Using analogies from nature, we investigated the possibility that tyrosinase-catalyzed reactions of 3,4-dihydroxyphenethylamine (dopamine) could confer water-resistant adhesive properties to semidilute solutions of the polysaccharide chitosan. Rheological measurements showed that the tyrosinase-catalyzed, and subsequent uncatalyzed, reactions lead to substantial increases in the viscosity of the chitosan solutions. Samples from these high-viscosity modified-chitosans were spread onto dry glass slides, the slides were lapped and clipped together either in air or after being submerged in water, and the bound slides were held under water for several hours. Adhesive shear strengths of over 400 kPa were observed for these modified chitosan samples, while control chitosan solutions conferred no adhesive strength (i.e., the glass slides separated in the absence of measurable forces). High viscosities and water-resistant adhesive strengths were also observed when semidilute chitosan solutions were treated with the known cross-linking agent, glutaraldehyde. Further studies indicate a relationship between the increased viscosities and water-resistant adhesion. These results demonstrate that the renewable biopolymer chitosan can be converted into a water-resistant adhesive.

Chitosan is a natural biopolymer whose rich amine functionality confers water solubility at low pH. At higher pH's (greater than 6.5), the amines are deprotonated and chitosan is insoluble. To attain water solubility under basic conditions we enzymatically grafted the hydrophilic compound chlorogenic acid onto chitosan. Despite its name, chlorogenic acid is a nonchlorinated phenolic natural product that has carboxylic acid and hydroxyl functionality. The enzyme in this study was tyrosinase, which converts a wide range of phenolic substrates into electrophilic o-quinones. The o-quinones are freely diffusible and can undergo reaction with the nucleophilic amino groups of chitosan. Using slightly acidic conditions (pH = 6), it was possible to modify chitosan under homogeneous conditions. When the amount of chlorogenic acid used in the modification reaction exceeded 30% relative to chitosan's amino groups, the modified chitosan was observed to be soluble under both acidic and basic conditions, and to have a pH window of insolubility at near neutral pH. 1 H NMR spectra confirmed that chitosan was chemically modified, although the degree of modification was low.