Bochenek Maria, Ciach Michał Aleksander, Smeets Sander, Beckers Omar, Vanderspikken Jochen, Miasojedow Błażej, Domżał Barbara, Valkenborg Dirk, Maes Wouter, Gambin Anna
Faculty of Mathematics, Informatics and Mechanics, University of Warsaw, Banacha 2, Warsaw 02-097, Poland.
Data Science Institute, Hasselt University, Hasselt 3500, Belgium.
J Am Soc Mass Spectrom. 2024 Oct 2;35(10):2366-2375. doi: 10.1021/jasms.4c00225. Epub 2024 Sep 18.
Conjugated organic polymers have substantial potential for multiple applications but their properties are strongly influenced by structural defects such as homocoupling of monomer units and unexpected end-groups. Detecting and/or quantifying these defects requires complex experimental techniques, which hinder the optimization of synthesis protocols and fundamental studies on the influence of structural defects. Mass spectrometry offers a simple way to detect these defects but a manual analysis of many complex spectra is tedious and provides only approximate results. In this work, we develop a computational methodology for analyzing complex mass spectra of organic copolymers. Our method annotates spectra similarly to a human expert and provides quantitative information about the proportions of signal assigned to each ion. Our method is based on the open-source Masserstein algorithm, which we modify to handle large libraries of reference spectra required for annotating complex mass spectra of polymers. We develop a statistical methodology to analyze the quantitative annotations and compare the statistical distributions of structural defects in polymer chains between samples. We apply this methodology to analyze commercial and lab-made samples of a benchmark polymer and show that the samples differ both in the amount and in the types of structural defects.
共轭有机聚合物在多种应用中具有巨大潜力，但其性能受到诸如单体单元的均偶联和意外端基等结构缺陷的强烈影响。检测和/或量化这些缺陷需要复杂的实验技术，这阻碍了合成方案的优化以及对结构缺陷影响的基础研究。质谱分析提供了一种检测这些缺陷的简单方法，但对许多复杂光谱进行人工分析既繁琐又只能提供近似结果。在这项工作中，我们开发了一种用于分析有机共聚物复杂质谱的计算方法。我们的方法与人类专家类似地对光谱进行注释，并提供有关分配给每个离子的信号比例的定量信息。我们的方法基于开源的Masserstein算法，我们对其进行了修改以处理注释聚合物复杂质谱所需的大量参考光谱库。我们开发了一种统计方法来分析定量注释，并比较样品之间聚合物链中结构缺陷的统计分布。我们应用这种方法来分析一种基准聚合物的商业样品和实验室制备的样品，并表明这些样品在结构缺陷的数量和类型上都有所不同。
