Polyphenolic compounds present in tea, red wine, and chocolate form thin adherent polyphenol films on substrates through spontaneous adsorption from solution. From this observation emerged a versatile and comprehensive approach to surface modification of a variety of solid, porous, and nanoparticulate substrates composed of metals, ceramics, and polymers (see picture; ROS=reactive oxygen species).

In conventional polymer materials, mechanical performance is traditionally engineered via material structure, using motifs such as polymer molecular weight, polymer branching, or copolymer-block design1. Here, by means of a model system of 4-arm poly(ethylene glycol) hydrogels crosslinked with multiple, kinetically distinct dynamic metal-ligand coordinate complexes, we show that polymer materials with decoupled spatial structure and mechanical performance can be designed. By tuning the relative concentration of two types of metal-ligand crosslinks, we demonstrate control over the material’s mechanical hierarchy of energy-dissipating modes under dynamic mechanical loading, and therefore the ability to engineer a priori the viscoelastic properties of these materials by controlling the types of crosslinks rather than by modifying the polymer itself. This strategy to decouple material mechanics from structure may inform the design of soft materials for use in complex mechanical environments.

Transient network hydrogels cross-linked through histidine-divalent cation coordination bonds were studied by conventional rheologic methods using histidine-modified star poly(ethylene glycol) (PEG) polymers. These materials were inspired by the mussel, which is thought to use histidine-metal coordination bonds to impart self-healing properties in the mussel byssal thread. Hydrogel viscoelastic mechanical properties were studied as a function of metal, pH, concentration, and ionic strength. The equilibrium metal-binding constants were determined by dilute solution potentiometric titration of monofunctional histidine-modified methoxy-PEG and were found to be consistent with binding constants of small molecule analogs previously studied. pH-dependent speciation curves were then calculated using the equilibrium constants determined by potentiometric titration, providing insight into the pH dependence of histidine-metal ion coordination and guiding the design of metal coordination hydrogels. Gel relaxation dynamics were found to be uncorrelated with the equilibrium constants measured, but were correlated to the expected coordination bond dissociation rate constants.

The mechanical holdfast of the mussel, the byssus, is processed at acidic pH yet functions at alkaline pH. Byssi are enriched in Fe3+ and catechol-containing proteins, species with chemical interactions that vary widely over the pH range of byssal processing. Currently, the link between pH, Fe3+-catechol reactions, and mechanical function are poorly understood. Herein, we describe how pH influences the mechanical performance of materials formed by reacting synthetic catechol polymers with Fe3+. Processing Fe3+-catechol polymer materials through a mussel-mimetic acidic-to-alkaline pH change leads to mechanically tough materials based on a covalent network fortified by sacrificial Fe3+-catechol coordination bonds. Our findings offer the first direct evidence of Fe3+-induced covalent cross-linking of catechol polymers, reveal additional insight into the pH dependence and mechanical role of Fe3+- catechol interactions in mussel byssi, and illustrate the wide range of physical properties accessible in synthetic materials through mimicry of mussel protein chemistry and processing.

Interactions between polymer molecules and inorganic nanoparticles can play a dominant role in nanocomposite material mechanics, yet control of such interfacial interaction dynamics remains a significant challenge particularly in water. This study presents insights on how to engineer hydrogel material mechanics via nanoparticle interface-controlled cross-link dynamics. Inspired by the adhesive chemistry in mussel threads, we have incorporated iron oxide nanoparticles (Fe3O4 NPs) into a catechol-modified polymer network to obtain hydrogels cross-linked via reversible metal-coordination bonds at Fe3O4 NP surfaces. Unique material mechanics result from the supra-molecular cross-link structure dynamics in the gels; in contrast to the previously reported fluid-like dynamics of transient catechol–Fe3+ cross-links, the catechol–Fe3O4 NP structures provide solid-like yet reversible hydrogel mechanics. The structurally controlled hierarchical mechanics presented here suggest how to develop hydrogels with remote-controlled self-healing dynamics.