Rapid Communications in Mass Spectrometry最新文献_第7页

Integrative Analysis of Curcuma kwangsiensis Reveals Markers for Distinguishing Rhizome, Radix, and Non-Medicinal Parts via LDA-Based Classification 基于lda分类的姜黄根茎、根茎和非药用成分的综合分析

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-09-01 DOI: 10.1002/rcm.10105

Qing Yang, Jiansang Wulu, Min He, Ming Chen, Zichang Liang, Juan Li, Jing Li, Zhifeng Zhang, Jianguang Zhang

Introduction

Curcumae Rhizoma (Ezhu) and Curcumae Radix (Yujin) are both derived from Curcuma kwangsiensis (CK), an important species in the Zingiberaceae family. They have different clinical applications in traditional Chinese medicine (TCM): The rhizome is mainly used for antitumor treatments, whereas the radix is known for antidepressant and cholagogic effects, both officially listed in the Chinese Pharmacopoeia. However, non-medicinal parts such as the aerial portions and fibrous roots are sometimes mixed in, leading to confusion in clinical formulation use.

Objective

This study aimed to analyze different parts of CK, including its rhizome (RHCK), radix (RACK), aerial parts (APCK), and fibrous root (FRCK) using inductively coupled plasma mass spectrometry (ICP-MS), ultra-high-performance liquid chromatography-quadrupole-electrostatic field Orbitrap high-resolution mass spectrometry (UPLC-Q Exactive Orbitrap-MS), and gas chromatography–mass spectrometry (GC-MS).

Methodology

These mineral elements of different parts in CK were determined by using (ICP-MS). The nonvolatile metabolites were achieved by UPLC-Q Exactive Orbitrap-MS, and the volatile metabolites were identified by GC-MS. Statistical analysis, including principal component analysis (PCA) and orthogonal partial least-squares discriminate analysis (OPLS-DA) model, was used to classify different parts of CK based on mineral elements and metabolites. Furthermore, linear discriminant analysis (LDA) was utilized to effectively differentiate the different parts by analyzing the data.

Results

In total, 26 mineral elements, 738 nonvolatile metabolites, and 87 volatile metabolites were identified. Multivariate analysis revealed 14 mineral elements, 390 nonvolatile metabolites, and 42 volatile metabolites (VIP > 1) as potential markers. A LDA model effectively distinguished the four plant parts, achieving a classification accuracy of 95%.

Conclusion

These findings offer a practical strategy for accurately identifying and differentiating medicinal from non-medicinal parts of CK, reducing misidentification in TCM formulations and enhancing clinical safety.

莪术（Curcumae Rhizoma, Ezhu）和莪术（Curcumae Radix, Yujin）均源自姜科重要植物姜黄（Curcuma kwangsiensis， CK）。它们在中医中有不同的临床应用：根茎主要用于抗肿瘤治疗，而根茎则以抗抑郁和胆道作用而闻名，这两种作用都已被正式列入中国药典。然而，非药用部分，如空气部分和纤维根有时混合在一起，导致临床配方使用混乱。目的采用电感耦合等离子体质谱法（ICP-MS）、超高效液相色谱-四极静电场轨道阱高分辨率质谱法（UPLC-Q Exactive Orbitrap- ms）和气相色谱-质谱法（GC-MS）对黄菊花根茎（RHCK）、根茎（RACK）、根部（APCK）和纤维根（FRCK）等不同部位进行分析。方法采用ICP-MS法测定CK中不同部位的矿质元素。非挥发性代谢物采用UPLC-Q萃取轨道质谱法测定，挥发性代谢物采用气相色谱-质谱法测定。采用主成分分析（PCA）和正交偏最小二乘判别分析（OPLS-DA）模型，对CK不同部位的矿质元素和代谢物进行分类。此外，利用线性判别分析（LDA）对数据进行分析，有效区分不同部位。结果共鉴定出26种矿物元素、738种非挥发性代谢物和87种挥发性代谢物。多因素分析显示，14种矿物元素、390种非挥发性代谢物和42种挥发性代谢物（VIP > 1）是潜在的标志物。LDA模型有效地区分了四种植物部位，分类准确率达到95%。结论本研究结果为准确识别和区分黄芪的药用部位和非药用部位，减少中药配方中的误认，提高临床安全性提供了可行的策略。

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引用次数: 0

Molecular Organ Lysate Imprinting: For Precision Recognition and Analysis of Organ-Derived Proteins 分子器官裂解物印迹：用于器官来源蛋白的精确识别和分析

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-08-27 DOI: 10.1002/rcm.10125

Jatinderpal K. Sandhu, Donald J. L. Jones, Colleen B. Maxwell, Charlotte L. Gwinnell, Geraldine Williams, Thong Huy Cao, Paulene A. Quinn, Leong L. Ng

Rationale

Molecular imprinting has emerged as a promising strategy to create custom imprints for precision recognition of proteins. This study proposes using dopamine polymers as a novel approach to enhance the retrieval of proteins from human plasma. Dopamine polymers possess adhesive properties due to their ability to form hydrophobic interactions, π-π, hydrogen bonding and van der Waals forces with various substrates; in this study, we have leveraged these adhesive properties to capture and retrieve proteins from complex biological samples.

Methods

We imprinted proteins derived from mouse heart lysate and evaluated the performance of the resulting molecularly imprinted polymer for retrieval of the human protein cardiovascular disease plasma samples.

Results

Our results demonstrated the retrieval of troponin T, fatty acid–binding protein, creatine kinase, lactate dehydrogenase, and myosin-binding protein C. This novel application of dopamine polymers in protein enrichment and analysis facilitates the discovery of novel biomarkers from complex matrices, such as plasma, and promotes deeper insights into complex biological processes.

Conclusions

This method, characterized by high specificity and stability, offers a new approach for the detection of low abundant proteins and provides a scientific basis for the future development of new diagnostic tools and personalized medical strategies.

基本原理分子印迹已经成为一种很有前途的策略来创建精确识别蛋白质的定制印迹。本研究提出使用多巴胺聚合物作为一种新的方法来增强从人血浆中提取蛋白质。多巴胺聚合物具有粘附性能，因为它们能够与各种底物形成疏水相互作用、π-π、氢键和范德华力；在这项研究中，我们利用这些粘附特性从复杂的生物样品中捕获和检索蛋白质。方法对从小鼠心脏裂解液中提取的蛋白进行印迹处理，并对所得分子印迹聚合物在人类心血管疾病血浆蛋白样品检索中的性能进行评价。我们的研究结果证明了肌钙蛋白T、脂肪酸结合蛋白、肌酸激酶、乳酸脱氢酶和肌球蛋白结合蛋白c的检索。多巴胺聚合物在蛋白质富集和分析中的新应用促进了从复杂基质（如血浆）中发现新的生物标志物，并促进了对复杂生物过程的更深入了解。结论该方法具有特异性和稳定性高的特点，为低丰度蛋白的检测提供了新的途径，为未来开发新的诊断工具和个性化医疗策略提供了科学依据。

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引用次数: 0

Stable Nitrogen Isotope Analysis of Amino Acids by Orbitrap Mass Spectrometry: Application for Extraterrestrial Samples 用轨道阱质谱法分析氨基酸的稳定氮同位素：在地外样品中的应用

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-08-26 DOI: 10.1002/rcm.10127

O. M. McIntosh, A. A. Baczynski, M. Matney, H. L. McLain, K. K. Farnsworth, J. P. Dworkin, D. P. Glavin, J. E. Elsila, H. Xie, K. H. Freeman

Background

Obtaining isotopic data on soluble organic compounds, such as amino acids, in extraterrestrial samples is crucial for understanding their origins, prebiotic chemistry, and potential contamination. Conventional GC-IRMS requires grams of material to measure isotopic compositions, limiting the analysis of low-concentration organics in meteorites and other astromaterials. We present an Orbitrap-based method optimized for nitrogen isotopic analysis of amino acids.

Results

This method determines δ¹⁵N values for picomole quantities (< 150 pmol) with 3‰–8‰ precision and accuracy within 2‰ compared with elemental analysis. Our approach was validated using amino acid enantiomer standards and a CM2 Murchison meteorite sample. The Murchison results demonstrate that comparable precision can be achieved on analytes extracted from a total sample size representing less than 7% of the mass previously required for CSIA analysis of the same meteorite.

Significance

These results highlight the potential of Orbitrap mass spectrometry for δ¹⁵N measurements with less material and lower analyte concentrations. This technique improves our ability to trace the origins and synthetic pathways of amino acids, providing valuable insights into prebiotic chemistry and possible abiotic mechanisms for organic compound formation in primitive solar system materials. Nitrogen isotopes serve as a powerful tool for distinguishing biological from non-biological sources, aiding in the identification of contamination in meteoritic samples and improving the reliability of analyses involving rare extraterrestrial materials.

获取地外样品中可溶性有机化合物（如氨基酸）的同位素数据对于了解它们的起源、益生元化学和潜在污染至关重要。传统的GC-IRMS需要克数的材料来测量同位素组成，限制了对陨石和其他天体材料中低浓度有机物的分析。我们提出了一种优化的基于轨道阱的氨基酸氮同位素分析方法。结果与元素分析法相比，该方法测定皮摩尔量(< 150 pmol) δ15N值的精密度为3‰~ 8‰，准确度在2‰以内。我们的方法通过氨基酸对映体标准和CM2 Murchison陨石样本进行了验证。Murchison的结果表明，从总样本量中提取的分析物可以达到相当的精度，这些分析物的质量不到以前CSIA分析同一颗陨石所需质量的7%。这些结果突出了Orbitrap质谱法在较少的材料和较低的分析物浓度下测量δ15N的潜力。这项技术提高了我们追踪氨基酸起源和合成途径的能力，为原始太阳系物质中有机化合物形成的益生元化学和可能的非生物机制提供了有价值的见解。氮同位素是区分生物和非生物来源的有力工具，有助于查明陨石样品中的污染，并提高涉及稀有外星物质的分析的可靠性。

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引用次数: 0

Identification of In Vivo Components in Shiduqing Capsule Using High-Resolution Mass Spectrometry and Network Pharmacology-Based Analysis of Its Therapeutic Mechanisms Against Eczema 高分辨率质谱法鉴定十毒清胶囊体内成分及基于网络药理学的湿疹治疗机制分析

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-08-26 DOI: 10.1002/rcm.10128

Shuang Li, Zhiyan Liu, Ping Sun, Ayiguzhali Yusun, Mo Sun, Chun Bao, Chenning Zhang

Rationale

Shiduqing Capsule, a clinically widely used Chinese patent medicine, is indicated for skin itching, dryness, and desquamation caused by blood deficiency with wind-dryness syndrome. However, the tissue distribution characteristics of its active components in vivo and its pharmacological mechanisms in treating eczema remain unclear. This study aims to identify the bioactive components of Shiduqing Capsule, characterize their in vivo tissue distribution patterns, and subsequently elucidate the underlying therapeutic mechanisms against eczema based on these findings.

Methods

This study employed high-resolution mass spectrometry (HRMS) coupled with the Global Natural Products Social Molecular Networking (GNPS) platform to comprehensively identify the chemical constituents of Shiduqing Capsule in vivo, while simultaneously characterizing their tissue-specific distribution profiles. Furthermore, network pharmacology approaches were utilized to systematically investigate the therapeutic mechanisms underlying Shiduqing Capsule's efficacy against eczema.

Results

Through systematic chemical composition analysis, 51 blood-absorbed components were identified in Shiduqing Capsule using advanced analytical techniques. Further GNPS-assisted mass spectrometry analysis revealed its predominant composition of flavonoids, lipids, terpenoids, and phenylpropanoids. Network pharmacology investigation demonstrated that the capsule's anti-eczema effects are mediated through critical pathways including TNF signaling and Th17 cell differentiation.

Conclusion

This study systematically analyzed the in vivo components of Shiduqing Capsule and their tissue distribution characteristics, while elucidating the underlying mechanisms of its therapeutic effects against eczema.

十毒清胶囊是临床上广泛使用的中成药，用于治疗血虚风燥证所致皮肤瘙痒、干燥、脱屑。然而，其有效成分在体内的组织分布特征及其治疗湿疹的药理机制尚不清楚。本研究旨在鉴定十毒清胶囊的生物活性成分，表征其体内组织分布模式，并在此基础上阐明其治疗湿疹的潜在机制。方法采用高分辨率质谱法（HRMS）结合全球天然产物社会分子网络（GNPS）平台，全面鉴定十毒清胶囊的体内化学成分，同时表征其组织特异性分布特征。利用网络药理学方法，系统探讨十毒清胶囊治疗湿疹的作用机制。结果采用先进的分析技术，对十毒清胶囊进行系统化学成分分析，鉴定出51种血吸收成分。进一步的gnps辅助质谱分析显示其主要成分为类黄酮、脂类、萜类和苯丙类。网络药理学研究表明，该胶囊的抗湿疹作用是通过TNF信号和Th17细胞分化等关键途径介导的。结论本研究系统分析了十毒清胶囊的体内成分及其组织分布特征，阐明了其治疗湿疹的作用机制。

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引用次数: 0

An Innovative Inter-Spectral Distance-Based Approach to Analyzing MALDI-TOF Mass Spectra of Closely Related Microbial Species 一种基于谱间距离的创新方法分析密切相关微生物物种的MALDI-TOF质谱

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-08-24 DOI: 10.1002/rcm.10121

Xutao Hu, Wen Liu, Xiaopeng Xing

Rationale: Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) is a highly efficient technique for microbial identification; however, the accuracy has always been a problem when identifying closely related microbial species. Improving spectral data identification algorithms is one of the key approaches to enhancing the discriminatory power and reliability of identification for the closely related species.

Methods: This study develops a dimensionality reduction method based on inter-spectral distance computation for the analysis of MALDI-TOF MS data. The method comprises four steps: average spectrum construction, peak matching, distance calculation, and spectral vectorization. We applied this method, along with the conventional principal component analysis (PCA) method, to a MALDI-TOF MS dataset of closely related microbial species. Binary classification experiments were conducted to compare the classification performance of the two methods, and multiclass classification experiments were conducted to evaluate the feasibility of the proposed approach for database construction.

Results: A systematic evaluation of the newly proposed distance-based method was conducted using MALDI-TOF mass spectral data from five pairs of closely related microbial species. The results indicated that this method effectively extracted spectral features and enabled accurate classification. It outperformed the conventional PCA method, and even other more sophisticated methods like LDA and t-SNE, in terms of both clustering performance and identification accuracy.

Conclusions: The findings suggest that the newly proposed distance-based dimensionality reduction algorithm (DbDRA) largely enhances the reliability of identifying closely related microbial species, highlighting its potential applicability in microbial identification using MALDI-TOF mass spectroscopy.

原理：基质辅助激光解吸/电离飞行时间质谱（MALDI-TOF MS）是一种高效的微生物鉴定技术；然而，在鉴定密切相关的微生物物种时，准确性一直是一个问题。改进光谱数据识别算法是提高近缘物种识别能力和可靠性的关键途径之一。方法：建立基于谱间距离计算的MALDI-TOF质谱降维方法。该方法包括平均光谱构建、峰值匹配、距离计算和光谱矢量化四个步骤。我们将该方法与传统的主成分分析（PCA）方法一起应用于密切相关微生物物种的MALDI-TOF MS数据集。通过二元分类实验比较两种方法的分类性能，通过多类分类实验评价所提方法构建数据库的可行性。结果：利用来自5对密切相关微生物物种的MALDI-TOF质谱数据，对新提出的基于距离的方法进行了系统评估。结果表明，该方法能有效提取光谱特征，实现准确分类。在聚类性能和识别精度方面，它优于传统的PCA方法，甚至优于LDA和t-SNE等更复杂的方法。结论：研究结果表明，新提出的基于距离的降维算法（DbDRA）在很大程度上提高了鉴定密切相关微生物物种的可靠性，突出了其在MALDI-TOF质谱微生物鉴定中的潜在适用性。

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引用次数: 0

Assessment of Nitrosamine Impurities in Lurasidone Hydrochloride Using APCI-LC–MS/MS in MRM Mode for Regulatory Compliance and Stability Evaluation APCI-LC-MS /MS在MRM模式下评价盐酸鲁拉西酮中亚硝胺类杂质的符合性和稳定性

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-08-24 DOI: 10.1002/rcm.10126

Anant D. Yadav, Ashish C. Alaspure, Pinal S. Bhavsar, Sandesh R. Lodha, Anil H. Gore

Rationale

Nitrosamine impurities, such as N-nitroso diethylamine (NDEA), N-nitroso dimethylamine (NDMA), and 1-nitroso piperazine (1-NP), have raised serious health concerns due to their carcinogenic and mutagenic properties. The pharmaceutical industry faces increasing regulatory pressure to monitor these compounds at trace levels. This study addresses the need for a robust analytical method to ensure the safety of lurasidone hydrochloride (LUR), an antipsychotic drug.

Methods

A sensitive and specific LC–MS/MS method was developed using atmospheric pressure chemical ionization (APCI) in positive mode and operated in multiple reaction monitoring (MRM). Chromatographic separation was performed on a Sapphirus C18 HP-classic column under gradient elution, with 0.1% formic acid in water and methanol as the mobile phase. Detection was carried out using an Agilent 6470B triple-quadrupole mass spectrometer.

Results

The method demonstrated excellent linearity (regression coefficient > 0.999) across a range extending to 200% of the specified limit. Limits of detection and quantitation were suitable for trace-level analysis. Accuracy was confirmed through recovery studies, with results ranging between 80 and 120%. The method met ICH Q2 (R2) validation criteria, ensuring reliability for regulatory use.

Conclusions

The developed APCI-LC–MS/MS method provides accurate and reproducible quantification of NDEA, NDMA, and 1-NP in lurasidone hydrochloride. Its sensitivity and compliance with regulatory standards make it suitable for routine quality control and stability testing of nitrosamine impurities in lurasidone hydrochloride drug substance.

亚硝胺类杂质，如n -亚硝基二乙胺（NDEA）、n -亚硝基二甲胺（NDMA）和1-亚硝基哌嗪（1-NP），由于其致癌和致突变特性，引起了严重的健康问题。制药业面临着越来越大的监管压力，需要监测这些化合物的微量含量。本研究解决了需要一个强大的分析方法，以确保盐酸鲁拉西酮（LUR）的安全性，一种抗精神病药物。方法采用常压化学电离（APCI）阳性模式，建立了一种灵敏、特异的LC-MS /MS方法，并应用于多反应监测（MRM）。色谱柱为Sapphirus C18 HP-classic，以0.1%甲酸水溶液和甲醇为流动相，梯度洗脱。采用Agilent 6470B三重四极杆质谱仪进行检测。结果该方法线性良好（回归系数>； 0.999），线性范围为规定限度的200%。检出限和定量限适用于痕量分析。通过恢复研究证实了准确性，结果在80%到120%之间。该方法符合ICH Q2 （R2）验证标准，确保了监管使用的可靠性。结论建立的APCI-LC-MS /MS方法定量盐酸鲁拉西酮中NDEA、NDMA和1-NP含量准确、重复性好。该方法灵敏度高，符合国家标准，适用于盐酸鲁拉西酮原料药中亚硝胺类杂质的常规质量控制和稳定性检测。

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引用次数: 0

Synthesis and In Vitro Metabolic Profiling of the Selective Androgen Receptor Modulator (SARM) LY305 选择性雄激素受体调节剂LY305的合成及体外代谢分析

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-08-15 DOI: 10.1002/rcm.10124

Giorgi Kobidze, Tristan Möller, Hui-Chung Wen, Francesco Paolo Busardò, Mario Thevis

Rationale

2-Chloro-4-[[(1R,2R)-2-hydroxy-2-methyl-cyclopentyl]amino]-3-methyl-benzonitrile (LY305) is a transdermal selective androgen receptor modulator (SARM) that has been under development as a potential therapeutic for conditions involving muscle wasting, osteoporosis, or hypogonadism. Due to its proven anabolic effects, its potential (and illicit) use in sport must be taken into consideration, necessitating information on its biotransformation for the implementation of adequate target analytes into routine doping control analytical procedures. In this study, the synthesis of LY305 and in vitro-derived metabolites of the SARM are described.

Methods

LY305 was synthesized by a Buchwald–Hartwig amination using 2-chloro-4-iodo-3-methylbenzonitrile and (1R,2R)-2-amino-1-methyl-cyclopentanol. The in vitro metabolism experiments were conducted using human liver microsomes (HLM) and the S9 fraction to allow for studying phase-I and phase-II biotransformations. For the detection and separation of LY305 and its metabolites, liquid chromatography–high-resolution tandem mass spectrometry was used.

Results

Overall, 18 metabolites were detected, nine of which were identified as phase-I metabolites and an additional nine were attributed to phase-II conjugates. Metabolic reactions were as follows: hydroxylation, dehydrogenation, oxidation, oxidation and hydroxylation, O-glucuronidation, hydroxylation with subsequent glucuronidation, and bis-hydroxylation with subsequent glucuronidation.

Conclusions

The transdermal SARM LY305 was successfully synthesized and subjected to in vitro metabolic studies, yielding chromatographic and mass spectral data that support improving comprehensive anti-doping tests. To the best of our knowledge, no published experimental data exist that report on the in vitro metabolic profile of LY305, a substance that might undergo further (pre)clinical evaluation.

2-氯-4-[[(1R,2R)-2-羟基-2-甲基-环戊基]氨基]-3-甲基-苯并腈（LY305）是一种经皮选择性雄激素受体调节剂（SARM），已被开发用于治疗肌肉萎缩、骨质疏松或性腺功能减退等疾病。由于其已证实的合成代谢作用，必须考虑其在体育运动中的潜在（和非法）使用，需要有关其生物转化的信息，以便在常规兴奋剂控制分析程序中实施足够的目标分析物。在这项研究中，LY305的合成和体外衍生的SARM代谢物进行了描述。方法以2-氯-4-碘-3-甲基苯腈和(1R,2R)-2-氨基-1-甲基环戊醇为原料，采用Buchwald-Hartwig胺化法合成LY305。体外代谢实验使用人肝微粒体（HLM）和S9部分进行，以便研究i期和ii期生物转化。采用液相色谱-高分辨率串联质谱法对LY305及其代谢产物进行检测和分离。结果共检测到18种代谢物，其中9种为i相代谢物，另外9种为ii相偶联物。代谢反应为：羟基化、脱氢、氧化、氧化和羟基化、o -葡萄糖醛酸化、羟基化和后续葡萄糖醛酸化、双羟基化和后续葡萄糖醛酸化。结论成功合成了经皮SARM LY305，并进行了体外代谢研究，获得了色谱和质谱数据，为完善全面的反兴奋剂检测提供了支持。据我们所知，没有发表的实验数据报告LY305的体外代谢谱，这种物质可能需要进一步（预）临床评估。

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引用次数: 0

Zinc/Silver-Based Hydrogen Sulfide Trapping as an Alternative to Cadmium for Sulfur Stable Isotope Analysis 锌/银基硫化氢捕获作为镉的替代品用于硫稳定同位素分析

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-08-14 DOI: 10.1002/rcm.10120

David Ure, Karlynne R. Dominato, Meagan L. Beaton, Scott O. C. Mundle

Rationale

Hydrogen sulfide (H₂S) sulfur stable isotope ratio (δ³⁴S) analyses use cadmium (Cd) or zinc (Zn) solutions; however, Cd is toxic, and Zn does not display an obvious change in color at low molar H₂S inputs. This study (i) developed a non-toxic, colorimetric mixed zinc/silver (Zn/Ag)-based method and (ii) evaluated the minimum H₂S input required for analysis.

Methods

Gaseous H₂S was trapped using the Cd- and Zn/Ag-based methods and converted to solid silver sulfide (Ag₂S). δ³⁴S stable isotope analysis was completed using elemental analysis–isotope ratio mass spectrometry (EA-IRMS).

Results

H₂S, from 8.4 × 10⁻⁶ mol up to 1.0 × 10⁻⁴ mol, was trapped using the Cd- and Zn/Ag-based methods. The Zn/Ag-based method retained stable δ³⁴S values at lower molar inputs than the Cd-based method. Environmental sampling had a usable detection range of approximately 4.1 × 10⁻⁴–7.8 × 10⁻¹ mol/m³ (~10–19 000 ppm). The mean δ³⁴S difference between methods was −0.1‰, ranging from −3.0‰ to +3.1‰, with 23 out of 27 samples falling within ±1.2‰.

Conclusions

The Zn/Ag-based method produced δ³⁴S values comparable with the Cd-based method and maintained accuracy with lower molar inputs of H₂S. The minimum molar input for analysis is ~8.4 × 10⁻⁶ mol. The Zn/Ag method is safer for human health and the environment, and a suitable alternative to Cd for H₂S trapping and subsequent δ³⁴S determination by IRMS.

硫化氢（H2S）硫稳定同位素比（δ34S）分析使用镉（Cd）或锌（Zn）溶液；然而，Cd是有毒的，而Zn在低摩尔H2S输入下没有明显的颜色变化。本研究(1)开发了一种无毒、比色的混合锌/银（Zn/Ag）方法；(2)评估了分析所需的最小H2S输入。方法采用Cd基和Zn/ ag基方法捕获气态H2S，转化为固体硫化银（Ag2S）。δ34S稳定同位素分析采用元素分析-同位素比值质谱法（EA-IRMS）完成。结果采用Cd和Zn/ ag两种方法捕获了8.4 ~ 1.0 × 10−6 mol的硫化氢。与基于cd的方法相比，基于Zn/ ag的方法在较低的摩尔输入下保持稳定的δ34S值。环境采样的可用检测范围约为4.1 × 10−4-7.8 × 10−1 mol/m3 （~10 - 19000 ppm）。各方法的平均δ34S差值为−0.1‰，范围为−3.0‰~ +3.1‰，27个样本中有23个样本的δ34S差值在±1.2‰以内。结论Zn/ ag基方法的δ34S值与cd基方法相当，且在较低H2S摩尔输入量下仍能保持准确性。用于分析的最小摩尔输入为~8.4 × 10−6 mol。Zn/Ag法对人体健康和环境更安全，适合替代Cd法进行H2S捕获和随后的IRMS测定δ34S。

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引用次数: 0

Simulation and Development of an Ion Funnel for Miniature Mass Spectrometers 微型质谱仪离子漏斗的模拟与研制

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-08-13 DOI: 10.1002/rcm.10123

Zhongyao Zhang, Baoqiang Li, Lin Zhang, Cuiping Li

Rationale

Miniature mass spectrometers are increasingly used in portable and on-site analysis due to their compact size and light weight. However, miniaturization, higher operating gas pressure, and complex airflow movement have significantly reduced ion transmission efficiency. Conventional ion guide devices are unsuitable under these conditions, severely limiting the performance and practicality of such spectrometers. Thus, developing a novel ion guiding device to improve ion transmission and detection performance is urgently needed.

Methods

We designed a miniature ion funnel with isobaric, tapered, and widened exit electrodes. Using SIMION and AXSIM software, we systematically studied the impact of radio frequency (RF) and direct current (DC) voltages, radial displacement, ion kinetic energy, mass-to-charge ratios, and gas pressure on ion transmission. Additionally, computational fluid dynamics simulations with Virtual Device software visualized temperature, velocity, and pressure fields in subvacuum regions.

Results

Based on simulation results, we precisely manufactured the ion funnel, measuring 6.2 × 3.4 × 3.2 cm³ and weighing 51.4 g. Tested on a continuous atmospheric pressure interface (CAPI) miniature mass spectrometer at 5.34 Torr, the new ion funnel showed a 44.3% increase in intensity compared to the previous version, validating its effectiveness.

Conclusions

The proposed ion funnel enables efficient ion focusing and transfer, overcoming miniaturization-related limitations. It enhances the detection performance of miniature mass spectrometers, offering a practical solution with important implications for the development of portable analytical instruments.

原理：微型质谱仪由于体积小、重量轻，越来越多地用于便携式和现场分析。然而，小型化、更高的操作气体压力和复杂的气流运动显著降低了离子传输效率。在这些条件下，传统的离子引导装置不适合，严重限制了这种光谱仪的性能和实用性。因此，迫切需要开发一种新型离子引导装置来提高离子传输和检测性能。方法采用等压、锥形、加宽出口电极设计微型离子漏斗。利用SIMION和AXSIM软件，系统研究了射频（RF）和直流（DC）电压、径向位移、离子动能、质荷比和气体压力对离子传输的影响。此外，利用Virtual Device软件进行的计算流体动力学模拟显示了亚真空区域的温度、速度和压力场。结果根据模拟结果，我们精确制造出尺寸为6.2 × 3.4 × 3.2 cm3、重量为51.4 g的离子漏斗。在5.34 Torr的连续大气压界面（CAPI）微型质谱仪上测试，新离子漏斗的强度比以前的版本提高了44.3%，验证了其有效性。结论所提出的离子漏斗能够实现高效的离子聚焦和转移，克服了小型化的限制。它提高了微型质谱仪的检测性能，为便携式分析仪器的发展提供了一种实用的解决方案。

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引用次数: 0

Acoustically Levitated Sample Introduction for GC–MS: A Novel Contactless Approach to Direct Volatile Analysis 气相色谱-质谱的声悬浮样品介绍：一种新的无接触直接挥发分析方法

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-08-12 DOI: 10.1002/rcm.10122

Erhan Akkaya, Ikbal Koyuncu

Conventional GC–MS sample introduction methods often involve physical contact, increasing contamination risk and analyte degradation, especially in sensitive matrices. This study introduces a novel, contactless interface using standing-wave acoustic levitation to suspend analytes in mid-air prior to GC–MS analysis. A 28 kHz ultrasonic transducer, powered by a high-voltage amplifier, generates stable levitation nodes inside a custom chamber, enabling droplets and solid particles to remain airborne during volatilization. Volatile analytes are transferred via heated gas mixture directly into the GC inlet. Acetone droplets yielded strong, reproducible m/z 58 ion signals, and real samples like cucumber (Cucumis sativus) skin demonstrated broader applicability. Helium–nitrogen gas mixture was optimized for both levitation stability and ionization efficiency. The system minimized surface contact, preserved sample morphology, and reduced cross-contamination risks. This platform establishes acoustic levitation as a viable sample delivery strategy for GC–MS, offering enhanced cleanliness, reduced sample loss, and novel handling of delicate or trace-level materials. It opens new directions for automation and integration in analytical workflows.

传统的GC-MS样品导入方法通常涉及物理接触，增加污染风险和分析物降解，特别是在敏感基质中。本研究引入了一种新颖的非接触式界面，使用驻波声悬浮将分析物悬浮在半空中，然后进行GC-MS分析。一个28千赫的超声波换能器，由一个高压放大器供电，在一个定制的腔室内产生稳定的悬浮节点，使液滴和固体颗粒在挥发过程中保持在空气中。挥发性分析物通过加热的气体混合物直接进入GC入口。丙酮液滴产生了强的、可重复的m/z 58离子信号，像黄瓜（Cucumis sativus）皮肤这样的真实样品显示了更广泛的适用性。对氦氮混合物的悬浮稳定性和电离效率进行了优化。该系统最大限度地减少了表面接触，保留了样品的形态，并降低了交叉污染的风险。该平台将声波悬浮作为气相色谱-质谱的一种可行的样品递送策略，提供更高的清洁度，减少样品损失，以及对微妙或痕量材料的新颖处理。它为分析工作流程的自动化和集成开辟了新的方向。

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引用次数: 0