Living crystallization-driven self-assembly (CDSA) provides robust access to uniform π-conjugated nanostructures (CNSs) from block copolymers (BCPs) containing a crystalline π-conjugated segment with controlled dimension, morphology and composition, which show appealing applications in biomedicine, photocatalysis and microelectronics. To further expand the application spectrum of these CNSs, the development of facile strategies toward diverse CNSs with varying structures/functionalities is highly desired. Herein, BCPs consisting of oligo(p-phenylene ethynylene)-b-poly(polypropyl-3-methanethiol acrylate) (OPE₉-b-PMTPA₃₅ and OPE₉-b-PMTPA₅₈; the subscript represents the number of repeat unit of each block) consisting of a crystalline π-conjugated core-forming OPE₉ segment and a corona-forming PMTPA block are synthesized. By efficient “click-type” alkylation of methylthio groups, OPE₉-b-PMTPA with varying contents of sulfonium unit is obtained. Uniform ribbon-like micelles with different widths and lengths can then be generated in a controlled manner via the self-seeding approach of living CDSA. Additionally, negatively charged polymeric and Ag nanoparticles can be immobilized on sulfonium/methylthio-containing shells by taking advantage of electrostatic attraction and coordination interaction, respectively. Interestingly, the ribbon-like micelles with positively charged shells exhibit antibacterial activity against E. coli. Given the ease of modification of PMTPA-based shell and attractive opto-electronic/photocatalytic properties of π-conjugated units, the combination of methylthio-chemistry and living CDSA opens a new avenue to generate multi-functional CNSs for widespread applications from biomedicine to photocatalysis.

活结晶驱动的自组装（CDSA）提供了从嵌段共聚物（BCP）中获得均匀π共轭纳米结构（CNS）的可靠方法，该嵌段共聚物包含具有受控尺寸、形态和组成的结晶π共轭链段，这在生物医学、光催化和微电子学。为了进一步扩大这些中枢神经系统的应用范围，非常需要针对具有不同结构/功能的多种中枢神经系统开发简便的策略。在此，BCP由低聚(对亚苯基乙炔基)-b-聚(聚丙基-3-甲硫醇丙烯酸酯)(OPE ₉ -b-PMTPA ₃₅ 和 OPE ₉ ；下标表示每个嵌段的重复单元数），由结晶π-共轭成核OPE ₉ 链段和冠-合成形成PMTPA嵌段。通过甲硫基的高效“点击式”烷基化，得到不同锍单元含量的OPE ₉ -b-PMTPA。然后可以通过活 CDSA 的自播种方法以受控方式生成具有不同宽度和长度的均匀带状胶束。此外，带负电的聚合物和银纳米颗粒可以分别利用静电吸引和配位相互作用固定在含锍/甲硫基的壳上。有趣的是，带有带正电外壳的带状胶束对大肠杆菌表现出抗菌活性。 鉴于基于 PMTPA 的壳易于修饰以及 π 共轭单元具有有吸引力的光电/光催化特性，甲硫化学和活性 CDSA 的结合开辟了生成多功能 CNS 的新途径，可广泛应用于从生物医学到光催化等领域。