2026-10-12T03:51:53Z https://api.figshare.com/v2/oai

oai:figshare.com:article/34024045 2026-09-29T13:35:35Z category_1 category_4 category_146 category_915 category_21 category_24 category_873 portal_63 item_type_6 month_year_09_2026

Spatially Defined Chemical Functionalization of Ordered Block Copolymer Materials Yuanzhi Li (1446397) Sarah A. Hesse (8927402) Wenlu Wang (7289159) Jörg G. Werner (1599277) Biophysics Biochemistry Space Science Physical Sciences not elsewhere classified Biotechnology Evolutionary Biology Chemical Sciences not elsewhere classified selective amine attachment robust 3d templates responsive smart materials intrinsically hindered due linked gyroidal network selective functionalization generates end c blocks conventional block copolymer c end block linked end block studying nanoconfined synthesis maintaining structural integrity linked blocks synthesis strategy nanoconfined hydration gel functionalization tethered non spatially defined nanoarchitected ion modular platform middle b independent manipulation gyroid nanoarchitecture generalizable concept exchange membranes equilibrium morphology design paradigm confined sulfonation combined sequential chemical versatility chemical functionality achieved selectively achieved decoupling 600 vol The independent manipulation of chemical functionality over the equilibrium morphology in conventional block copolymer (BCP) self-assembly is intrinsically hindered due to the tight composition–structure coupling. Here, we report a synthesis strategy that breaks this constraint by employing self-assembled ABC triblock terpolymer base materials with a gyroid nanoarchitecture and one cross-linked end block as robust 3D templates for the spatially defined in-gel functionalization of the tethered non-cross-linked blocks. We demonstrate this generalizable concept with selective amine attachment in the C end block for selective metal ion coordination, uptake, and nanostructure-directed metal nanoparticle synthesis. Additionally, phase-confined sulfonation is achieved selectively on both the middle B and end C blocks, respectively, producing, to the best of our knowledge, the first monolithic gyroidal hydrogels exhibiting tunable swelling up to 600 vol % and nanoconfined hydration while maintaining structural integrity. Combined sequential and block-selective functionalization generates a nanostructured, pH-responsive polyampholyte material bearing blocked cationic and anionic polymer chains tethered to the continuous and cross-linked gyroidal network. The achieved decoupling of structural and chemical versatility in these cross-linked BCP gels provides a modular platform and design paradigm for studying nanoconfined synthesis, nanoarchitected ion-exchange membranes, and stimuli-responsive smart materials. 2026-09-29T00:00:00Z Text Journal contribution 10.1021/jacs.6c09785.s001 https://figshare.com/articles/journal_contribution/Spatially_Defined_Chemical_Functionalization_of_Ordered_Block_Copolymer_Materials/34024045 CC BY-NC 4.0