Progress in ATRP-derived materials for biomedical applications

The continuing wave of technological breakthroughs and advances is critical for engineering well-defined materials, particularly biomaterials, with tailored microstructure and properties. Over the last few decades, controlled radical polymerization (CRP) has become a very promising option for the synthesis of precise polymeric materials with an unprecedented degree of control over molecular architecture. Atom transfer radical polymerization (ATRP), one of the most robust and efficient CRPs, has been at the forefront of the synthesis of well-defined polymers with controlled/predetermined molecular weights, polydispersity, topology, composition, and site-specific functionality. ATRP has been leveraged to prepare a wide range of polymers with properties tailored for a number of biomedical applications. Furthermore, ATRP can also be utilized to introduce stimuli-responsive properties into the chemical structure of polymers. Moreover, the degradation behavior of ATRP-derived polymers can be tailored by incorporating chemical bonds susceptible to hydrolysis or proteolysis. This strategy allows the design of degradable polymers for in vivo applications. This review summarizes the recent advances in ATRP for the design of functional materials and techniques implemented to advance the biomedical field, such as surface modification and functionalization. Additionally, the latest applications and progress of ATRP-derived materials in various biomedical arenas such as drug delivery, tissue engineering, bioimaging, and biosensing are reported. Lastly, the current limitations and future perspectives of ATRP-derived biomaterials are carefully discussed to support further improvement of their properties and performance for translatability into the clinic. Moving forward, there is a need for further development of ATRP to align with green chemistry principles. This entails exploring the use of renewable monomers, environmentally friendly and nontoxic solvents, as well as metal-free and biocompatible catalysts. Additionally, researchers should thoroughly investigate the bioactivity, biodegradation behavior, and in vivo fate of ATRP-derived polymers and polymer conjugates before considering their translation into clinical applications.