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The ‘LSVEC problem’ for the Vienna Peedee belemnite carbon isotope-delta scale 维也纳皮迪贝壳岩碳同位素-δ尺度的 "LSVEC 问题"。
IF 1.8 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2024-06-24 DOI: 10.1002/rcm.9841
Philip J. H. Dunn, Federica Camin

Since 2016 there have been intense discussions within several established communities and networks regarding the consequences of the withdrawal of the LSVEC lithium carbonate reference material for carbon isotope-delta measurement calibration. These include the Isotope Ratio Working Group (IRWG) of the Consultative Committee for the Amount of Substance (CCQM, French: Comité Consultatif pour la Quantité de Matière) of the International Committee of Weights and Measures (CIPM, French: Comité International des Poids et Mesures); participants within the 2016, 2021 and 2024 Technical Meetings on International Atomic Energy Agency (IAEA) stable isotope ratio reference products; and the International Union of Pure and Applied Chemistry's Commission on Isotopic Abundances and Atomic Weights (IUPAC CIAAW) amongst others. The reasons for these intensive discussions relate to the privileged position that LSVEC has occupied for traceability of carbon isotope-delta measurements relative to Vienna Peedee belemnite (VPDB) and the potential implications of its withdrawal for all current and future measurements of carbon isotope-delta values. This perspective summarises the background information regarding the LSVEC material in the context of the VPDB carbon isotope-delta scale. The various proposals to address the LSVEC problem that have been discussed within those committees and networks are also presented. The information herein was used as a foundation for discussions at the 2024 IAEA Consultancy Meetings on the Development of IAEA Stable Isotope Reference Materials and Related Products and on the Definition and Realisation of the Isotopic Delta Scales for Light Elements (22–26 January 2024, Vienna, Austria). A summary of those 2024 meetings and associated outcomes can be found elsewhere.

自2016年以来,一些既有的社区和网络就撤消LSVEC碳酸锂参考材料用于碳同位素-Δ测量校准的后果展开了激烈的讨论。其中包括国际度量衡委员会(CIPM,法语:Comité Consultatif pour la Quantité de Matière)物质数量咨询委员会(CCQM,法语:Comité Consultatif pour la Quantité de Matière)同位素比值工作组(IRWG):国际计量委员会(CIPM,法语:Comité International des Poids et Mesures);国际原子能机构(IAEA)2016、2021 和 2024 年稳定同位素比值参考产品技术会议的与会者;以及国际理论化学和应用化学联合会同位素丰度和原子量委员会(IUPAC CIAAW)等。进行这些深入讨论的原因与 LSVEC 在溯源维也纳裴迪海泡石(VPDB)碳同位素-Δ测量方面所处的优越地位有关,也与撤销 LSVEC 对当前和未来所有碳同位素-Δ值测量的潜在影响有关。本视角总结了在 VPDB 碳同位素-δ尺度背景下 LSVEC 材料的背景信息。此外,还介绍了在这些委员会和网络中讨论的解决 LSVEC 问题的各种建议。本文中的信息被用作 2024 年国际原子能机构关于开发国际原子能机构稳定同位素参 考材料和相关产品以及关于定义和实现轻元素同位素三角标度的咨询会议(2024 年 1 月 22 日至 26 日,奥地利维也纳)讨论的基础。这些 2024 年会议及相关成果的摘要可在其他地方查阅。
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引用次数: 0
High-accuracy measurement of 36SF5+ signal using an ultrahigh-resolution isotope ratio mass spectrometer 使用超高分辨率同位素比质谱仪高精度测量 36SF5 + 信号。
IF 1.8 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2024-06-24 DOI: 10.1002/rcm.9845
Xiang Sun, Fengtai Tong, Yongbo Peng, Huiming Bao

Rationale

The Δ36S standard deviation measured in a conventional isotope ratio mass spectrometer such as MAT 253 is ca 0.1‰ to 0.3‰. At this precision, it is difficult to resolve the origin of non-mass-dependent sulfur isotope fractionation in tropospheric sulfate aerosol and in Martian meteorites or small deviations from the canonical mass-dependent fractionation laws. Interfering ions with m/z at 131 of 36SF5+ are suggested by the community as the cause of the poor precision, but the exact ion species has not been identified or confirmed.

Methods

Here we examined the potential interfering ions by using a Thermo Scientific ultrahigh-resolution isotope ratio mass spectrometer to measure SF6 working gas and SF6 gases converted from IAEA-S1/2/3 Ag2S reference materials.

Results

We found that there are two resolvable peaks to the right of the 36SF5+ peak when a new filament was installed, which are 186WF42+ followed by 12C3F5+. However, only the 12C3F5+ interference peak was observed after more than three days of filament use. 12C3F5+ is generated inside the instrument during the ionization process. Avoiding the interfering signals, we were able to achieve a Δ36S standard deviation of 0.046‰ (n = 8) for SF6 zero-enrichment and 0.069‰ (n = 8) for overall measurement start from silver sulfide IAEA-S1.

Conclusions

Aging the filament with SF6 gas can avoid the interference of 186WF42+. Minimizing the presence of carbon-bearing compounds and avoiding the interfering signals of 12C3F5+ from 36SF5+, we can improve Δ36S measurement accuracy and precision, which helps to open new territories for research using quadruple sulfur isotope composition.

理由:在传统的同位素比质谱仪(如 MAT 253)上测量到的Δ36S 标准偏差约为 0.1‰至 0.3‰。在这种精度下,很难确定对流层硫酸盐气溶胶和火星陨石中与质量无关的硫同位素分馏的起源,或与质量有关的典型分馏定律的微小偏差。方法:在此,我们使用 Thermo Scientific 超高分辨率同位素比质谱仪测量 SF6 工作气体和从 IAEA-S1/2/3 Ag2S 参考材料转换而来的 SF6 气体,研究了潜在的干扰离子:我们发现,安装新灯丝后,在 36SF5 + 峰右侧有两个可分辨的峰,即 186WF4 2+ 峰和 12C3F5 + 峰。然而,在使用灯丝超过三天后,只观察到 12C3F5 + 干扰峰。12C3F5 + 是在电离过程中在仪器内部产生的。在避免干扰信号的情况下,SF6 零富集的 Δ36S 标准偏差为 0.046‰(n = 8),从硫化银 IAEA-S1 开始的总体测量标准偏差为 0.069‰(n = 8):用 SF6 气体老化灯丝可以避免 186WF4 2+ 的干扰。尽量减少含碳化合物的存在,避免 36SF5 + 对 12C3F5 + 信号的干扰,可以提高 Δ36S 的测量精度和准确度,有助于为利用四重硫同位素组成的研究开辟新的领域。
{"title":"High-accuracy measurement of 36SF5+ signal using an ultrahigh-resolution isotope ratio mass spectrometer","authors":"Xiang Sun,&nbsp;Fengtai Tong,&nbsp;Yongbo Peng,&nbsp;Huiming Bao","doi":"10.1002/rcm.9845","DOIUrl":"10.1002/rcm.9845","url":null,"abstract":"<div>\u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>The Δ<sup>36</sup>S standard deviation measured in a conventional isotope ratio mass spectrometer such as MAT 253 is <i>ca</i> 0.1‰ to 0.3‰. At this precision, it is difficult to resolve the origin of non-mass-dependent sulfur isotope fractionation in tropospheric sulfate aerosol and in Martian meteorites or small deviations from the canonical mass-dependent fractionation laws. Interfering ions with <i>m</i>/<i>z</i> at 131 of <sup>36</sup>SF<sub>5</sub><sup>+</sup> are suggested by the community as the cause of the poor precision, but the exact ion species has not been identified or confirmed.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>Here we examined the potential interfering ions by using a Thermo Scientific ultrahigh-resolution isotope ratio mass spectrometer to measure SF<sub>6</sub> working gas and SF<sub>6</sub> gases converted from IAEA-S1/2/3 Ag<sub>2</sub>S reference materials.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>We found that there are two resolvable peaks to the right of the <sup>36</sup>SF<sub>5</sub><sup>+</sup> peak when a new filament was installed, which are <sup>186</sup>WF<sub>4</sub><sup>2+</sup> followed by <sup>12</sup>C<sub>3</sub>F<sub>5</sub><sup>+</sup>. However, only the <sup>12</sup>C<sub>3</sub>F<sub>5</sub><sup>+</sup> interference peak was observed after more than three days of filament use. <sup>12</sup>C<sub>3</sub>F<sub>5</sub><sup>+</sup> is generated inside the instrument during the ionization process. Avoiding the interfering signals, we were able to achieve a Δ<sup>36</sup>S standard deviation of 0.046‰ (<i>n</i> = 8) for SF<sub>6</sub> zero-enrichment and 0.069‰ (<i>n</i> = 8) for overall measurement start from silver sulfide IAEA-S1.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusions</h3>\u0000 \u0000 <p>Aging the filament with SF<sub>6</sub> gas can avoid the interference of <sup>186</sup>WF<sub>4</sub><sup>2+</sup>. Minimizing the presence of carbon-bearing compounds and avoiding the interfering signals of <sup>12</sup>C<sub>3</sub>F<sub>5</sub><sup>+</sup> from <sup>36</sup>SF<sub>5</sub><sup>+</sup>, we can improve Δ<sup>36</sup>S measurement accuracy and precision, which helps to open new territories for research using quadruple sulfur isotope composition.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"38 17","pages":""},"PeriodicalIF":1.8,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141454221","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
Analysis of mutation-originated gain-of-glycosylation using mass spectrometry-based N-glycoproteomics 利用基于质谱的 N-糖蛋白组学分析突变引发的糖基化增益。
IF 1.8 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2024-06-24 DOI: 10.1002/rcm.9838
Hailun Yang, Zhixin Tian

Rationale

A general N-glycoproteomics analysis pipeline has been established for characterization of mutation-related gain-of-glycosylation (GoG) at intact N-glycopeptide molecular level, generating comprehensive site and structure information of N-glycosylation.

Methods

This study focused on mutation-originated GoG using a mass spectrometry-based N-glycoproteomics analysis workflow. In brief, GoG intact N-glycopeptide databases were built, consisting of 2701 proteins (potential GoG N-glycosites and amino acids derived from MUTAGEN, VARIANT and VAR_SEQ in UniProt) and 6709 human N-glycans (≤50 sequence isomers per monosaccharide composition). We employed the site- and structure-specific N-glycoproteomics workflow utilizing intact N-glycopeptides search engine GPSeeker to identify GoG intact N-glycopeptides from parental breast cancer stem cells (MCF-7 CSCs) and adriamycin-resistant breast cancer stem cells (MCF-7/ADR CSCs).

Results

With the criteria of spectrum-level false discovery rate control of ≤1%, we identified 87 and 94 GoG intact N-glycopeptides corresponding to 37 and 35 intact N-glycoproteins from MCF-7 CSCs and MCF-7/ADR CSCs, respectively. Micro-heterogeneity and macro-heterogeneity of N-glycosylation from GoG intact N-glycoproteins with VAR_SEQ and VARIANT were found in both MCF-7 CSCs and MCF-7/ADR CSCs systems.

Conclusions

The integration of site- and structure-specific N-glycoproteomics approach, conjugating with GoG characterization, provides a universal workflow for revealing comprehensive N-glycosite and N-glycan structure information of GoG. The analysis of mutation-originated GoG can be extended to GoG characterization of other N-glycoproteome systems including complex clinical tissues and body fluids.

基本原理:已经建立了一个通用的N-糖蛋白组学分析流水线,用于在完整的N-糖肽分子水平表征突变相关的糖基化增益(GoG),生成全面的N-糖基化位点和结构信息:本研究采用基于质谱的 N-糖蛋白组学分析工作流程,重点研究突变引发的 GoG。简而言之,我们建立了由 2701 个蛋白质(从 UniProt 中的 MUTAGEN、VARIANT 和 VAR_SEQ 中提取的潜在 GoG N-糖基和氨基酸)和 6709 个人类 N-聚糖(每个单糖组成的序列异构体≤50 个)组成的 GoG 完整 N-糖肽数据库。我们利用完整N-糖肽搜索引擎GPSeeker的位点和结构特异性N-糖蛋白组学工作流程,从亲代乳腺癌干细胞(MCF-7 CSCs)和阿霉素抗性乳腺癌干细胞(MCF-7/ADR CSCs)中鉴定了GoG完整N-糖肽:以频谱级假发现率控制在≤1%为标准,我们分别从MCF-7 CSCs和MCF-7/ADR CSCs中鉴定出87个和94个GoG完整N-糖肽,对应37个和35个完整N-糖蛋白。在MCF-7造血干细胞和MCF-7/ADR造血干细胞系统中,发现VAR_SEQ和VARIANT与GoG完整N-糖蛋白的N-糖基化存在微异质性和大异质性:结论:位点和结构特异性 N-糖蛋白组学方法与 GoG 表征相结合,为揭示 GoG 的全面 N-糖复合体和 N-糖结构信息提供了通用的工作流程。对突变引起的GoG的分析可扩展到其他N-糖蛋白组系统(包括复杂的临床组织和体液)的GoG表征。
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引用次数: 0
On-site analysis and rapid identification of citrus herbs by miniature mass spectrometry and machine learning 利用微型质谱仪和机器学习对柑橘药材进行现场分析和快速鉴定。
IF 2 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2024-06-18 DOI: 10.1002/rcm.9780
Xingyu Wang, Yanqiao Xie, Jinliang Yu, Ye Chen, Yun Tian, Ziying Wang, Zhengtao Wang, Linnan Li, Li Yang

Background

Natural medicines present a considerable analytical challenge due to their diverse botanical origins and complex multi-species composition. This inherent complexity complicates their rapid identification and analysis. Tangerine peel, a product of the Citrus species from the Rutaceae family, is widely used both as a culinary ingredient and in traditional Chinese medicine. It is classified into two primary types in China: Citri Reticulatae Pericarpium (CP) and Citri Reticulatae Pericarpium Viride (QP), differentiated by harvest time. A notable price disparity exists between CP and another variety, Citri reticulatae “Chachi” (GCP), with differences being based on the original variety.

Methods

This study introduces an innovative method using portable miniature mass spectrometry for swift on-site analysis of QP, CP, and GCP, requiring less than a minute per sample. And combined with machine learning to differentiate the three types on site, the method was used to try to distinguish GCP from different storage years.

Results

This novel method using portable miniature mass spectrometry for swift on-site analysis of tangerine peels enabled the characterization of 22 compounds in less than one minute per sample. The method simplifies sample processing and integrates machine learning to distinguish between the CP, QP, and GCP varieties. Moreover, a multiple-perceptron neural network model is further employed to specifically differentiate between CP and GCP, addressing the significant price gap between them.

Conclusions

The entire analytical time of the method is about 1 minute, and samples can be analyzed on site, greatly reducing the cost of testing. Besides, this approach is versatile, operates independently of location and environmental conditions, and offers a valuable tool for assessing the quality of natural medicines.

背景:天然药物的植物来源多样,多物种成分复杂,给分析带来了相当大的挑战。这种固有的复杂性使其快速鉴定和分析变得更加复杂。陈皮是芸香科柑橘属植物的产物,被广泛用作烹饪配料和传统中药。在中国,橘皮主要分为两种类型:橘皮(Citri Reticulatae Pericarpium,CP)和橘皮(Citri Reticulatae Pericarpium Viride,QP),以收获时间区分。CP 和另一个品种 Citri reticulatae "Chachi" (GCP)之间存在明显的价格差异,差异取决于原始品种:本研究采用一种创新方法,利用便携式微型质谱仪对 QP、CP 和 GCP 进行快速现场分析,每个样品的分析时间不到一分钟。并结合机器学习来现场区分这三种类型,该方法还被用于尝试区分不同储存年份的 GCP:结果:这种使用便携式微型质谱仪对橘子皮进行现场快速分析的新方法能够在每个样品不到一分钟的时间内鉴定出 22 种化合物。该方法简化了样品处理过程,并结合了机器学习来区分 CP、QP 和 GCP 品种。此外,该方法还进一步采用了多重感知器神经网络模型来专门区分 CP 和 GCP,以解决它们之间的巨大价格差距:该方法的整个分析时间约为 1 分钟,样品可在现场进行分析,大大降低了检测成本。此外,该方法用途广泛,不受地点和环境条件的影响,是评估天然药物质量的重要工具。
{"title":"On-site analysis and rapid identification of citrus herbs by miniature mass spectrometry and machine learning","authors":"Xingyu Wang,&nbsp;Yanqiao Xie,&nbsp;Jinliang Yu,&nbsp;Ye Chen,&nbsp;Yun Tian,&nbsp;Ziying Wang,&nbsp;Zhengtao Wang,&nbsp;Linnan Li,&nbsp;Li Yang","doi":"10.1002/rcm.9780","DOIUrl":"10.1002/rcm.9780","url":null,"abstract":"<div>\u0000 \u0000 <section>\u0000 \u0000 <h3> Background</h3>\u0000 \u0000 <p>Natural medicines present a considerable analytical challenge due to their diverse botanical origins and complex multi-species composition. This inherent complexity complicates their rapid identification and analysis. Tangerine peel, a product of the <i>Citrus</i> species from the Rutaceae family, is widely used both as a culinary ingredient and in traditional Chinese medicine. It is classified into two primary types in China: Citri Reticulatae Pericarpium (CP) and Citri Reticulatae Pericarpium Viride (QP), differentiated by harvest time. A notable price disparity exists between CP and another variety, Citri reticulatae “Chachi” (GCP), with differences being based on the original variety.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>This study introduces an innovative method using portable miniature mass spectrometry for swift on-site analysis of QP, CP, and GCP, requiring less than a minute per sample. And combined with machine learning to differentiate the three types on site, the method was used to try to distinguish GCP from different storage years.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>This novel method using portable miniature mass spectrometry for swift on-site analysis of tangerine peels enabled the characterization of 22 compounds in less than one minute per sample. The method simplifies sample processing and integrates machine learning to distinguish between the CP, QP, and GCP varieties. Moreover, a multiple-perceptron neural network model is further employed to specifically differentiate between CP and GCP, addressing the significant price gap between them.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusions</h3>\u0000 \u0000 <p>The entire analytical time of the method is about 1 minute, and samples can be analyzed on site, greatly reducing the cost of testing. Besides, this approach is versatile, operates independently of location and environmental conditions, and offers a valuable tool for assessing the quality of natural medicines.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"38 16","pages":""},"PeriodicalIF":2.0,"publicationDate":"2024-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141417083","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
Development of a quantum cascade laser absorption spectrometer for simultaneous measurement of 13C–18O and 18O–18O clumping in CO2 开发量子级联激光吸收光谱仪,用于同时测量二氧化碳中的 13C-18O 和 18O-18O 凝聚。
IF 2 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2024-06-18 DOI: 10.1002/rcm.9836
Scott T. Wieman, Jason Kapit, Anna P. M. Michel, Weifu Guo

Rationale

Dual clumped isotope paleothermometry determines carbonate formation temperatures by measuring the frequency of 13C–18O (∆638) and 18O–18O (∆828) pairs in carbonates. It resolves isotopic kinetic biases and thus enables more accurate paleotemperature reconstructions. However, high-precision measurements of 18O–18O clumping using current techniques requires large sample sizes and long acquisition times.

Methods

We developed a mid-infrared isotope ratio laser spectrometer (IRLS) for simultaneous measurement of the isotopologue ratios ∆638 and ∆828 in gas-phase carbon dioxide (CO2) at room temperature. Our IRLS uses a single laser scanning from 2290.7 to 2291.1 cm−1 and a 31 m pathlength optical cell, and it simultaneously measures the five isotopologues required for calculating ∆638 and ∆828: 16O12C16O, 16O13C16O, 16O12C18O, 16O13C18O, and 18O12C18O. In addition, our IRLS can measure 16O12C17O, enabling ∆17O analysis.

Results

At ~20°C and a CO2 pressure of ~2 Torr, our IRLS system achieved precisions of 0.128‰ and 0.140‰ within 20 s for abundances of the clumped isotopologues 16O13C18O and 18O12C18O, respectively, and precisions of 0.267‰, 0.245‰, and 0.128‰ for 16O12C16O, 16O13C16O, and 16O12C18O. This yielded precisions of 0.348‰ (∆638) and 0.302‰ (∆828) within 25 s. Simulated sample–reference switching highlights the potential of our system and the need for further development.

Conclusions

We demonstrated simultaneous measurements of ∆638 and ∆828 in CO2 to precisions of <0.35‰ within 25 s using a room-temperature, single-laser IRLS. Future developments on better resolving 16O12C16O and 16O13C16O peaks and system temperature control could further improve the measurement precision.

理由:双块同位素古温度测定法通过测量碳酸盐中 13C-18O (∆638) 和 18O-18O (∆828) 对的频率来确定碳酸盐的形成温度。它可以消除同位素动力学偏差,从而实现更精确的古温度重建。然而,利用现有技术对 18O-18O 凝块进行高精度测量需要大量样本和较长的采集时间:我们开发了一种中红外同位素比激光光谱仪(IRLS),可在室温下同时测量气相二氧化碳(CO2)中的同位素比∆638和∆828。我们的 IRLS 使用从 2290.7 厘米-1 到 2291.1 厘米-1 的单激光扫描和一个 31 米路径长度的光学单元,可同时测量计算 ∆638 和 ∆828 所需的五个同位素:16O12C16O、16O13C16O、16O12C18O、16O13C18O 和 18O12C18O。此外,我们的 IRLS 还可以测量 16O12C17O,从而进行 ∆17O 分析:结果:在 ~20°C 和约 2 托的二氧化碳压力下,我们的 IRLS 系统在 20 秒内对成块同位素 16O13C18O 和 18O12C18O 的丰度分别达到了 0.128‰ 和 0.140‰,对 16O12C16O、16O13C16O 和 16O12C18O 的丰度分别达到了 0.267‰、0.245‰ 和 0.128‰。这样,25 秒内的精确度分别为 0.348‰(∆638)和 0.302‰(∆828)。模拟样品-参照物切换凸显了我们系统的潜力和进一步开发的必要性:我们展示了在二氧化碳中同时测量 ∆638 和 ∆828 的结果,精确度达到 16O12C16O 和 16O13C16O 峰,系统温度控制可进一步提高测量精度。
{"title":"Development of a quantum cascade laser absorption spectrometer for simultaneous measurement of 13C–18O and 18O–18O clumping in CO2","authors":"Scott T. Wieman,&nbsp;Jason Kapit,&nbsp;Anna P. M. Michel,&nbsp;Weifu Guo","doi":"10.1002/rcm.9836","DOIUrl":"10.1002/rcm.9836","url":null,"abstract":"<div>\u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>Dual clumped isotope paleothermometry determines carbonate formation temperatures by measuring the frequency of <sup>13</sup>C–<sup>18</sup>O (∆<sub>638</sub>) and <sup>18</sup>O–<sup>18</sup>O (∆<sub>828</sub>) pairs in carbonates. It resolves isotopic kinetic biases and thus enables more accurate paleotemperature reconstructions. However, high-precision measurements of <sup>18</sup>O–<sup>18</sup>O clumping using current techniques requires large sample sizes and long acquisition times.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>We developed a mid-infrared isotope ratio laser spectrometer (IRLS) for simultaneous measurement of the isotopologue ratios ∆<sub>638</sub> and ∆<sub>828</sub> in gas-phase carbon dioxide (CO<sub>2</sub>) at room temperature. Our IRLS uses a single laser scanning from 2290.7 to 2291.1 cm<sup>−1</sup> and a 31 m pathlength optical cell, and it simultaneously measures the five isotopologues required for calculating ∆<sub>638</sub> and ∆<sub>828</sub>: <sup>16</sup>O<sup>12</sup>C<sup>16</sup>O, <sup>16</sup>O<sup>13</sup>C<sup>16</sup>O, <sup>16</sup>O<sup>12</sup>C<sup>18</sup>O, <sup>16</sup>O<sup>13</sup>C<sup>18</sup>O, and <sup>18</sup>O<sup>12</sup>C<sup>18</sup>O. In addition, our IRLS can measure <sup>16</sup>O<sup>12</sup>C<sup>17</sup>O, enabling ∆<sup>17</sup>O analysis.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>At ~20°C and a CO<sub>2</sub> pressure of ~2 Torr, our IRLS system achieved precisions of 0.128‰ and 0.140‰ within 20 s for abundances of the clumped isotopologues <sup>16</sup>O<sup>13</sup>C<sup>18</sup>O and <sup>18</sup>O<sup>12</sup>C<sup>18</sup>O, respectively, and precisions of 0.267‰, 0.245‰, and 0.128‰ for <sup>16</sup>O<sup>12</sup>C<sup>16</sup>O, <sup>16</sup>O<sup>13</sup>C<sup>16</sup>O, and <sup>16</sup>O<sup>12</sup>C<sup>18</sup>O. This yielded precisions of 0.348‰ (∆<sub>638</sub>) and 0.302‰ (∆<sub>828</sub>) within 25 s. Simulated sample–reference switching highlights the potential of our system and the need for further development.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusions</h3>\u0000 \u0000 <p>We demonstrated simultaneous measurements of ∆<sub>638</sub> and ∆<sub>828</sub> in CO<sub>2</sub> to precisions of &lt;0.35‰ within 25 s using a room-temperature, single-laser IRLS. Future developments on better resolving <sup>16</sup>O<sup>12</sup>C<sup>16</sup>O and <sup>16</sup>O<sup>13</sup>C<sup>16</sup>O peaks and system temperature control could further improve the measurement precision.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"38 16","pages":""},"PeriodicalIF":2.0,"publicationDate":"2024-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/rcm.9836","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141417080","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Sensitive detection of oxytocin in nonhuman primate plasma using a novel liquid chromatography–tandem mass spectrometry assay 利用新型液相色谱-串联质谱测定法灵敏检测非人灵长类动物血浆中的催产素。
IF 2 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2024-06-18 DOI: 10.1002/rcm.9839
Kristopher M. Fecteau, Tatiana A. Shnitko, Kathleen A. Grant, David W. Erikson
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引用次数: 0
Data-independent acquisition combined with liquid chromatography mass spectrometry technique to detect prognostic protein markers in type I gastric neuroendocrine neoplasm 独立数据采集结合液相色谱质谱技术检测 I 型胃神经内分泌肿瘤的预后蛋白标记物
IF 2 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2024-06-18 DOI: 10.1002/rcm.9849
Meng Zhang, Xiuli Zheng, Chunyan Wang, Shengmian Li

Rationale

This study used proteomics-based data-independent acquisition (DIA) technology with the aim of screening for differential expression proteins in type I gastric neuroendocrine neoplasm (g-NEN).

Methods

Differential expression proteins in type I g-NEN and peritumoral tissues were screened using DIA with liquid chromatography/tandem mass spectrometry (DIA-LC/MS/MS). The identified proteins were then functionally analysed using bioinformatics methods. We selected the three most highly expressed proteins, combined with patients' clinical data, for prognostic analysis.

Results

Compared with peritumoral tissues, 224 proteins were up-regulated, and 70 were down-regulated. The most significantly enriched biological processes and pathways were vacuolar proton-transporting V-type ATPase complex assembly and metabolism-related pathways. PCSK1, FBXO2, ACSL1, IRS2, and PTPRZ1 expression was markedly up-regulated in type I g-NENs. High IRS2 expression significantly correlated with a shorter time to recurrence.

Conclusions

Our study provides a comprehensive proteomic signature based on DIA-LC/MS/MS and highlights high IRS2 expression as a potential prognostic marker for type I gNENs.

理由:本研究采用基于蛋白质组学的数据独立获取(DIA)技术,旨在筛选I型胃神经内分泌肿瘤(g-NEN)中的差异表达蛋白:方法:利用液相色谱/串联质谱(DIA-LC/MS/MS)技术筛选 I 型胃神经内分泌瘤和瘤周组织中的差异表达蛋白。然后使用生物信息学方法对鉴定出的蛋白质进行功能分析。我们选择了三种表达量最高的蛋白质,结合患者的临床数据进行预后分析:结果:与瘤周组织相比,224个蛋白上调,70个蛋白下调。最明显富集的生物过程和通路是空泡质子转运V型ATP酶复合物组装和代谢相关通路。在I型g-NENs中,PCSK1、FBXO2、ACSL1、IRS2和PTPRZ1的表达明显上调。IRS2的高表达与较短的复发时间明显相关:我们的研究提供了基于 DIA-LC/MS/MS 的全面蛋白质组特征,并强调 IRS2 高表达是 I 型 g-NENs 的潜在预后标志物。
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引用次数: 0
Lipid extraction alters amino acid composition and bulk, but not amino acid, carbon and nitrogen isotope values 脂质提取会改变氨基酸组成和体积,但不会改变氨基酸、碳和氮同位素值。
IF 2 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2024-06-18 DOI: 10.1002/rcm.9848
Kelton W. McMahon

Rationale

Concerns exist over observed shifts in value and variance of nitrogen isotopes following physicochemical extraction of lipids from organic matter. The mechanisms behind these apparent changes in bulk tissue δ15N values are not fully understood yet have major implications for analytical costs and integrity of data interpretations.

Methods

Changes in proximate analysis, amino acid composition, C:N ratios, bulk tissue and amino acid δ13C and δ15N values, and resulting isotope-based food web metrics were compared between lipid-intact and lipid-extracted muscle tissue of fishes spanning <1% to >20% muscle fat content to identify mechanisms of nitrogen isotope fractionation associated with physicochemical lipid extraction.

Results

Bulk δ13C and δ15N values increased and %N, C:N ratios and crude protein content decreased following lipid extraction. Resulting bulk isotope niche spacing and overlap varied significantly between lipid-intact and lipid-extracted tissues. While amino acid composition significantly changed during lipid extraction, particularly for lipid-associated amino acids (e.g., Glu, Lys, Ser), individual amino acid δ13C and δ15N values, and their associated compound-specific isotope analysis of amino acids (CSIA-AA)-based food web metrics, did not.

Conclusions

Physicochemical lipid extraction caused significant tissue composition changes (e.g., leaching of amino acids and 15N-deplete nitrogenous waste) that affected δ13C and δ15N values and tissue %C and %N beyond simply removing lipids. However, lipid extraction did not alter individual amino acid δ13C or δ15N values or their associated CSIA-AA-based food web metrics.

理由从有机物中物理化学提取脂质后,观察到氮同位素的值和方差发生了变化,这引起了人们的关注。大量组织 δ15N 值明显变化背后的机制尚未完全清楚,但对分析成本和数据解释的完整性有重大影响:方法:比较了肌肉脂肪含量为 20% 的鱼类的无脂肌肉组织和脂质提取肌肉组织的近似分析、氨基酸组成、C:N 比值、块状组织和氨基酸 δ13C 和 δ15N 值的变化,以及由此产生的基于同位素的食物网指标,以确定与物理化学脂质提取有关的氮同位素分馏机制:结果:提取脂质后,大体积δ13C和δ15N值增加,%N、C:N比和粗蛋白含量降低。在未提取脂质的组织和提取脂质的组织之间,大体同位素位点间距和重叠度差异显著。虽然氨基酸组成在脂质提取过程中发生了明显变化,特别是脂质相关氨基酸(如 Glu、Lys、Ser),但单个氨基酸的 δ13C 和 δ15N 值以及与之相关的基于氨基酸化合物特异性同位素分析(CSIA-AA)的食物网指标并未发生变化:结论:物理化学脂质提取会导致组织成分发生显著变化(如氨基酸和15N贫氮废物的沥滤),从而影响δ13C和δ15N值以及组织中的%C和%N,而不仅仅是去除脂质。然而,脂质提取不会改变单个氨基酸的δ13C或δ15N值,也不会改变与之相关的基于CSIA-AA的食物网指标。
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引用次数: 0
Study on the impurity profiles of cloxacillin and flucloxacillin based on liquid chromatography tandem ion trap/time-of-flight mass spectrometry 基于液相色谱串联离子阱/飞行时间质谱法的氯唑西林和氟氯西林杂质谱研究
IF 2 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2024-06-18 DOI: 10.1002/rcm.9840
Bingyong Xu, Jiarui Gao, Jian Wang, Fan Wang

Rationale

Cloxacillin and flucloxacillin are prone to degradation and polymerization in humid and hot environments, and their polymers have long been recognized to trigger allergic manifestations. A series of the degradation and polymerized impurities in cloxacillin and flucloxacillin were separated and characterized to ensure safe use of these drugs by the public.

Methods

By studying the chromatographic behavior of the degradation impurities and polymerized impurities in reversed-phase high-performance liquid chromatography (RP-HPLC) gradient elution, the impurities in cloxacillin and flucloxacillin were effectively separated and eluted. RP-HPLC tandem ion trap/time-of-flight mass spectrometry (MS) was applied to characterize the structures of unknown impurities eluted from the RP-HPLC methods for cloxacillin and flucloxacillin. The mechanisms of formation of the impurities in cloxacillin and flucloxacillin were also investigated.

Results

The structures of 10 unknown impurities in cloxacillin and 8 unknown impurities in flucloxacillin were elucidated based on the high-resolution MSn data at positive and negative modes, respectively. Six polymerized impurities were found and characterized, of which three were from the polymerization of cloxacillin and three were from the polymerization of flucloxacillin.

Conclusions

The study on the impurity profiles of cloxacillin and flucloxacillin provided a scientific basis for improving their production processes and quality control.

理由:氯唑西林和氟氯唑西林在潮湿和炎热的环境中容易降解和聚合,其聚合物长期以来一直被认为会引发过敏表现。为了确保公众安全使用这些药物,我们对氯唑西林和氟氯西林中的一系列降解和聚合杂质进行了分离和鉴定:通过研究降解杂质和聚合杂质在反相高效液相色谱(RP-HPLC)梯度洗脱中的色谱行为,有效地分离和洗脱了氯唑西林和氟氯西林中的杂质。应用 RP-HPLC 串联离子阱/飞行时间质谱(MS)分析了氯唑西林和氟氯西林 RP-HPLC 方法洗脱出的未知杂质的结构。同时还研究了这些杂质在氯唑西林和氟氯西林中的形成机制:结果:根据正、负模式的高分辨率 MSn 数据,分别阐明了氯唑西林中 10 个未知杂质和氟氯西林中 8 个未知杂质的结构。发现并鉴定了 6 个聚合杂质,其中 3 个来自氯唑西林的聚合,3 个来自氟氯西林的聚合:对氯唑西林和氟氯西林杂质谱的研究为改进其生产工艺和质量控制提供了科学依据。
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引用次数: 0
Lipid A double bond position determination using ozone and laser-induced dissociation 利用臭氧和激光诱导解离测定脂质 A 双键的位置。
IF 2 3区 化学 Q4 BIOCHEMICAL RESEARCH METHODS Pub Date : 2024-06-18 DOI: 10.1002/rcm.9854
Abanoub Mikhael, Helena Pětrošová, Derek Smith, Robert K. Ernst, David R. Goodlett
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引用次数: 0
期刊
Rapid Communications in Mass Spectrometry
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