Effect of ionic functional groups on the oxidation state and interfacial binding property of catechol-based adhesive

Ameya Ravindra Narkar, Michigan Technological University
Jonathan D, Kelley, Michigan Technological University
Rattapol Pinnaratip, Michigan Technological University
Bruce P. Lee, Michigan Technological University

Copyright © 2017 American Chemical Society. Publisher's version of record: https://doi.org/10.1021/acs.biomac.7b01311

Abstract

Adhesive hydrogels were prepared by copolymerizing dopamine methacrylamide with either acrylic acid (AAc) or N-(3-aminopropyl)methacrylamide hydrochloride (APMH). The effect of incorporating the anionic and cationic side chains on the oxidation state of catechol was characterized using the FOX assay to track the production of hydrogen peroxide byproduct generated during the autoxidation of catechol, and the interfacial binding property of the adhesive was determined by performing Johnson–Kendall–Roberts contact mechanics tests tested over a wide range of pH values (pH 3.0–9.0). The ionic species contributed to interfacial binding to surfaces with the opposite charge with measured work of adhesion values that were comparable to or in some cases higher than those of catechol. Addition of AAc minimized the oxidation of catechol even at a pH of 8.5 and correspondingly preserved the elevated adhesive property of catechol to both quartz and amine-functionalized surfaces. However, AAc lost its buffering capacity at pH 9.0, and catechol was oxidized at this pH. On the other hand, catechol formed a cohesive covalent bond with the network-bound amine side chain of APMH at basic pH, which interfered with the interfacial binding capability of APMH and the catechol.