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

doi:10.6023/A20080339

Abstract

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.

Key words: triblock copolymer, ring-opening polymerization, atom transfer radical polymerization, self-assembly, pH responsive, nanostructure

Cite this article

Li Rongye, Khiman Mehul, 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.

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两亲性聚氨基酸三嵌段共聚物构筑pH/溶剂可控多级纳米结构