Fouquet Thierry N J, Cody Robert B, Charles Laurence
Bausch + Lomb, Inc., Rochester, New York, USA.
JEOL USA Inc, Peabody, Massachusetts, USA.
Mass Spectrom Rev. 2024 Aug 2. doi: 10.1002/mas.21903.
With the advent of soft ionization techniques such as electrospray (ESI) and matrix-assisted laser desorption/ionization (MALDI) to produce intact gas-phase ions from nonvolatile macromolecules, mass spectrometry has become an essential technique in the field of polymeric materials. However, (co)polymers of very high molecular weight or with reticulated architectures still escape ESI or MALDI, mainly due to solubility issues. Strategies developed to tackle such an analytical challenge all rely on sample degradation to produce low-mass species amenable to existing ionization methods. Yet, chain degradation needs to be partial and controlled to generate sufficiently large species that still contain topological or architectural information. The present article reviews the different analytical degradation strategies implemented to perform mass spectrometry of these challenging synthetic polymers, covering thermal degradation approaches in sources developed in the 2000s, off-line sample pre-treatments for controlled chemical degradation of polymeric substrates, and most recent achievements employing reactive ionization modes to perform chemolysis on-line with MS.
随着诸如电喷雾（ESI）和基质辅助激光解吸/电离（MALDI）等软电离技术的出现，能够从非挥发性大分子产生完整的气相离子，质谱已成为聚合物材料领域的一项重要技术。然而，极高分子量或具有网状结构的（共）聚物仍然无法通过ESI或MALDI进行分析，主要是由于溶解度问题。为应对这一分析挑战而开发的策略都依赖于样品降解，以产生适合现有电离方法的低质量物种。然而，链降解需要是部分的且可控的，以生成仍然包含拓扑或结构信息的足够大的物种。本文综述了为对这些具有挑战性的合成聚合物进行质谱分析而实施的不同分析降解策略，涵盖了21世纪开发的源内热降解方法、用于聚合物底物可控化学降解的离线样品预处理，以及采用反应性电离模式与质谱在线进行化学裂解的最新成果。
