Department of Chemistry, University of Warwick, Coventry, Midlands CV4 7AL, U.K.
Chemical Development, Pharmaceutical Technology & Development, Operations, AstraZeneca, Macclesfield, Cheshire SK10 2NA, U.K.
Anal Chem. 2020 Oct 6;92(19):12852-12859. doi: 10.1021/acs.analchem.0c01224. Epub 2020 Sep 9.
The structure and sequence elucidation of complex homo- and copolymers is key for further understanding polymers, polymer synthesis, and polymer interactions in biological processes. In this contribution, poly(dimethylacrylamide) homo- and dimethylacrylamide/4-acryloylmorpholine block copolymers were synthesized and analyzed by electron capture dissociation (ECD) and Fourier transform ion cyclotron resonance (FT-ICR) tandem mass spectrometry. Double-resonance experiments were carried out, providing a better understanding of the fragmentation process. A novel radical dissociation process is presented, and electron capture caused a specific cleavage at the terminal butyl-trithiocarbonate group, which initiated a free radical dissociation process.
复杂均聚物和共聚物的结构和序列阐明对于进一步了解聚合物、聚合物合成以及生物过程中的聚合物相互作用至关重要。在本研究中，通过电子捕获解离（ECD）和傅里叶变换离子回旋共振（FT-ICR）串联质谱法合成并分析了聚（二甲基丙烯酰胺）均聚物和二甲基丙烯酰胺/4-丙烯酰吗啉嵌段共聚物。进行了双共振实验，为碎裂过程提供了更好的理解。提出了一种新的自由基解离过程，电子捕获导致末端丁基三硫代碳酸盐基团的特异性断裂，从而引发自由基解离过程。
