Citation: Li Rongye, Mehul Khiman, Sheng Li, Sun Jing. pH/Solvent Tunable Hierarchical Nanostructures Assembled from an Amphiphilic Polypeptide-containing Triblock Copolymer[J]. Acta Chimica Sinica, ;2020, 78(11): 1235-1239. doi: 10.6023/A20080339 shu

pH/Solvent Tunable Hierarchical Nanostructures Assembled from an Amphiphilic Polypeptide-containing Triblock Copolymer

Li Rongye ^† ,
Mehul Khiman ^† ,
Sheng Li ,
Sun Jing ^,

College of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China

Corresponding author: Sun Jing, jingsun@qust.edu.cn
Received Date: 1 August 2020
Available Online: 4 September 2020
Fund Project: the National Natural Science Foundation of China 21674054Project supported by the National Natural Science Foundation of China (Nos. 51722302 and 21674054) and the Natural Science Foundation of Shandong Province (No. ZR2019JQ17)the National Natural Science Foundation of China 51722302the Natural Science Foundation of Shandong Province ZR2019JQ17

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Similar to natural proteins, polypeptides can form secondary structures depending on their physical properties. Many efforts have been made towards the self-assembly of triblock copolymer containing polypeptide as an important component to construct hierarchical structures by utilizing the pH-responsive conformation transformation. In this work, a pH-responsive poly(ethylene glycol)-b-poly(L-lysine)-b-poly(styrene) (PEG-b-PLL-b-PS) triblock copolymer was prepared via a combination of controlled ring opening polymerization (ROP) and atom transfer radical polymerization (ATRP). In the triblock copolymer, PLL is water-soluble in acidic solution with random coil conformation, but becomes insoluble helix in alkaline solution. PEG has excellent water solubility that can exhibit protein-resistant property. PS serves as hydrophobic part. Self-assembly of the polymer was examined by transmission electron microscopy (TEM), atomic force microscopy (AFM) and attenuated total reflection-infrared spectrometer (ATR-IR). The triblock copolymer forms spherical micelles in 1:1 volume ratio of tetrahydrofuran-water mixed solvent, in which the hydrophobic PS segment forms a core and the two hydrophilic segments PLL and PEG serve as shell and corona, respectively. The spheres as the subunits further transform into hierarchical 1D fiber-like structure in the presence of THF after 7 d of aging, confirmed by both TEM and AFM techniques. Upon removing THF, the spherical shape was re-obtained with slightly smaller diameter, so called "frozen micelles". Further, the diameter of the spheres increases with pH increasing. A sphere-to-vesicle transition was observed at pH 13 as the secondary conformation of PLL transforms from coil to α-helix. The dialysis of these solutions can convert the vesicles back into spherical morphology with slightly smaller diameter.
- triblock copolymer,
- ring-opening polymerization,
- atom transfer radical polymerization,
- self-assembly,
- pH responsive,
- nanostructure
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