The adhesive capabilities of intertidal marine species, such as mussels, have recently provided a wealth of inspiration toward the design and development of new materials. Mussels show a unique ability to affix themselves to wet, heterogeneous surfaces such as rocks, and maintain adhesion under the high-energy, turbulent environment of the intertidal zones. While the natural adhesives employed by these organisms are a complex mixture of proteins, 3,4-dihydroxyphenylalanine (DOPA) has been identified as a common constituent that plays a central role in the curing and interfacial interactions of the adhesive plaques. DOPA is thought to play two primary roles in such bioadhesives: first, to facilitate cross-linking via the formation of di-DOPA linkages leading to solidification of precursor proteins, where cross-linking may occur via oxidative, enzymatic, or redox induced radical chemistry and, second, to facilitate adhesion to heterogeneous substrates via DOPA's ability to undergo hydrogen bonding, p�p aromatic interactions, and metal�ligand complexation with a variety of surface functionalities. Inspired by the salient features of natural bioadhesives, interest in designing synthetic polymeric systems that incorporate DOPA and analogous catecholic moieties as active adhesive constituents has proliferated in recent years. In this presentation, we report the synthesis of a dihydroxy eugenol derivative, 4-prop-2-enylbenzene-1,2-diol (EugOH), and its subsequent incorporation into a thiol-ene network based on pentaerythritol triallyl ether (APE) and pentaerythritol tetra(3-mercaptopropionate) (PETMP). The catechol monomer shows improved miscibility with multifunctional thiols and enes commonly used in thiol-ene polymerizations enabling solvent-free resin systems. Comparing to the naturally occurring eugenol and its methylated analogue, methyl eugenol, the effect of the pendant catechol moiety, in the nonoxidized form, on photopolymerization kinetics, thermal, thermomechanical, and adhesive properties has been evaluated.

�Sticky� thiol-ene polymer networks using natural product derivatives

247th National Meeting (2014)

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