Molecular Design Institute and Department of Chemistry, New York University, 100 Washington Square East, New York, NY, 10003, USA.
Angew Chem Int Ed Engl. 2016 Dec 19;55(51):15873-15878. doi: 10.1002/anie.201609103. Epub 2016 Nov 17.
We report supramolecular AB diblock copolymers comprised of well-defined telechelic building blocks. Helical motifs, formed via reversible addition-fragmentation chain-transfer (RAFT) or anionic polymerization, are assembled with coil-forming and sheet-featuring blocks obtained via atom-transfer radical polymerization (ATRP) or ring-opening metathesis polymerization (ROMP). Interpolymer hydrogen bonding or metal-coordination achieves dynamic diblock architectures featuring hybrid topologies of coils, helices, and/or π-stacked sheets that, on a basic level, mimic protein structural motifs in fully synthetic systems. The intrinsic properties of each block (e.g., circular dichroism and fluorescence) remain unaffected in the wake of self-assembly. This strategy to develop complex synthetic polymer scaffolds from functional building blocks is significant in a field striving to produce architectures reminiscent of biosynthesis, yet fully synthetic in nature. This is the first plug-and-play approach to fabricate hybrid π-sheet/helix, π-sheet/coil, and helix/coil architectures via directional self-assembly.
我们报告了由定义明确的遥爪嵌段共聚物组成的超分子 AB 嵌段共聚物。通过可逆加成-断裂链转移（RAFT）或阴离子聚合形成的螺旋结构，与通过原子转移自由基聚合（ATRP）或开环复分解聚合（ROMP）获得的具有线圈形成和片状特征的嵌段组装在一起。通过聚合物间氢键或金属配位作用，可以得到具有混合拓扑结构的嵌段共聚物，包括线圈、螺旋和/或π堆积片层，在基本水平上，在完全合成的系统中模拟蛋白质结构基序。在自组装之后，每个嵌段的固有性质（例如圆二色性和荧光）保持不变。从功能构建块开发复杂的合成聚合物支架的这种策略在一个努力生产类似于生物合成的结构但本质上完全是合成的领域中具有重要意义。这是通过定向自组装制造混合π-片层/螺旋、π-片层/线圈和螺旋/线圈结构的第一种即插即用方法。
