RT Journal Article T1 Bioactive polymeric scaffolds: multivalent functionalization by Thermal Azide–Alkyne Cycloaddition with Alkynyl Dicarbamates A1 Tawara, Maun H. A1 Correa Chinea, Juan Francisco A1 Leire, Emma A1 Delgado González, Bruno A1 Parcero Bouzas, Samuel A1 Liko, Flonja A1 Fernández Megía, Eduardo K1 Dendrons K1 Fluorescence K1 Functionalization K1 Hydrocarbons K1 Micelles AB Multivalency enables interactions with higher affinities and specificities than monovalent interactions. The strategy exploited by nature to modulate biorecognition has inspired the design of multivalent conjugates with therapeutic properties. However, chemical functionalization often requires coupling agents, additives, or metal catalysts that complicate isolation and purification. Herein, azide–alkyne cycloaddition (AAC) with alkynyl dicarbamates (Alk-R) is presented as a flexible, reliable, atom-economical, and user-friendly strategy for the multivalent functionalization of polymeric scaffolds. Alk-R functionalized with biologically relevant ligands have been prepared and used for the multivalent AAC functionalization of azide-bearing dendrimers and block copolymers. The resulting polymers with double multivalency reveal a platform for the development of bioinspired functional systems with promising applications in drug delivery: block copolymer micelles and multifunctional nanocarriers with synergistically integrated probes-ligands-drugs. The extension of this strategy to other ligands and scaffolds is expected to open up a wide range of therapeutic and diagnostic opportunities. PB American Chemical Society SN 1525-7797 YR 2025 FD 2025 LK https://hdl.handle.net/10347/43316 UL https://hdl.handle.net/10347/43316 LA eng NO Tawara, M. H., Correa, J., Leire, E., Gonzalez, B. D., Parcero-Bouzas, S., Liko, F., & Fernandez-Megia, E. (2025). Bioactive Polymeric Scaffolds: Multivalent Functionalization by Thermal Azide–Alkyne Cycloaddition with Alkynyl Dicarbamates. "Biomacromolecules". https://doi.org/10.1021/acs.biomac.5c00038 NO This work was supported by grant PID2021-127684OB-I00 funded by MCIN/AEI/10.13039/501100011033 and by ERDF “A way of making Europe.” The authors thank the f inancial support from Xunta de Galicia (ED431C 2022/21, and Centro de Investigación do Sistema Universitario de Galicia accreditation 2023-2027, ED431G 2023/03) and the European Union (European Regional Development Fund� ERDF). B.D.G. thanks Xunta de Galicia for a predoctoral grant. E.L. and F.L. thank the European Commission, Education, Audiovisual and Cultural Executive Agency (EACEA) for an Erasmus Mundus grant under the NanoFar Joint Doctoral Program DS Minerva RD 3 may 2026