Gao Pan, Cao Hui, Ding Yi, Cai Meng, Cui Zhigang, Lu Xinhua, Cai Yuanli
State-Local Joint Engineering Laboratory of Novel Functional Polymeric Materials, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China.
ACS Macro Lett. 2016 Dec 20;5(12):1327-1331. doi: 10.1021/acsmacrolett.6b00796. Epub 2016 Nov 16.
Analogous to cellulose, polymers whose monomer units possess both hydrogen donators and acceptors are generally insoluble in ambient water because of hydrogen bonding (HB). Herein we present stimuli-responsive long aqueous cylindrical vesicles (nanotubes) synthesized directly using HB-driven polymerization-induced self-assembly (PISA) under visible-light-mediated RAFT aqueous dispersion polymerization at 25 °C. The PISA undergoes an unprecedented film/silk-to-ribbon-to-vesicle transition and films/silks/ribbons formed at low DPs (∼25-85) of core-forming block in free-flowing aqueous solution. Pore-switchable nanotubes are synthesized by electrostatic repulsive perturbation of the HB association in anisotropic vesicular membranes via inserting minor ionized monomer units into the core-forming block. These nanotubes are synthesized at >35% solids, and tubular membranes are more sensitive than spherical counterparts in response to aqueous surroundings. This facile, robust, and general strategy paves a new avenue toward scale-up production of advanced intelligent nanomaterials.
与纤维素类似，其单体单元同时具有氢供体和受体的聚合物，由于氢键作用（HB），通常在环境水中不溶。在此，我们展示了在25℃可见光介导的可逆加成-断裂链转移（RAFT）水分散聚合反应中，通过氢键驱动的聚合诱导自组装（PISA）直接合成的刺激响应性长水性圆柱形囊泡（纳米管）。PISA经历了前所未有的膜/丝到带再到囊泡的转变，并且在自由流动的水溶液中，在成核嵌段的低聚合度（约25 - 85）下形成膜/丝/带。通过将少量离子化单体单元插入成核嵌段，对各向异性囊泡膜中的氢键缔合进行静电排斥扰动，合成了孔隙可切换的纳米管。这些纳米管在固体含量>35%时合成，并且管状膜对水环境的响应比球形膜更敏感。这种简便、稳健且通用的策略为先进智能纳米材料的放大生产开辟了一条新途径。
