2026-10-09T17:12:54Z https://api.figshare.com/v2/oai

oai:figshare.com:article/34038044 2026-10-01T04:11:15Z category_7 category_19 category_21 category_873 category_734 category_61 category_64 portal_63 item_type_6 month_year_10_2026

Photoinitiated Radical Thiol–Ene/Methacrylate versus Thia-Michael Addition in Polyurethane-Grafted Networks: A Comparative Study of Polymeric Drug Delivery Platforms Amita Santra (18262309) Souvik Debnath (20552111) Alaka T. Panicker (25151543) Kaushik Chatterjee (1452559) Pralay Maiti (1611559) Medicine Pharmacology Biotechnology Chemical Sciences not elsewhere classified Biological Sciences not elsewhere classified Developmental Biology Cancer tuning backbone chemistry providing fresh hope greater thiol conversion evaluating anticancer efficacy dynamic shear rheology combine therapeutic functionality biomedical practice necessitates alamarblue alongside ros advanced healthcare applications homogeneous network compared advanced polymer science cancer cell mortality 1 </ sup methacrylate versus thia especially cancer treatment methacrylate reaction grafted network based polymer thermoplastic behavior subtle variations subsequently grafted structural analysis state viscoelasticity results show regenerative medicine practical outcomes photoinitiated approach nuanced comprehension next generation molecular precision michael addition integrative approach highly cross h nmr grafted networks engineered biomaterials comprehensive comparison complex diseases comparative study catalyzed thia biomaterial platforms biological interactions better predictive adaptable chemistries 8 %). 72 h 5 %) 3 assays 231 cells In the age of advanced polymer science and regenerative medicine, biomaterial platforms are being developed that combine therapeutic functionality and molecular precision, providing fresh hope for the treatment of complex diseases, such as cancer. Translating these adaptable chemistries into biomedical practice necessitates a nuanced comprehension of how subtle variations in network formation mechanisms affect the practical outcomes. Herein, copolymers were synthesized using a base-catalyzed thia-Michael addition and a photoinitiated radical thiol–ene/methacrylate reaction, respectively, and subsequently grafted with polyurethane to yield corresponding grafted copolymers. A comprehensive comparison was carried out using ¹H NMR and GPC for structural analysis, dynamic shear rheology for melt-state viscoelasticity, and alamarBlue alongside ROS and caspase-3 assays for evaluating anticancer efficacy against MDA-MB-231 cells. Results show that the base-initiated click reaction yielded a greater thiol conversion (47.5%) and a more homogeneous network compared to the photoinitiated approach (22.8%). While both graft copolymers exhibited significant shear thinning and thermoplastic behavior, the highly cross-linked photo-based polymer (Graft-P) showed a greater steady shear viscosity. Ultimately, the thia-Michael polyurethane-grafted network (Graft-C) with tailored hydrophilic–hydrophobic balance provided better sustained paclitaxel release, resulting in about 70% cancer cell mortality over 72 h as opposed to 55% for the photo-based grafted polymer network. Through this integrative approach, we demonstrate how tuning backbone chemistry and postsynthetic grafting drives functional performance and shape the next generation of engineered biomaterials: more resilient, tunable, and better predictive in their biological interactions, well-suited for advanced healthcare applications, especially cancer treatment. 2026-10-01T00:00:00Z Text Journal contribution 10.1021/acsapm.6c02793.s001 https://figshare.com/articles/journal_contribution/Photoinitiated_Radical_Thiol_Ene_Methacrylate_versus_Thia-Michael_Addition_in_Polyurethane-Grafted_Networks_A_Comparative_Study_of_Polymeric_Drug_Delivery_Platforms/34038044 CC BY-NC 4.0