Université de Strasbourg, CNRS, Institut Charles Sadron UPR22, 23 rue du Loess, Strasbourg Cedex 2, 67034, France.
Aix Marseille Université, CNRS, UMR 7273, Institute of Radical Chemistry, Marseille, Cedex 20 13397, France.
Macromol Rapid Commun. 2020 Jun;41(12):e2000215. doi: 10.1002/marc.202000215. Epub 2020 May 24.
The collision-induced dissociation (CID) of sequence-defined poly(alkoxyamine phosphodiester)s is studied by electrospray ionization mass spectrometry. These informational polymers are synthesized using three different nitroxide building blocks, namely proxyl-, SG1-, and TEMPO-derivatives. For a polymer containing TEMPO- and SG1-based main chain alkoxyamines, it is found that both types of alkoxyamines break in CID tandem mass spectrometry (MS/MS). However, SG1-sites are preferentially cleaved and this predominance can be increased by reducing collision energy, even though selective bond fragmentation is not observed. On the other hand, for a polymer containing proxyl- and SG1-alkoxyamines, selective bond cleavage is observed at all studied collision energies. The SG1-alkoxyamines can be first cleaved in MS/MS conditions and secondly the proxyl-alkoxyamines in pseudo-MS conditions. These results open up interesting new avenues for the design of readable, erasable or programmable informational polymers.
采用电喷雾质谱法研究了序列定义的聚（烷氧基胺磷酸二酯）的碰撞诱导解离（CID）。这些信息聚合物是使用三种不同的氮氧自由基构建块，即 PROXYL、SG1 和 TEMPO 衍生物合成的。对于含有 TEMPO 和 SG1 为主链烷氧基胺的聚合物，发现两种类型的烷氧基胺在 CID 串联质谱（MS/MS）中都会断裂。然而，SG1 位点优先被切断，这种优势可以通过降低碰撞能量来增加，尽管没有观察到选择性键断裂。另一方面，对于含有 PROXYL 和 SG1 烷氧基胺的聚合物，在所有研究的碰撞能量下都观察到选择性键断裂。在 MS/MS 条件下可以首先切断 SG1-烷氧基胺，然后在 pseudo-MS 条件下切断 PROXYL-烷氧基胺。这些结果为设计可读、可擦除或可编程的信息聚合物开辟了有趣的新途径。
