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It starts with the evolution of synthetic polymers in biomedical applications, from early non-degradable and biodegradable materials to advanced smart responsive systems. The fundamental principles of radical polymerization are introduced, followed by a systematic classification of strategies employed in cellular settings, including thermal decomposition initiation, photoinitiation, intracellular environment-triggered polymerization, and controlled radical polymerization techniques such as atom transfer radical polymerization (ATRP) and reversible addition\u2212fragmentation chain transfer polymerization (RAFT). This article highlights key innovations in cell surface engineering, intracellular imaging, drug delivery, and cancer therapy, with an emphasis on strategies that leverage cellular metabolism or disease-specific microenvironments for endogenous polymerization initiation. Current challenges, including spatiotemporal control, biocompatibility, and oxygen tolerance, are critically discussed, along with potential solutions. Finally, future perspectives on the application of radical polymerization in tissue engineering, immunomodulation, and precision medicine are presented.<\/jats:p>","DOI":"10.1021\/acs.biomac.6c00909","type":"journal-article","created":{"date-parts":[[2026,9,8]],"date-time":"2026-09-08T13:01:53Z","timestamp":1788872513000},"page":"6260-6288","source":"Crossref","is-referenced-by-count":0,"title":["Strategies and Applications of Radical Polymerization in Cellular Microenvironments"],"prefix":"10.1021","volume":"27","author":[{"given":"Shiyi","family":"Xiao","sequence":"first","affiliation":[{"name":"Nanjing University of Science and Technology , , , ,","place":["Nanjing, Jiangsu, China, 210094"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shijin","family":"Zhou","sequence":"additional","affiliation":[{"name":"Nanjing University of Science and Technology , , , ,","place":["Nanjing, Jiangsu, China, 210094"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhidan","family":"Tian","sequence":"additional","affiliation":[{"name":"Nanjing Medical University , , , ,","place":["Nanjing, Jiangsu, China, 210006"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5721-6513","authenticated-orcid":true,"given":"Jinming","family":"Kong","sequence":"additional","affiliation":[{"name":"Nanjing University of Science and Technology , , , ,","place":["Nanjing, Jiangsu, China, 210094"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0035-3821","authenticated-orcid":true,"given":"Xueji","family":"Zhang","sequence":"additional","affiliation":[{"name":"Shenzhen University Health Science Center , , ,","place":["Shenzhen, China, 518060"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,8]]},"reference":[{"key":"2026101210513484900_cit1","doi-asserted-by":"publisher","first-page":"167","DOI":"10.1016\/j.matpr.2019.04.188","article-title":"Strength analysis of Cranioplasty PMMA flap material","volume":"15","author":"Archana","year":"2019","journal-title":"Materials Today: Proc."},{"issue":"1","key":"2026101210513484900_cit2","doi-asserted-by":"publisher","first-page":"35","DOI":"10.1615\/critrevbiomedeng.2021037591","article-title":"PMMA Bone Cement in Interventional Oncology","volume":"49","author":"Garnon","year":"2021","journal-title":"Crit. 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