Hierarchical Self-Assembly of a Dandelion-Like Supramolecular Polymer into Nanotubes for use as Highly Efficient Aqueous Light-Harvesting Systems
Hierarchical Self-Assembly of a Dandelion-Like Supramolecular Polymer into Nanotubes for use as Highly Efficient Aqueous Light-Harvesting Systems
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蒲公英状超分子聚合物分层自组装成纳米管，用作高效水性光捕获系统
DOI：
10.1002/adfm.201603118
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发表时间：
2016
影响因子：
19
通讯作者：
Yan Deyue
中科院分区：
文献类型：
--
作者：
Zhang Dapeng;Liu Yannan;Fan Yujiao;Yu Chunyang;Zheng Yongli;Jin Haibao;Fu Li;Zhou Yongfeng;Yan Deyue
通过环糊精端部超支化多臂共聚物（宿主）和许多功能化金刚烷（每个金刚烷都有三个烷基链臂）之间的非共价主-客偶联，构建了蒲公英状超分子聚合物（DSP），该聚合物具有“球-星-伞”拓扑结构，由球形超支化核心和许多伞状臂组成。获得的dsp可以通过连续的囊泡聚集和融合步骤，以分层的方式从囊泡到纳米管在水中自组装成纳米管。纳米管具有由多个“疏水-超支化-亲水”层组成的双层结构。这种结构对于构建类似于叶绿体的人工水光收集系统非常有用，如本文所示，通过将疏水性4‐（2‐羟乙基胺）‐7‐硝基‐2,1,3‐苯并恶二唑作为供体结合在纳米管的超支化核心内，并将亲水性罗丹明B作为受体固定在纳米管表面。这种制备的纳米管光收集系统在水中表现出意想不到的高能量传递效率（超过90%）。这扩展了具有更复杂拓扑结构、特殊自组装行为和新功能的超分子聚合物。
A dandelion‐like supramolecular polymer (DSP) with a “sphere‐star‐parachute” topological structure consisting of a spherical hyperbranched core and many parachute‐like arms is constructed by the non‐covalent host–guest coupling between a cyclodextrin‐endcapped hyperbranched multi‐arm copolymer (host) and many functionalized adamantanes with each having three alkyl chain arms (guests). The obtained DSPs can further self‐assemble into nanotubes in water in a hierarchical way from vesicles to nanotubes through sequential vesicle aggregation and fusion steps. The nanotubes have a bilayer structure consisting of multiple “hydrophobic‐hyperbranched‐hydrophilic” layers. Such a structure is very useful for constructing a chlorosome‐like artificial aqueous light‐harvesting system, as demonstrated here, via the incorporation of hydrophobic 4‐(2‐hydroxyethylamino)‐7‐nitro‐2,1,3‐benzoxadiazole as donors inside the hyperbranched cores of the nanotubes and the hydrophilic Rhodamine B as the acceptors immobilized on the nanotube surfaces. This as‐prepared nanotube light harvesting system demonstrates unexpectedly high energy transfer efficiency (above 90%) in water. This extends supramolecular polymers with more complex topological structure, special self‐assembly behavior, and new functionality.