Facile synthesis of dopa-functional polycarbonates via thiol-Ene-coupling chemistry towards self-healing gels

Abstract

Since extraction of the naturally occurring musselfoot proteins is expensive and time-consuming, routes towards synthetic analogues are continuously being explored. Often, these methods involve several protection and deprotection steps, making the synthesis of synthetic analogues timeconsuming and expensive as well. Herein, we show that UVinitiated thiol-ene coupling between a thiol-functional dopamine derivative and an allyl-functional aliphatic polycarbonate can be used as a fast and facile route to dopa-functional materials. Different thiol-to-allyl ratios and irradiation protocols were used and it was found that nearly 50% of the allyl groups could be functionalized with dopa within short reaction times, without the need of protecting the catechol. It is also demonstrated herein that the dopa-functional polymers can be used to form self-healing gels through complexation with Fe 31 ions at increased pH.

Functional biodegradable polymers via ring-opening polymerization of monomers without protective groups

“…252 Thiol-ene reaction was applied to attach folic acid, 253 or nucleobases 254 (for core-crosslinking of micelles by base pairing) 255 for drug delivery applications, to cross-link hydrogels, 256 to microstereolithography resins as biocompatible 3D extracellular constructs, 257 or to attach dopamine for self-healing gels via Fe 3+ -ion complexation. 258 Wooley and coworkers polymerized 5-methyl-5-allyloxycarbonyl-1,3-dioxan-2one (C13) to allyl-functionalized polycarbonates. The allyl bond was transformed into aldehyde-functional polycarbonates via ozonolysis and reductive work-up.…”

Versatile cross-linked fatty acid-based polycarbonate networks obtained by thiol–ene coupling reaction

“…Indeed, such synthetic methodology was already reported for the functionalization of linear polymers but also as a mean to form cross-linked materials. [16][17][18][19][20] With this objective, the linear lipidic polycarbonate, illustrated in Fig. 2, was reacted in DCM with several dithiols in the presence of Irgacure 2959 used as radical initiator in catalytic amounts (1 mol%), to yield transparent exible materials ( Fig.…”

Postpolymerization Modifications of Alkene‐Functional Polycarbonates for the Development of Advanced Materials Biomaterials

“…The reliability of this self‐healing property was demonstrated by repeated application and removal of strain, with the complete reformation of the gel shown to occur in under 6 s after each test. DOPA‐functionalized PMAC therefore demonstrates the possibility of developing biomedical devices based on aliphatic polycarbonates which are capable of self‐healing following damage resulting from the application of excess strain …”

“…DOPA-functionalized PMAC therefore demonstrates the possibility of developing biomedical devices based on aliphatic polycarbonates which are capable of selfhealing following damage resulting from the application of excess strain. [63] The thiol-ene reaction has also been utilized for the direct conjugation of biologically active molecules. In 2008, Hu et al synthesized P(LA-co-MAC) copolymers conjugated with folic acid.…”