Self-Assembly of Maltoheptaose-block-polycaprolactone Copolymers: Carbohydrate-Decorated Nanoparticles with Tunable Morphology and Size in Aqueous Media
2016
Isono, Takuya | Miyachi, Kana | Satoh, Yusuke | Nakamura, Ryosuke | Zhang, Yao | Otsuka, Issei | Tajima, Kenji | Kakuchi, Toyoji | Borsali, Redouane | Satoh, Toshifumi
This paper describes the systematic investigation into the aqueous self-assembly of a series of block copolymers (BCPs) consisting of maltoheptaose (MH; as the A block) and poly(ε-caprolactone) (PCL; as the B block), i.e., linear AB-type diblock copolymers with varied PCL molecular weights (MH-b-PCL₍₂.₅ₖ,₃.₃ₖ,₅ₖ,₁₀ₖ₎), ABy-type (y = 2, MH-b-(PCL₅ₖ)₂; y = 3, MH-b-(PCL₃.₃ₖ)₃), A₂B₂-type ((MH)₂-b-(PCL₅ₖ)₂), and AₓB-type miktoarm star polymers (x = 2, (MH)₂-b-PCL₁₀ₖ; x = 3, (MH)₃-b-PCL₁₀ₖ), which had been precisely synthesized via the combination of the living ring-opening polymerization and click reaction. Under similar conditions, the nanoprecipitation method was employed to self-assemble them in an aqueous medium. Imaging and dynamic light scattering techniques indicated the successful formation of the carbohydrate-decorated nanoparticles via self-assembly. The MH-b-PCLs formed regular core–shell micellar nanoparticles with the hydrodynamic radius (Rₕ) of 17–43 nm. MH-b-(PCL₅ₖ)₂ and MH-b-(PCL₃.₃ₖ)₃, which have an NPCL comparable to MH-b-PCL₁₀ₖ, were found to form large compound micelles with relatively large radii (Rₕ of 49 and 56 nm, respectively). On the other hand, (MH)₂-b-(PCL₅ₖ)₂, (MH)₂-b-PCL₁₀ₖ, and (MH)₃-b-PCL₁₀ₖ predominantly formed the regular core–shell micellar nanoparticles (Rₕ = 29–39 nm) with a size smaller than that of MH-b-PCL₁₀ₖ (Rₕ = 43 nm).
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