Rapid Communications in Mass Spectrometry最新文献_第5页

Ultratrace Determination of Cd (II) in Water, Salt, Environmental, Alloy, and Biological Samples by Liquid–Liquid Extraction Followed by Inductively Coupled Plasma Mass Spectrometry Technique 液液萃取-电感耦合等离子体质谱法超痕量测定水、盐、环境、合金和生物样品中的Cd （II）

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-09-30 DOI: 10.1002/rcm.10150

Chandramauly Sharma, Kuldeep Sharma, Bignesh Thakur, Aniket Dixit

Rationale

Cadmium is a highly toxic heavy metal associated with severe environmental and health risks, making its precise quantification in complex matrices critical. Inductively coupled plasma mass spectrometry (ICP–MS) is one of the most powerful tools for trace metal analysis due to its exceptional sensitivity, selectivity, and multielement capability. However, accurate detection often requires effective preconcentration and matrix elimination strategies.

Method

A liquid–liquid extraction procedure was developed using N,N′-diphenyl sebacoyl dihydroxamic acid (DPSDHA) as a selective complexing ligand for cadmium. The Cd–DPSDHA binary complex formed at pH 9.5 was extracted into dichloromethane, effectively preconcentrating cadmium and minimizing matrix interference prior to ICP–MS measurement. The optimized conditions ensured maximum recovery and stability of the analyte, thereby improving detection limits and analytical precision.

Result

Coupling the DPSDHA extraction with ICP–MS enabled trace-level determination of cadmium with excellent sensitivity and reproducibility. The method exhibited a wide linear dynamic range, low detection limits, and strong resistance to matrix interferences, ensuring accurate quantification in complex samples. Application to water, alloy, environmental, and biological samples yielded accurate results, which were consistent with certified reference values.

Conclusions

The combination of selective DPSDHA-based extraction with ICP–MS provides a robust, highly sensitive approach for cadmium determination in diverse sample matrices. This methodology enhances detection accuracy by reducing matrix effects, making it well-suited for environmental monitoring, industrial quality control, and biological studies where trace-level cadmium analysis is essential.

镉是一种高毒性重金属，具有严重的环境和健康风险，因此在复杂基质中对其进行精确定量至关重要。电感耦合等离子体质谱（ICP-MS）由于其卓越的灵敏度、选择性和多元素能力，是痕量金属分析最强大的工具之一。然而，准确的检测往往需要有效的预富集和基质消除策略。方法以N，N′-二苯基皮脂酰二羟肟酸（DPSDHA）作为镉的选择性络合配体，建立了液液萃取工艺。在pH 9.5下形成的Cd-DPSDHA二元配合物被提取到二氯甲烷中，有效地富集了镉，并在ICP-MS测量之前最大限度地减少了基质干扰。优化的条件确保了分析物的最大回收率和稳定性，从而提高了检出限和分析精度。结果DPSDHA萃取与ICP-MS耦合，可测定痕量镉，灵敏度高，重现性好。该方法线性动态范围宽，检出限低，抗基质干扰能力强，可保证复杂样品的准确定量。应用于水、合金、环境和生物样品，结果准确，与认证参考值一致。结论基于选择性dpsdha的萃取与ICP-MS相结合，为不同样品基质中镉的测定提供了一种可靠、高灵敏度的方法。该方法通过减少基质效应来提高检测精度，使其非常适合环境监测，工业质量控制和痕量镉分析必不可少的生物研究。

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引用次数: 0

Nanostructure-Dependent Signal Intensity in Through-Hole Porous Alumina Membranes for Mass Spectrometry Imaging 纳米结构依赖的信号强度在多孔氧化铝膜质谱成像

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-09-30 DOI: 10.1002/rcm.10149

Masahiro Kotani, Takashi Yanagishita

Rationale

Matrix-assisted laser desorption/ionization (MALDI) is a widely used analytical technique for measuring high-molecular-weight compounds such as proteins. However, in the low-molecular-weight region, interference peaks derived from the matrix occur. Surface-assisted laser desorption/ionization (SALDI), which is matrix-free, does not generate background noise in the low-molecular-weight region and has the advantages of simple sample preparation and reproducibility. We previously developed an ionization method using an anodic porous alumina membrane (APAM) as a SALDI substrate. In this study, we examined the effects of the surface nanostructural properties of APAMs, such as hole diameter and pitch, on the signal intensity in mass spectrometry (MS) imaging.

Methods

APAMs were fabricated using electrolytes of oxalic, malonic, and malic acids and were evaluated by MS using droplet samples and MS imaging. Droplet samples were applied to the back surface of the APAMs. MS imaging was conducted using 20-μm-thick mouse brain sections to compare the signal-to-noise ratio (SNR) of each APAM.

Results

APAMs were fabricated with hole diameters (D_h) of 24–419 nm, interhole distances (D_int) of 100–625 nm, and open area ratios (OAR) of 5%–46%. From MS and MS imaging results, signal intensity at the same OAR increased in the order of D_int = 100, 625, and 270 nm, and the condition D_h/D_int = 131/270 nm provided the highest SNR. In addition, APAMs with a D_h of less than 84 nm and an OAR lower than 10% exhibited lower signal intensities.

Conclusions

We fabricated APAMs under various conditions and identified the processing conditions that provided the highest SNR of SALDI imaging. SALDI imaging using the APAMs fabricated under these high SNR conditions is expected to be applicable in various fields such as materials science and metabolomics, as it does not generate interference peaks in the low-molecular-weight region.

基质辅助激光解吸/电离（MALDI）是一种广泛应用于测量高分子量化合物（如蛋白质）的分析技术。然而，在低分子量区域，会出现来自基质的干涉峰。表面辅助激光解吸/电离（SALDI）是一种无基体的激光解吸/电离技术，在低分子量区域不会产生背景噪声，具有样品制备简单、重复性好等优点。我们之前开发了一种使用阳极多孔氧化铝膜（APAM）作为SALDI衬底的电离方法。在这项研究中，我们研究了APAMs表面纳米结构特性，如孔直径和节距，对质谱成像信号强度的影响。方法以草酸、丙二酸和苹果酸为电解液制备APAMs，采用液滴样品和质谱成像对APAMs进行鉴定。液滴样品被施加到apam的背面。采用20 μm厚的小鼠脑切片进行MS成像，比较各APAM的信噪比。结果制备的APAMs孔直径（Dh）为24 ~ 419 nm，孔间距（Dint）为100 ~ 625 nm，开孔率（OAR）为5% ~ 46%。从MS和MS成像结果来看，同一声腔处的信号强度按Dint = 100、625、270 nm依次增大，其中Dh/Dint = 131/270 nm时信噪比最高。此外，当偏h小于84 nm，桨距小于10%时，apam的信号强度较低。结论制备了不同条件下的apam，并确定了SALDI成像信噪比最高的处理条件。使用在这些高信噪比条件下制造的apam进行SALDI成像，预计将适用于材料科学和代谢组学等各个领域，因为它不会在低分子量区域产生干扰峰。

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引用次数: 0

Extreme Rainfall Contribution and Isotopic Excursion of Tropical Storm Alberto in Northeastern Mexico 墨西哥东北部热带风暴阿尔贝托的极端降雨贡献和同位素偏移

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-09-30 DOI: 10.1002/rcm.10146

Odalys J. Ibarra-Alejos, Ricardo Sánchez-Murillo, Rene Ventura-Houle, Oscar Guevara Mansilla, Tomas Peña-Alonso, Bárbara A. Macías-Hernández, Luis González-Hita, Miguel A. Mejía-González

Rationale

Tropical cyclones are critical extreme rainfall events that can temporarily mitigate drought impacts in semiarid regions. Despite the well-known North Atlantic hurricane season, the propagation of isotopically distinct rainfall pulses across semiarid landscapes of Mesoamerica is largely unknown.

Methods

In June 2024, tropical storm (TS) Alberto made landfall in northeastern Mexico. This study evaluates TS Alberto's monthly and annual rainfall contribution across Tamaulipas and Nuevo León and the isotopic excursions (δ¹⁸O and d-excess) in precipitation and surface water. Rainfall data from 86 stations and high-frequency isotope samples from Ciudad Victoria, Tampico, Chetumal, and the San Marcos River were analyzed.

Results

Results show that TS Alberto produced unprecedented rainfall, ranging from 0.22 to 11.41 times the 10-year June average, and up to 123% of the annual average in orographically influenced regions (i.e., variation is based on 86 locations across the region). Reservoir data highlight a rapid hydrological recovery, with dam levels in Tamaulipas and Nuevo León increasing significantly within weeks. Rainfall isotopic composition exhibited a broad spectrum (δ¹⁸O: −15.82‰ to −2.80‰), reflecting varying moisture sources, convective activity, and orographic effects. TS Alberto reproduced nearly the entire annual δ¹⁸O variability within a few hours, underscoring the strong isotopic imprint of extreme events. During TS Alberto's landfall and passage, an inverse trend between δ¹⁸O and precipitation amount was observed.

Conclusions

The storm's isotopic signature was traced into surface waters, providing evidence of rapid river response and potentially for aquifer recharge. These findings emphasize the dual hydrological and isotopic role of TCs in modulating water scarcity and improving hydroclimate reconstructions in drought-prone landscapes.

基本原理热带气旋是可以暂时缓解半干旱地区干旱影响的关键极端降雨事件。尽管众所周知的北大西洋飓风季节，但在中美洲半干旱地区，同位素不同的降雨脉冲的传播在很大程度上是未知的。2024年6月，热带风暴阿尔贝托在墨西哥东北部登陆。本研究评估了TS Alberto在塔毛利帕斯州和新evo州的月和年降雨量贡献León以及降水和地表水中的同位素偏移（δ18O和d-excess）。分析了来自86个站点的降雨数据和来自维多利亚城、坦皮科、切图马尔和圣马科斯河的高频同位素样本。结果表明，TS阿尔贝托产生了前所未有的降雨，其降雨量范围为10年6月平均值的0.22 - 11.41倍，在地形影响地区（即基于该地区86个地点的变化），降雨量高达年平均值的123%。水库数据强调水文恢复迅速，塔毛利帕斯州和新evo León的大坝水位在几周内显著上升。降水同位素组成具有广谱特征（δ18O:−15.82‰~−2.80‰），反映了不同的水汽来源、对流活动和地形效应。TS Alberto在几小时内重现了几乎整个年度δ18O变化，强调了极端事件的强烈同位素印记。在TS Alberto登陆和通过过程中，δ18O与降水量呈负相关。风暴的同位素特征被追踪到地表水中，为河流的快速反应和潜在的含水层补给提供了证据。这些发现强调了碳水化合物在干旱易发地区调节水资源短缺和改善水文气候重建中的双重水文和同位素作用。

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引用次数: 0

Mapping the Metabolic Fate of Suzetrigine in Equine and Camel Models: A Step Toward Reliable Antidoping Detection 绘制苏泽三嗪在马和骆驼模型中的代谢命运：迈向可靠的反兴奋剂检测的一步

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-09-30 DOI: 10.1002/rcm.10147

Shino Ann Koshy, Meleparappil Muhammed Ajeebsanu, Abdul Khader Karakka Kal, Michael Benedict Subhahar, Tajudheen K. Karatt, Moses Philip

Rationale

Effective pain management remains a persistent challenge, with opioids limited by tolerance, dependence, respiratory depression, and misuse. This has created demand for safer, nonaddictive alternatives. Suzetrigine (VX-548, Journavx) is a novel analgesic with promising efficacy, but its potential misuse in competitive racing requires investigation. Limited information is available on its metabolism and detection, emphasizing the need for metabolic characterization to aid antidoping strategies.

Methods

In vitro metabolism of suzetrigine was evaluated using equine liver microsomes and homogenized camel liver. Metabolic profiling was carried out using high-resolution LC–HRMS. Fragmentation analysis was performed to assign metabolite structures and characterize biotransformation pathways.

Results

Seven phase I metabolites (M1–M7) were identified, primarily via hydroxylation, methylation, demethylation, detrifluoromethylation, and cleavage of the pyridine-2-carboxamide moiety. One phase II metabolite (M8), formed by sulfation of the demethylated metabolite M5, was detected exclusively with camel liver. Metabolite structures were tentatively assigned based on mass fragmentation data, which showed characteristic neutral losses and diagnostic ions. Comparative analysis revealed that both species shared common phase I pathways, but camel liver demonstrated additional conjugation capacity.

Conclusion

This study provides the first comprehensive characterization of suzetrigine metabolism in equine and camel liver systems. The results underscore metabolic variations, propose a biotransformation pathway, and offer crucial insights to support the development of antidoping detection strategies.

有效的疼痛管理仍然是一个持续的挑战，阿片类药物受到耐受性，依赖性，呼吸抑制和滥用的限制。这就产生了对更安全、不会上瘾的替代品的需求。suzetriine （VX-548, Journavx）是一种具有良好疗效的新型镇痛药，但其在竞技比赛中的潜在滥用还有待研究。关于其代谢和检测的信息有限，强调需要代谢表征来帮助反兴奋剂策略。方法采用马肝微粒体和匀浆骆驼肝，对苏三嗪体外代谢进行研究。代谢谱分析采用高分辨率LC-HRMS进行。碎片化分析用于分配代谢物结构和表征生物转化途径。结果通过羟基化、甲基化、去甲基化、去三氟甲基化和吡啶-2-羧酰胺片段的裂解，共鉴定出7个I相代谢物（M1-M7）。一种II期代谢物（M8），由去甲基代谢物M5的磺化形成，仅在骆驼肝脏中检测到。代谢物结构暂定基于质量碎片数据，这显示了典型的中性损失和诊断离子。比较分析表明，这两个物种具有共同的I期通路，但骆驼肝脏表现出额外的偶联能力。结论本研究首次全面表征了马和骆驼肝脏系统中苏三氨酸的代谢。研究结果强调了代谢变化，提出了生物转化途径，并为支持反兴奋剂检测策略的发展提供了重要见解。

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引用次数: 0

Transcriptomic and Metabolomic Mechanism of Ibuprofen, Chondroitin Sulfate, and Vitamins With Minerals Tablets (21) for Kashin–Beck Disease Treatment 布洛芬、硫酸软骨素和矿物质维生素片治疗大骨节病的转录组学和代谢机制（21）

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-09-29 DOI: 10.1002/rcm.10130

Jinfeng Wen, Xingxing Deng, Zhengjun Yang, Hui Niu, Qian Zhang, Yijun Zhao, Gaowa Naren, Huan Liu, Feng Zhang, Xiaodong Yang, Cuiyan Wu

Background

Kashin–Beck disease (KBD) is an osteoarthropathy with no specific drug treatment. This study seeks to uncover the molecular mechanisms of ibuprofen, chondroitin sulfate, and vitamins with minerals tablets (21) in treating KBD.

Methods

Integrated transcriptomic and metabolomic analyses were performed on peripheral blood samples collected from four KBD patients before and 1 month after treatment. Differential gene expression was assessed using the DESeq package, while differential metabolites were identified through univariate and multivariate statistical analyses.

Results

After treatment, 5671 differential genes (|log₂FC| ≥ 1, q < 0.05) were identified, with 4954 upregulated and 717 downregulated. Enriched pathways included PI3K-Akt, MAPK, ECM-receptor interaction, Rap1, and Ras signaling. Untargeted metabolomics analyses revealed five differentially expressed metabolites (VIP ≥ 1, |log₂FC| > 0.58, p < 0.05): L-glutamine, 2-methylpropan-2-amine, epsilon-caprolactam, phosphocholine, and 1-palmitoyl-2-linoleoyl-sn-glycero-3-phosphocholine. Metabolite enrichment analysis suggested alterations in amino acid and fatty acid metabolism. Integrated analysis revealed key pathways such as alanine, aspartate, and glutamate metabolism and arginine biosynthesis.

Conclusions

The combination of ibuprofen, chondroitin sulfate, and vitamins with minerals tablets (21) may alleviate KBD through modulation of key genes (GDNF, BDNF, CCL2, VEGFA, and PPARG) and glutamine-related metabolic pathways.

背景：大骨节病（KBD）是一种无特异性药物治疗的骨关节病。本研究旨在揭示布洛芬、硫酸软骨素和矿物质维生素片治疗大骨节的分子机制（21）。方法：对4例大骨节病患者治疗前和治疗后1个月的外周血样本进行转录组学和代谢组学综合分析。使用DESeq软件包评估差异基因表达，通过单变量和多变量统计分析鉴定差异代谢物。结果：治疗后发现5671个差异基因（|log2FC|≥1,q 2FC| > 0.58, p）。结论：布洛芬、硫酸软骨素、维生素矿物质片联合用药（21）可通过调节关键基因（GDNF、BDNF、CCL2、VEGFA、PPARG）及谷氨酰胺相关代谢途径缓解大骨节病。

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引用次数: 0

Direct Metabolic Profiling of Biofluids via Wimshurst Machine–Nanoelectrospray Ionization Mass Spectrometry 通过Wimshurst机器-纳米电喷雾电离质谱分析生物流体的直接代谢谱。

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-09-29 DOI: 10.1002/rcm.10142

Qiming Kang, Guangming Huang

Rationale

Direct metabolic analysis is crucial for understanding the mechanisms of various diseases. However, it is still difficult to perform direct metabolic analysis of native biofluids for many biological sample types because conventional workflows often necessitate extensive sample pretreatment to mitigate matrix interference from high salt concentrations.

Methods

In this study, we developed a novel approach using a Wimshurst Machine–nanoelectrospray ionization (WM-nanoESI) system for direct metabolic analysis of native biofluids. This device achieves direct metabolic analysis due to its sampling method (injecting biofluid directly into nanoESI emitters with an orifice diameter of approximately 10 μm) and the adaptive electricity provided by the Wimshurst machine (preventing tip clogging and extending duration time).

Results

This method enables qualitative analysis of drugs and metabolites, prevents tip clogging when analyzing PBS and serum, and extends the duration time by approximately 15-fold longer than traditional DC nanoESI does. HeLa and MCF-7 cells were distinguished according to their metabolic profiles.

Conclusions

Our results indicate that the WM-nanoESI will offer significant advancements for real-time metabolic monitoring, boost disease understanding, and therapeutic monitoring.

原理：直接代谢分析对于理解各种疾病的机制至关重要。然而，对许多生物样品类型进行天然生物流体的直接代谢分析仍然很困难，因为传统的工作流程通常需要大量的样品预处理，以减轻高盐浓度对基质的干扰。方法：在这项研究中，我们开发了一种新的方法，使用Wimshurst机器-纳米电喷雾电离（WM-nanoESI）系统对天然生物体液进行直接代谢分析。由于其采样方法（将生物流体直接注入直径约10 μm的纳米esi发射器中）和Wimshurst机器提供的自适应电（防止尖端堵塞和延长持续时间），该设备实现了直接代谢分析。结果：该方法可以对药物和代谢物进行定性分析，在分析PBS和血清时防止针尖堵塞，持续时间比传统的直流纳米esi延长约15倍。根据其代谢谱来区分HeLa和MCF-7细胞。结论：我们的研究结果表明，WM-nanoESI将在实时代谢监测、促进疾病理解和治疗监测方面取得重大进展。

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引用次数: 0

A Novel Conjugated Octupole–Quadrupole Ion Guide Achieving High Transmission 一种新型高传输共轭八极-四极离子波导

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-09-26 DOI: 10.1002/rcm.10136

Masuyuki Sugiyama, Hideki Hasegawa, Yuichiro Hashimoto

Rationale

Ion transmission efficiency from the atmospheric pressure ion source to the vacuum is critical for the sensitivity of mass spectrometers. In this study, we developed a novel conjugated octupole–quadrupole ion guide—the 8–4 pole ion guide—that achieves high transmission efficiency.

Methods

The dependence of signal intensity on parameters, including DC voltages, RF voltage applied to the 8–4 pole ion guide, and pressure within the ion guide, was measured. The transmission efficiency of the 8–4 pole ion guide was estimated from the ion current introduced into the ion guide and passing through the aperture downstream of the guide. The sensitivity of the mass spectrometer equipped with the 8–4 pole ion guide was evaluated using testosterone. Potential calculations and ion trajectory simulations were employed to better understand ion behavior within the 8–4 pole ion guide.

Results

The dependence of signal intensity on pressure within the 8–4 pole ion guide suggests that the device achieves high ion transmission in the pressure range of 100–200 Pa. The ion current introduced into the 8–4 pole ion guide was 1.8 nA, while the ion current passing through the downstream aperture was 1.0 nA, resulting in a transmission efficiency of 56%. The mass spectrometer with the 8–4 pole ion guide achieved a coefficient of variation of 2.9% for 1 pg/mL testosterone. The lower limit of detection for testosterone was 0.12 pg/mL.

Conclusions

We successfully developed a novel 8–4 pole ion guide. The high transmission efficiency, demonstrated by ion current measurements, and the enhanced sensitivity of the mass spectrometer equipped with this ion guide indicate that it can maintain high transmission efficiency even under a high inlet gas flow of 5 L/min.

从大气压离子源到真空的离子传输效率对质谱仪的灵敏度至关重要。在本研究中，我们开发了一种新型的共轭八极-四极离子波导- 8-4极离子波导，它具有很高的传输效率。方法测量信号强度与直流电压、8-4极离子波导射频电压、离子波导内压力等参数的关系。通过引入离子波导并通过离子波导下游孔径的离子流估算了8-4极离子波导的传输效率。用睾酮评价配备8-4极离子向导的质谱仪的灵敏度。利用电位计算和离子轨迹模拟更好地理解了8-4极离子波导中的离子行为。结果8-4极离子波导内的信号强度随压力的变化表明，该器件在100-200 Pa的压力范围内实现了高离子传输。引入8-4极离子波导的离子电流为1.8 nA，通过下游孔径的离子电流为1.0 nA，传输效率为56%。采用8-4极离子导向的质谱计对1 pg/mL睾酮的变异系数为2.9%。睾酮的检测下限为0.12 pg/mL。结论我们成功研制了一种新型的8-4极离子波导。离子电流测量结果表明，该离子波导具有较高的传输效率，且安装该离子波导的质谱计灵敏度提高，表明即使在高入口气体流量为5 L/min的情况下，该离子波导也能保持较高的传输效率。

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引用次数: 0

Untargeted Metabolomics Analysis Combined With Network Pharmacology Reveals Differences in Chemical Profiles and Activities of Different Processed Products of Clematis chinensis Osbeck 结合网络药理学的非靶向代谢组学分析揭示了中国铁线莲不同加工产品的化学特征和活性差异

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-09-25 DOI: 10.1002/rcm.10143

Jianlin Ke, Lei Wang, Lili Huang, Chongchong Li, Jingjing Yang, Chao Zhang

Rationale

Clematis chinensis Osbeck (WLX), an herbal medicine, has been used to treat diseases for thousand years. In clinic, WLX presents four forms, including unprocessed WLX (SZ), WLX mixed with yellow wine (JB), WLX soaked in yellow wine (JJ), and WLX stir-fried with yellow wine (JC). However, few studies have focused on revealing differences in its composition and activity.

Methods

In this study, metabolomics was used to screen featured metabolites of WLX and its processed products. Subsequently, network pharmacology was applied to reveal the differences in their activity.

Results

The results showed that a total of 310 metabolites were identified, and 11 featured metabolites were selected, such as tracheloside, astilbin, and genistein. Network pharmacology analysis suggested that SZ samples mainly exert its specific therapeutic effects by regulating pain pathways, including glutamatergic synapse, spinocerebellar ataxia, and retrograde endocannabinoid signaling. JB, JJ, and JC groups predominantly exert their effects through pathways, including calcium signaling pathway, estrogen signaling pathway, and cAMP signaling pathway, thereby inhibiting the development of inflammatory and pain transmission.

Conclusion

This study will provide a theoretical basis for clinical application of WLX and its processed products and offer a reference for their quality control.

中国铁线莲（Clematis chinensis Osbeck， WLX）是一种草药，几千年来一直被用来治疗疾病。临床上，黄芪有四种形态，分别为未加工的黄芪（SZ）、黄酒混合的黄芪（JB）、黄酒浸泡的黄芪（JJ）、黄酒炒的黄芪（JC）。然而，很少有研究关注于揭示其组成和活性的差异。方法本研究采用代谢组学方法筛选枸杞及其加工产品的特征代谢物。随后，应用网络药理学来揭示它们的活性差异。结果共鉴定出310种代谢物，筛选出11种具有代表性的代谢物，如风草苷、astilbin、染料木素等。网络药理学分析表明，SZ样品主要通过调节谷氨酸能突触、脊髓小脑共济失调、逆行内源性大麻素信号通路等疼痛通路发挥其特异性治疗作用。JB、JJ和JC组主要通过钙信号通路、雌激素信号通路和cAMP信号通路发挥作用，从而抑制炎症和疼痛传递的发生。结论本研究将为枸杞及其炮制品的临床应用提供理论依据，并为其质量控制提供参考。

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引用次数: 0

Stable Carbon Isotope Analysis of Perfluorooctanoic Acid (PFOA) by Microflow-High Pressure Liquid Chromatography-Orbitrap Mass Spectrometry 微流-高压液相色谱-轨道阱质谱法分析全氟辛酸（PFOA）的稳定碳同位素

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-09-23 DOI: 10.1002/rcm.10139

Paul K. Wojtal, Brett Davidheiser-Kroll, Chad S. Lane, Ralph N. Mead

Rationale

As contamination of perfluoroalkyl and polyfluoroalkyl substances (PFAS) in the environment becomes better understood, it is increasingly important to develop forensic tools capable of tracing contamination to emission sources. Isotopic methods have been previously inaccessible for PFAS due to limitations of the instrumentation, but high-pressure liquid chromatography (HPLC) coupled to Orbitrap mass spectrometry (Orbitrap MS) through electrospray ionization (ESI) allows measurement of the isotopic composition of individual PFAS compounds, such as perfluorooctanoic acid (PFOA).

Methods

Six separate supplier-procured powders of PFOA were analyzed for their δ¹³C isotopic composition by microflow-HPLC-ESI-Orbitrap MS.

Results

The method presented replicated, within error, the δ¹³C values measured using an elemental analyzer-isotope ratio mass spectrometer (EA-IRMS) for the six different supplier-procured PFOA powders. The offset from the EA-IRMS values for repeated analysis was between 0.2‰ and 1.1‰ and the error was between 0.8‰ and 1.5‰. Our Orbitrap-MS method requires approximately 0.04% of the material required to make an EA-IRMS measurement.

Conclusions

We developed a method capable of measuring the carbon isotopic composition of PFOA, using HPLC-Orbitrap MS, with high precision and accuracy. This will allow future research to expand analytical capabilities for additional isotopologues of PFOA and other PFAS compounds.

随着人们对环境中全氟烷基和多氟烷基物质（PFAS）的污染有了更好的了解，开发能够追踪污染到排放源的法医工具变得越来越重要。由于仪器的限制，以前无法使用同位素方法检测PFAS，但高压液相色谱法（HPLC）与Orbitrap质谱法（Orbitrap MS）通过电喷雾电离（ESI）可以测量单个PFAS化合物的同位素组成，如全氟辛酸（PFOA）。方法采用microflow-HPLC-ESI-Orbitrap质谱法对6种不同供应商采购的PFOA粉末的δ13C同位素组成进行了分析。结果该方法与元素分析仪-同位素比质谱仪（EA-IRMS）测量的6种不同供应商采购的PFOA粉末的δ13C值在误差范围内完全相同。与重复分析EA-IRMS值的偏移量在0.2‰~ 1.1‰之间，误差在0.8‰~ 1.5‰之间。我们的Orbitrap-MS方法所需的材料约为EA-IRMS测量所需材料的0.04%。结论建立了HPLC-Orbitrap质谱法测定PFOA碳同位素组成的方法，具有较高的精密度和准确度。这将使未来的研究能够扩大对全氟辛酸和其他全氟辛酸化合物的其他同位素物的分析能力。

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引用次数: 0

From MS1 to Structure: A Van Krevelen–DBE–Aromaticity-Based Framework for Annotating Specialized Metabolites via High-Resolution Mass Spectrometry 从MS1到结构：一个基于Van krevelen - dbe芳香性的框架，通过高分辨率质谱法注释专门的代谢物

IF 1.7 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry

Pub Date : 2025-09-22 DOI: 10.1002/rcm.10145

Nerilson M. Lima, Luana A. Pereira, Lucas S. Tironi, Matheus P. G. do Carmo, Milbya L. Costa, Renato A. Oliveira, Salva Asghar, Vinicius Fortes da Silva

Rationale

Classifying specialized metabolites in untargeted metabolomics remains a major challenge, particularly when relying solely on high-resolution mass spectrometry (HRMS) data at the MS1 level. Traditional approaches using Van Krevelen diagrams often lack sufficient resolution to distinguish structurally similar metabolite classes.

Methods

We developed a chemoinformatic framework that combines Van Krevelen analysis (H/C vs. O/C) with double bond equivalent (DBE) calculations to refine metabolite class annotation at Level 3 of the Metabolomics Standards Initiative (MSI). Molecular formulas were retrieved from curated structure databases and natural product repositories, and DBE values were used to refine structural classification. A dataset of over 600 curated molecular formulas representing phenolics, alkaloids, and isoprenoids was analyzed to define class-specific patterns.

Results

The combined use of DBE and Van Krevelen plots enabled improved discrimination between overlapping metabolite classes, including flavonoids, phenolic acids, coumarins, and tannins. Our framework revealed structural trends associated with aromaticity and unsaturation that are not captured by conventional MS1-based tools. It outperforms existing Level 3 annotation strategies that rely on in silico MS/MS fragmentation or substructure matching. A case study using Eugenia jambolana fruit extract validated the method, revealing dominant classes such as flavonoids, phenolic acids, and tannins using only MS1 data.

Conclusions

This is the first scalable framework to annotate specialized metabolites from MS1 data alone using integrated elemental ratios and structural descriptors. It enhances the annotation confidence for untargeted metabolomics, especially in complex, undercharacterized plant matrices, without requiring MS2 fragmentation.

在非靶向代谢组学中对特定代谢物进行分类仍然是一个主要挑战，特别是当仅依赖MS1水平的高分辨率质谱（HRMS）数据时。使用Van Krevelen图的传统方法通常缺乏足够的分辨率来区分结构相似的代谢物类别。我们开发了一个化学信息学框架，将Van Krevelen分析（H/C vs. O/C）与双键当量（DBE）计算相结合，以完善代谢组学标准倡议（MSI）第3级的代谢物类别注释。分子式从精心策划的结构数据库和天然产物库中检索，并使用DBE值来细化结构分类。研究人员分析了600多个分子式的数据集，这些分子式代表了酚类、生物碱和类异戊二烯，以确定类特定的模式。结果DBE和Van Krevelen图的联合使用可以提高对重叠代谢物类别的区分，包括黄酮类、酚酸类、香豆素类和单宁类。我们的框架揭示了传统的基于ms1的工具无法捕捉到的与芳香性和不饱和性相关的结构趋势。它优于现有的依赖于计算机MS/MS碎片或子结构匹配的Level 3注释策略。一项使用白桦果提取物的案例研究验证了该方法，仅使用MS1数据就揭示了黄酮类、酚酸类和单宁类等主要类别。这是第一个可扩展的框架，可以单独使用综合元素比率和结构描述符从MS1数据中注释专门的代谢物。它提高了对非靶向代谢组学的注释可信度，特别是在复杂的、未充分表征的植物基质中，而不需要MS2片段化。

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引用次数: 0