Increasing spontaneous wet adhesion of DOPA with gelation characterized by EPR spectroscopy

The presence of water molecules around both adhesive materials and surface results in the hydration barriers that weaken adhesion. In nature, mussels attach to various types of surfaces by using 3,4-dihydroxyphenylalanine (DOPA) containing mussel foot proteins. DOPA shows wet adhesive properties before and after contribution in the hydrogel formation. Here, the wet adhesive properties of DOPA modified four armed poly (ethylene glycol) polymer (PEG-(DOPA)(4)) and its hydrogels induced by (IO4)(-) or (Cr2O7)(2-) ions are compared by using electron paramagnetic resonance (EPR) spectroscopy in terms of their surface coverages. In water, spin labeled hydrophobic polystyrene (SL-PS) and hydrophilic silica (SL-SiO2) nanoparticles are prepared, and the percentages of their covered surface values are obtained. Without applying force, the adhesion to SL-PS increases in the order of PEG-(DOPA)(4) < PEG-(DOPA)(4) + (IO4)(-) hydrogel < PEG-(DOPA)(4) + (Cr2O7)(2-) hydrogel with the percentages of surface coverages 65%, 76% and 93%, respectively. Although, neither of PEG-(DOPA)(4) polymer and (IO4)(-) induced PEG-(DOPA)(4) hydrogel adhere to SL-SiO2 nanoparticle spontaneously, (Cr2O7)(2-) induced PEG-(DOPA)(4) hydrogel adhere to SL-SiO2 with a 59% of surface coverage. These results show that gelation mechanisms of DOPA have effect on the spontaneous adhesion of DOPA to the wet surfaces even for the hydrophilic silica surface.