Abstract

While the design of responsive and/or proactive polymeric chains mimicking biological systems are essential building blocks for future developments of smart coatings, the physico‐chemical aspects of processes associated with the film formation are equally important. Chemistries that are key enablers to many next‐generation materials that will become capable of mimicking biological systems involve amino acids, hydroxyls, phosphate esters, acetyls, thiols, acryloamides, and carboxyl‐terminated species. Equally important is how these species may generate various forms of responsiveness in synthetic polymers, either by chemical reactions with other groups, or hydrophilic and/or hydrophobic interactions where the placement of oligosacchrides, peptides, or nucleaic acid groups in a specific position will generate intra and intermolecular interactions leading to supramolecular assemblies. Regardless of internal or external stimuli, typical responses lead to shape, size, and orientation changes, which is why the majority of stimuli‐responsive processes occur at the interfacial or inter‐phase regions. Creating “network space” within polymer arrays allowing favorable rearrangements of macromolecular arrays may be accomplished by creating environments with localized glass transition temperature gradients, creating phase separated networks, or a deliberate addition of other architectures.

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