Molecular surface chemistry in marine bioadhesion

• Marine biofouling on manmade structures has both economic and environmental costs.
• Marine bioadhesive compositions are revealed by surface-sensitive spectroscopies.
• Binding modes of recurrent adhesive functionalities to metal oxides are reviewed.
• Competitive adsorption studies of surveyed adhesive functionalities are reported.
• Specific ion effects explain differences in metal–ligand binding affinities.

This review covers the in situ molecular physicochemical characterisation of bioadhesives at solid/liquid interfaces, with the aim of elucidating the adhesion strategies that lie at the root of marine biofouling. It focuses on three major foulers: mussels, algae and barnacles. The dispersal of these organisms, their colonisation of surfaces, and ultimately their survival rely critically on the ability of the organisms' larvae or spores to locate a favourable settlement site and undergo metamorphosis, thus initiating their sessile existence. Differences in the composition of adhesive secretions and the strategies employed for their temporary or permanent implementation exists between the larval and adult life stages. To date, only a few adhesive secretions from marine fouling organisms have been adequately described in terms of their chemical composition, and a survey revealed the presence of certain recurrent functional groups, specifically catechol, carboxylate, monoester-sulphate and -phosphate. This review will describe the binding modes of such functionalities to wet mineral/metal oxides surfaces. Such functionalities will be ranked based on their ability to bind to hydrophilic surfaces replacing surface-bound water (Langmuir adsorption constant) as well as other adsorbates (competitive adsorption). A plausible explanation for the propensity of the reviewed adhesive functionalities to bind to hydrous metal oxide surfaces will be given on the basis of the Hard and Soft Acids and Bases principle, Hofmeister effects and entropic considerations. From the in situ analysis of marine organism bioadhesives and adsorption studies of functionalities relevant to the bioadhesion process, insights can be gleaned for a knowledge-based innovation of antifouling strategies and the synthesis of strong, durable adhesive materials, which are suitable for implementation in wet environments.

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