{"title":"热重法--同步、无参照定量质谱法,用于在事先不了解成分的情况下对聚合物体系进行精确成分分析","authors":"Yusuke Hibi, Shiho Uesaka, Masanobu Naito","doi":"10.1039/d4an00624k","DOIUrl":null,"url":null,"abstract":"Compositional analysis (CA)—identification and quantification of the system constituents—is the most fundamental and decisive approach to investigate the system of interest. Pyrolysis mass spectrometry (MS) with high resolution over 10,000 is very effective for chemical identification and directly applicable to polymer materials regardless of their solubilities; however, it is less helpful for quantification especially when the references, i.e., pure constituents, are unknown, non-isolable and thus unpreparable. To compensate this weakness, herein we propose reference-free quantitative mass spectrometry (RQMS) with enhanced quantification accuracy assisted by synchronized thermogravimetry (TG). The key to success lies in correlating the instantaneous weight loss from TG with MS signal, enabling the quantitative evaluation of the distinct ionization efficiency for each fragment individually. The determined ionization efficiencies allow conversion of MS signal intensities of pyrolyzed fragments into weight abundances. In a benchmark test using ternary polymer systems, this new framework named TG-RQMS demonstrates accurate CA within ±1.3 wt% errors without using any knowledge nor spectra of the references. This simple yet accurate and versatile CA method would be an invaluable tool to investigate polymer materials whose composition is hardly accessible via other analytical methods.","PeriodicalId":63,"journal":{"name":"Analyst","volume":null,"pages":null},"PeriodicalIF":3.6000,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Thermogravimetry-Synchronized, Reference-Free Quantitative Mass Spectrometry for Accurate Compositional Analysis of Polymer Systems Without Prior Knowledge of Constituents\",\"authors\":\"Yusuke Hibi, Shiho Uesaka, Masanobu Naito\",\"doi\":\"10.1039/d4an00624k\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Compositional analysis (CA)—identification and quantification of the system constituents—is the most fundamental and decisive approach to investigate the system of interest. Pyrolysis mass spectrometry (MS) with high resolution over 10,000 is very effective for chemical identification and directly applicable to polymer materials regardless of their solubilities; however, it is less helpful for quantification especially when the references, i.e., pure constituents, are unknown, non-isolable and thus unpreparable. To compensate this weakness, herein we propose reference-free quantitative mass spectrometry (RQMS) with enhanced quantification accuracy assisted by synchronized thermogravimetry (TG). The key to success lies in correlating the instantaneous weight loss from TG with MS signal, enabling the quantitative evaluation of the distinct ionization efficiency for each fragment individually. The determined ionization efficiencies allow conversion of MS signal intensities of pyrolyzed fragments into weight abundances. In a benchmark test using ternary polymer systems, this new framework named TG-RQMS demonstrates accurate CA within ±1.3 wt% errors without using any knowledge nor spectra of the references. This simple yet accurate and versatile CA method would be an invaluable tool to investigate polymer materials whose composition is hardly accessible via other analytical methods.\",\"PeriodicalId\":63,\"journal\":{\"name\":\"Analyst\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":3.6000,\"publicationDate\":\"2024-06-26\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Analyst\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d4an00624k\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, ANALYTICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Analyst","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4an00624k","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, ANALYTICAL","Score":null,"Total":0}
引用次数: 0
摘要
成分分析(CA)--系统成分的鉴定和定量--是研究相关系统的最基本、最具决定性的方法。热解质谱(MS)的分辨率高达 10,000 分以上,对化学鉴定非常有效,可直接用于聚合物材料(无论其溶解度如何);但它对定量的帮助较小,尤其是当参照物(即纯成分)未知、不可分离,因而无法定量时。为了弥补这一不足,我们在此提出了无参照物定量质谱法(RQMS),在同步热重仪(TG)的辅助下提高了定量精度。成功的关键在于将热重仪测得的瞬时重量损失与质谱信号相关联,从而对每个片段的不同电离效率进行定量评估。根据确定的电离效率,可将热解片段的 MS 信号强度转换为重量丰度。在使用三元聚合物体系进行的基准测试中,这种名为 TG-RQMS 的新框架在不使用任何知识或参照物光谱的情况下证明了 CA 的准确性,误差在 ±1.3 wt% 以内。这种简单而准确的多功能 CA 方法将成为研究聚合物材料的宝贵工具,因为其他分析方法很难获得这些材料的成分。
Thermogravimetry-Synchronized, Reference-Free Quantitative Mass Spectrometry for Accurate Compositional Analysis of Polymer Systems Without Prior Knowledge of Constituents
Compositional analysis (CA)—identification and quantification of the system constituents—is the most fundamental and decisive approach to investigate the system of interest. Pyrolysis mass spectrometry (MS) with high resolution over 10,000 is very effective for chemical identification and directly applicable to polymer materials regardless of their solubilities; however, it is less helpful for quantification especially when the references, i.e., pure constituents, are unknown, non-isolable and thus unpreparable. To compensate this weakness, herein we propose reference-free quantitative mass spectrometry (RQMS) with enhanced quantification accuracy assisted by synchronized thermogravimetry (TG). The key to success lies in correlating the instantaneous weight loss from TG with MS signal, enabling the quantitative evaluation of the distinct ionization efficiency for each fragment individually. The determined ionization efficiencies allow conversion of MS signal intensities of pyrolyzed fragments into weight abundances. In a benchmark test using ternary polymer systems, this new framework named TG-RQMS demonstrates accurate CA within ±1.3 wt% errors without using any knowledge nor spectra of the references. This simple yet accurate and versatile CA method would be an invaluable tool to investigate polymer materials whose composition is hardly accessible via other analytical methods.