Self?Immolative RAFT?Polymer End Group Modification

Reversible modifications of reversible addition–fragmentation chain transfer (RAFT)-polymerization derived end groups are usually limited to reductive degradable disulfide conjugates. However, self-immolative linkers can promote ligation and traceless release primary secondary amines as well alcohols via carbonates or carbamates in ?-position disulfides. In this study, these two strategies combined the concept RAFT-polymer group is introduced: As model compounds, benzylamine, dibenzylamine, benzyl alcohol first attached a symmetrical disulfide, straightforward one-pot reaction reversibly aminolyzed trithiocarbonate RAFT-polymerized poly(N,N-dimethylacrylamide). Quantitative modification confirmed by 1H NMR spectroscopy, size exclusion chromatography, mass spectrometry, while compounds under physiological conditions successfully monitored diffusion ordered spectroscopy thin layer chromatography. Additionally, further expanded protein-reactive, carbonate species that enable bioconjugation lysozyme ?-macrophage mannose receptor (MMR) nanobodies proteins. Altogether, RAFT form new basis for introduction various functionalities polymer ends including protein bioconjugates and, thus, opening novel opportunities stimuli-responsive hybrids.