Bone and Joint Institute

Multiresponsive azobenzene end-cap for self-immolative polymers

Document Type

Article

Publication Date

11-18-2014

Journal

ACS Macro Letters

Volume

3

Issue

11

First Page

1191

Last Page

1195

URL with Digital Object Identifier

10.1021/mz500613d

Abstract

© 2014 American Chemical Society. Azobenzene was introduced as a new multiresponsive end-cap for self-immolative polymers. Using small-molecule model compounds, it was demonstrated that reducing agents including hydrazine and dithiothreitol could reduce the azobenzene to the corresponding hydrazobenzene, resulting in a 1,6-elimination reaction with the potential to initiate the depolymerization of self-immolative polycarbamates. An activated azobenzene derivative was then prepared, allowing for its incorporation as an end-cap for polycarbamates based on alternating N,N'-dimethylethylene diamine and 4-hydroxybenzyl alcohol. Upon treatment with hydrazine, depolymerization proceeded. To demonstrate the versatility of this end-cap, the chemistry was also applied to polycarbamates based on 4-aminobenzyl alcohol. In addition to allowing triggered depolymerization, the azobenzene end-cap also provides a visual signal upon triggering owing to the strong visible absorption of the azobenzene, which shifts to the UV range upon reduction. Furthermore, azobenzene is capable of undergoing trans-cis isomerization in response to UV light, providing multiple functions in a single end-cap.

Notes

Article is openly available from the journal

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