Development of Sequence‐Controlled, Degradable, and Cytocompatible Oligomers with Explicit Fragmentation Pathways.

Sequence‐defined and degradable polymers can mimic biopolymers, such as peptides and DNA, to undertake life‐supporting functions in a chemical way. The design and development of well‐structured oligomers/polymers is the most concern for the public, even to further uncover their degradation process illustrating the degraded products and their properties. However, seldom investigation has been reported on the aforementioned aspects. In this work, the alternating photo‐reversible addition‐fragmentation chain‐transfer (photo‐RAFT) single unit monomer insertion (SUMI) of different N‐substituted maleimides and thermal radical ring‐opening SUMI of a cyclic ketene acetal monomer (i.e., 5,6‐benzo‐2‐methylene‐1,3‐dioxepane (BMDO)) is adopted, to produce two degradable pentamers owing to the conversion of the exo‐methylene group of BMDO into ester bonds along the main chains of the prepared products. Moreover, the possible degraded approach of pentamers is studied by combining high‐resolution mass spectrometry (HRMS) and liquid chromatography‐mass spectrometry (LC‐MS) for the first time. This work also sheds light on the precise structures and cytotoxicity of SUMI products and their degraded compounds, proposing a detailed and credible outlook for biomedical applications. [ABSTRACT FROM AUTHOR]