Citation: Li Huimei, Wang Jie, Ni Yunzhou, Zhou Yongfeng, Yan Deyue. Synthesis of a Linear-Hyperbranched Supramolecular Polymer and Its Light-Responsive Self-Assembly Behavior[J]. Acta Chimica Sinica, ;2016, 74(5): 415-421. doi: 10.6023/A16020076 shu

Synthesis of a Linear-Hyperbranched Supramolecular Polymer and Its Light-Responsive Self-Assembly Behavior

1.
College of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240

Corresponding author: Zhou Yongfeng, yfzhou@sjtu.edu.cn
Received Date: 1 February 2016

Fund Project: the National Natural Science Foundation of China 21474062the National Basic Research Program 2013CB834506the National Natural Science Foundation of China 91527304the China National Funds for Distinguished Young Scholar 21225420

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Herein we reported the synthesis, self-assembly and light-responsive disassembly of a "linear-hyperbranched" supramolecular polymer. Firstly, a hyperbranched polymer CD-g-HPG composed of hyperbranched polyglycerol with a β-cyclodextrin group in the center was synthesized by ring-opening multibranching polymerization (ROMBP). Secondly, a linear polymer AZO-PS composed of polystyrene with an azobenzene group at the end was synthesized via atom transfer radical polymerization (ATRP). Then, the linear AZO-PS and hyperbranched CD-g-HPG were conjugated together through the specific CD/AZO host-guest interactions, leading to the formation of the "linear-hyperbranched" supramolecular polymer PS-b-HPG. This supramolecular polymer was amphiphilic and could self-assemble into vesicles in water. The host-guest complexation ability was characterized by UV-Vis titration. In the case of keeping the concentration of AZO-PSs unchanged, the absorption peak at 330 nm increased gradually with the addition of CD-g-HPGs, which supported the occurrence of complexation between β-CD groups in CD-g-HPGs and AZO groups in AZO-PSs. The host-guest CD/AZO complexation constant of 4.14×10⁴ M^-¹ was calculated by the Benesi-Hildebrand plot. A Job plot was generated, from which it was determined that the binding stoichiometry between AZO-PS and CD-g-HPG is 1:1. The self-assemblies of the amphiphlic linear-hyperbranched supramolecular polymers were characterized by SEM and TEM. The SEM images showed that the self-assemblies were spherical particles, and the holes directly be seen in some particles indicated that they were vesicles or hollow spheres with a very thin wall thickness. The TEM images of self-assemblies stained with ruthenium tetroxide (RuO₄) indicated that the spherical particles were vesicles according to a clear contrast difference between the inner pool and the outer thin wall. At last, we showed that the vesicles could disassemble under UV light due to the trans-to-cis isomerisation of the AZO groups. With the continuous UV irradiation on vesicles, the absorption peak of trans-AZO diminished gradually and almost completely disappeared after 900 seconds. Meanwhile, the solution was transformed from turbid to transparent followed with the appearance of yellow precipitates in the bottom of the bottle.
- supramolecular polymers,
- linear-hyperbranched,
- host-guest interactions,
- self-assembly,
- light responsive
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沈阳化工大学材料科学与工程学院沈阳 110142