▪ Abstract Photoinitiated polymerization and polymer crosslinking are viable strategies for biomaterial synthesis because of the mild temperatures and neutral pH environments in which these reactions typically take place. This review summarizes the relevant theories as well as current status of photoinitiated polymerizations in biomaterials. Photoinitiation, photoinitiated polymerization, and photoinitiators are discussed with consideration toward the biological nature of the intended application. Recent investigations into biomaterials, including hydrogels, biodegradable materials, and hard tissue resorbable scaffolds are presented. Lastly, studies of cell interactions with photoinitiated biomaterials are discussed. The work herein illustrates the potential use of photoinitiated polymerization in the development of novel biomaterials for tissue engineering.
Synthetic hydrogels are investigated extensively in tissue engineering for their tunable physicochemical properties but are bioinert and lack the tissue-specific cues to produce appropriate biological responses. To introduce tissue-specific biochemical cues to these hydrogels, we have developed a modular hydrogel cross-linker, poly(glycolic acid)–poly(ethylene glycol)–poly(glycolic acid)-di(but-2-yne-1,4-dithiol) (PdBT), that can be functionalized with small peptide-based cues and large macromolecular cues simply by mixing PdBT in water with the appropriate biomolecules at room temperature. Cartilage- and bone-specific PdBT macromers were generated by functionalization with a cartilage-associated hydrophobic N-cadherin peptide, a hydrophilic bone morphogenetic protein peptide, and a cartilage-derived glycosaminoglycan, chondroitin sulfate. These biofunctionalized PdBT macromers can spontaneously cross-link polymers such as poly(N-isopropylacrylamide) to produce rapidly cross-linking, highly swollen, cytocompatible, and hydrolytically degradable hydrogels suitable for mesenchymal stem cell encapsulation. These favorable properties, combined with PdBT’s modular design and ease of functionalization, establish strong potential for its usage in tissue engineering applications.
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