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‐MS³ conditions. These results open up interesting new avenues for the design of readable, erasable or programmable informational polymers.

中文翻译：

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信息性聚（烷氧基胺磷酸二酯）中的选择性键裂解。

通过电喷雾电离质谱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一氧化氮构建基合成的，分别是proxyl，SG1和TEMPO衍生物。对于包含基于TEMPO和SG1的主链烷氧基胺的聚合物，发现在CID串联质谱（MS / MS）中两种类型的烷氧基胺均会断裂。但是，SG1位点优先被切割，即使未观察到选择性键断裂，也可通过减少碰撞能量来增加这一优势。另一方面，对于包含取代基和SG1烷氧基胺的聚合物，在所有研究的碰撞能量下均观察到选择性键裂解。^3个条件。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。