Self-healing hydrogels

Self-healing hydrogels are a specialized type of polymer hydrogel. A hydrogel is a macromolecular polymer gel constructed of a network of crosslinked polymer chains. Hydrogels are synthesized from hydrophilic monomers by either chain or step growth, along with a functional crosslinker to promote network formation. A net-like structure along with void imperfections enhance the hydrogel's ability to absorb large amounts of water via hydrogen bonding. As a result, hydrogels, self-healing alike, develop characteristic firm yet elastic mechanical properties. Self-healing refers to the spontaneous formation of new bonds when old bonds are broken within a material. The structure of the hydrogel along with electrostatic attraction forces drive new bond formation through reconstructive covalent dangling side chain or non-covalent hydrogen bonding. These flesh-like properties have motivated the research and development of self-healing hydrogels in fields such as reconstructive tissue engineering as scaffolding, as well as use in passive and preventive applications.Other chain growth methods include anionic and cationic polymerization. Both anionic and cationic methods suffer from extreme sensitivity toward aqueous environments and therefore, are not used in the synthesis of polymeric hydrogels. Self-healing hydrogels are a specialized type of polymer hydrogel. A hydrogel is a macromolecular polymer gel constructed of a network of crosslinked polymer chains. Hydrogels are synthesized from hydrophilic monomers by either chain or step growth, along with a functional crosslinker to promote network formation. A net-like structure along with void imperfections enhance the hydrogel's ability to absorb large amounts of water via hydrogen bonding. As a result, hydrogels, self-healing alike, develop characteristic firm yet elastic mechanical properties. Self-healing refers to the spontaneous formation of new bonds when old bonds are broken within a material. The structure of the hydrogel along with electrostatic attraction forces drive new bond formation through reconstructive covalent dangling side chain or non-covalent hydrogen bonding. These flesh-like properties have motivated the research and development of self-healing hydrogels in fields such as reconstructive tissue engineering as scaffolding, as well as use in passive and preventive applications. A variety of different polymerization methods may be utilized for the synthesis of the polymer chains that make up hydrogels. Their properties depend to an important extent on how these chains are crosslinked. Crosslinking is the process of joining two or more polymer chains. Both chemical and physical crosslinking exists. In addition, both natural polymers such as proteins or synthetic polymers with a high affinity for water may be used as starting materials when selecting a hydrogel. Different crosslinking methods can be implemented for the design of a hydrogel. By definition, a crosslinked polymer gel is a macromolecule that solvent will not dissolve. Due to the polymeric domains created by crosslinking in the gel microstructure, hydrogels are not homogenous within the selected solvent system. The following sections summarize the chemical and physical methods by which hydrogels are crosslinked. Hydrogen bonding is a strong intermolecular force that forms a special type of dipole-dipole attraction. Hydrogen bonds form when a hydrogen atom bonded to a strongly electronegative atom is around another electronegative atom with a lone pair of electrons. Hydrogen bonds are stronger than normal dipole-dipole interactions and dispersion forces but they remain weaker than covalent and ionic bonds. In hydrogels, structure and stability of water molecules are highly affected by the bonds. The polar groups in the polymer strongly bind water molecules and form hydrogen bonds which also cause hydrophobic effects to occur. These hydrophobic effects can be exploited to design chemically crosslinked hydrogels that exhibit self healing abilities. The hydrophobic effects combined with the hydrophilic effects within the hydrogel structure can be balanced through dangling side chains that mediates the hydrogen bonding that occurs between two separate hydrogel pieces or across a ruptured hydrogel. A dangling side chain is a hydrocarbon chain side chains that branch off of the backbone of the polymer. Attached to the side chain are polar functional groups. The side chains 'dangle' across the surface of the hydrogel, allowing it to interact with other functional groups and form new bonds. The ideal side chain would be long and flexible so it could reach across the surface to react, but short enough to minimize steric hindrance and collapse from the hydrophobic effect. The side chains need to keep both the hydrophobic and hydrophilic effects in balance. In a study performed by the University of California San Diego to compare healing ability, hydrogels of varying side chain lengths with similar crosslinking contents were compared and the results showed that healing ability of the hydrogels depends nonmonotonically on the side chain length. With shorter side chain lengths, there is limited reach of the carboxyl group which decreases the mediation of the hydrogen bonds across the interface. As the chain increases in length, the reach of the carboxyl group becomes more flexible and the hydrogen bonds can mediated. However, when a side chain length is too long, the interruption between the interaction of the carboxyl and amide groups that help to mediate the hydrogen bonds. It can also accumulate and collapse the hydrogel and prevent the healing from occurring. Most self-healing hydrogels rely on electrostatic attraction to spontaneously create new bonds. The electrostatic attraction can be masked using protonation of the polar functional groups. When the pH is raised the polar functional groups become deprotonated, freeing the polar functional group to react.Since the hydrogels rely on electrostatic attraction for self-healing, the process can be affected by electrostatic screening. The effects of a change in salinity can be modeled using the Gouy-Chapman-Stern theory Double Layer .