Poly(O-Propargyl-N-Amino Carbamate), a Reactive Polymer to Underpin Biomedical Applications of Poly(Acetylene)S

Abstract

[Abstract] Synthetic polymers are widely used in biomedical applications, yet most lack defined secondary structures common in nature,such as helices or β-sheets. In particular, dynamic helical polymers such as poly(acetylene)s have been rarely explored in thisfield. Here, we report the preparation of a new reactive poly(acetylene), poly(O-propargyl-N-amino carbamate) (P1), as a platformfor the preparation of functional poly(acetylene)s in water. P1 was prepared from readily available starting materials throughRh-catalyzed polymerization and acid-mediated deprotection. 1 H-NMR indicated that the formed polymer had a high content ofcis double bonds, while UV–vis and DSC suggested a predominant cis-cisoid conformation. This conformation was also observedvia CD for chiral derivatives of Boc-protected P1, while a partially deprotected chiral derivative of P1 could be adopting multipleconformations in solution, including cis-transoid and cis-cisoid conformations. P1 was functionalized under aqueous conditionswith a small set of aldehydes, including cationic, aliphatic, and aromatic derivatives, as well as a small set of carbohydrates. Finally,we demonstrate that P1, and a guanidinium derivative P1-mod-4, were well tolerated by cells, highlighting the potential of thispolymer to underpin the development of biomedical applications of poly(acetylene)s