。方法采用电子冲击气相色谱-质谱(GC-MS)法测定34种标准生物碱的破碎模式。此外,还采用气相色谱-质谱法分析了几种香蓟科植物的未叶化和硅烷化生物碱组分。结果大多数化合物具有良好的分离性和特异的质谱碎片,可快速测定其结构。环C和C3、C6、C11取代基的饱和程度影响了这些分子的断裂。GC-MS允许C3处的外显体分化。含有C6和C11羟基的化合物的硅基化提高了分辨率,特别是C6- oh外显体。通过对不同苋菜科植物的生物碱组分进行分析,并与标准化合物的质谱比较,初步鉴定出5种新的生物碱。结论气相色谱-质谱法可以有效地用于发现和鉴定新的生物活性化合物,以及化学分类学和化学生态学等方面的研究。
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引用次数: 0
期刊
Rapid Communications in Mass Spectrometry
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