Responsive polymer materials can adapt to surrounding environments, regulate transport of ions and molecules, change wettability and adhesion of different species on external stimuli, or convert chemical and biochemical signals into optical, electrical, thermal and mechanical signals, and vice versa. These materials are playing an increasingly important part in a diverse range of applications, such as drug delivery, diagnostics, tissue engineering and 'smart' optical systems, as well as biosensors, microelectromechanical systems, coatings and textiles. We review recent advances and challenges in the developments towards applications of stimuli-responsive polymeric materials that are self-assembled from nanostructured building blocks. We also provide a critical outline of emerging developments.

Inspired by nature, self-healing materials represent the forefront of recent developments in materials chemistry and engineering. This review outlines the recent advances in the field of self-healing polymers. The first part discusses thermodynamic requirements for self-healing networks in the context of conformation changes that contribute to the Gibbs free energy. The chain flexibility significantly contributes to the entropy changes, whereas the heat of reaction and the external energy input are the main contributors to enthalpy changes. The second part focuses on chemical reactions that lead to self-healing, and the primary classes are the covalent bonding, supramolecular assemblies, ionic interactions, chemo-mechanical self-healing, and shape memory polymers. The third part outlines recent advances using encapsulation, remote self-healing and the role of shape memory polymers. Recent developments in the field of self-healing polymers undeniably indicate that the main challenge will be the designing of high glass transition (Tg) functional materials, which also exhibit stimuli-responsive attributes. Build-in controllable hierarchical heterogeneousness at various length scales capable of remote self-healing by physical and chemical responses will be essential in designing future materials of the 21st century.

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Polyurethanes have many properties that qualify them as high-performance polymeric materials, but they still suffer from mechanical damage. We report the development of polyurethane networks that exhibit self-repairing characteristics upon exposure to ultraviolet light. The network consists of an oxetane-substituted chitosan precursor incorporated into a two-component polyurethane. Upon mechanical damage of the network, four-member oxetane rings open to create two reactive ends. When exposed to ultraviolet light, chitosan chain scission occurs, which forms crosslinks with the reactive oxetane ends, thus repairing the network. These materials are capable of repairing themselves in less than an hour and can be used in many coatings applications, ranging from transportation to packaging or fashion and biomedical industries.

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The concept of self-healing synthetic materials emerged a couple of decades ago and continues to attract scientific community. Driven primarily by an opportunity to develop lifelike materials on one hand, and sustainable technologies on the other, several successful approaches to repair mechanically damaged materials have been explored. This review examines chemical and physical processes occurring during self-healing of polymers as well as examines the role of interfaces in rigid nano-objects in multicomponent composites. The complex nature of processes involved in self-healing demands understanding of multi-level molecular and macroscopic events. Two aspects of self-healing are particularly intriguing: physical flow (macro) of matter at or near a wound and chemical re-bonding (molecular)of cleaved bonds. These events usually occur concurrently, and depending upon interplay between kinetics and thermodynamics of the processes involved, these transient relations as well as efficiency are critical in designing self-healing materials. This review examines covalent bonding and supramolecular chemistry in the context of molecular heterogeneities in repair processes. Interfacial regions in nanocomposites also facilitate an opportunity for supramolecular assemblies or covalent bonding which, if designed properly, are capable of self-repairs.

Self-healing materials are notable for their ability to recover from physical or chemical damage. We report that commodity copolymers, such as poly(methyl methacrylate)/n-butyl acrylate [p(MMA/nBA)] and their derivatives, can self-heal upon mechanical damage. This behavior occurs in a narrow compositional range for copolymer topologies that are preferentially alternating with a random component (alternating/random) and is attributed to favorable interchain van der Waals forces forming key-and-lock interchain junctions. The use of van der Waals forces instead of supramolecular or covalent rebonding or encapsulated reactants eliminates chemical and physical alterations and enables multiple recovery upon mechanical damage without external intervention. Unlike other self-healing approaches, perturbation of ubiquitous van der Waals forces upon mechanical damage is energetically unfavorable for interdigitated alternating/random copolymer motifs that facilitate self-healing under ambient conditions.

Reversible addition−fragmentation chain transfer (RAFT) is a versatile, controlled free radical polymerization technique that operates via a degenerative transfer mechanism in which a thiocarbonylthio compound acts as a chain transfer agent. The subsequent reduction of the dithioester end groups to thiols allows the preparation of (co)polymer-modified gold surfaces. Herein we report the immobilization of poly(sodium 4-styrenesulfonate), poly((ar-vinylbenzyl) trimethylammonium chloride), poly(N,N-dimethylacrylamide), and poly(3-[2-(N-methylacrylamido)-ethyldimethyl ammonio]propane sulfonate-b-N,N-dimethylacrylamide) onto gold films. The presence of the immobilized (co)polymers was confirmed by atomic force microscopy, attenuated total reflectance Fourier transform infrared spectroscopy, and surface contact angle measurements. The gold film modified with the block copolymer demonstrated stimuli-responsive behavior as evidenced by its water contact angle being similar to that of poly(N,N-dimethylacrylamide) even though the block based on 3-[2-(N-methylacrylamido)-ethyldimethyl ammonio] propane sulfonate was expected to be exposed to the aqueous environment.