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. 2019 Jul 16;8(7):835-840.
doi: 10.1021/acsmacrolett.9b00335. Epub 2019 Jun 20.

Crystallization-Driven Self-Assembly of Metallo-Polyelectrolyte Block Copolymers with a Polycaprolactone Core-Forming Segment

Yujin Cha  1 , Charles Jarrett-Wilkins  2 , Md Anisur Rahman  1 , Tianyu Zhu  1 , Ye Sha  1 , Ian Manners  2   3 , Chuanbing Tang  1
Affiliations

Crystallization-Driven Self-Assembly of Metallo-Polyelectrolyte Block Copolymers with a Polycaprolactone Core-Forming Segment

Yujin Cha et al. ACS Macro Lett. .

Abstract

We report crystallization-driven self-assembly (CDSA) of metallo-polyelectrolyte block copolymers that contain cationic polycobaltocenium in the corona-forming block and crystallizable polycaprolactone (PCL) as the core-forming block. Dictated by electrostatic interactions originating from the cationic metalloblock and crystallization of the PCL, these amphiphilic block copolymers self-assembled into two-dimensional platelet nanostructures in polar protic solvents. The 2D morphologies can be varied from elongated hexagons to diamonds, and their stability to fragmentation was found to be dependent on the ionic strength of the solution.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1.
Figure 1.
(A) Schematic illustration of the formation of 2D hexagonal platelets by CDSA of block copolymer PCL61-b-PCoAEMA58. (B) TEM micrograph of hexagonal platelets from PCL61-b-PCoAEMA58 obtained by heating the polymer solution in methanol at 40 °C for 1 h followed by cooling and aging at room temperature for 1 month. (C) TEM SAED of hexagonal platetes. (D) AFM height image. (E) AFM height profile from image D.
Figure 2.
Figure 2.
TEM micrographs of PCL61-b-PCoAEMA58 in methanol: (A) before heating; (B) aging for 1 day; (C) aging for 3 days; and (D) aging for 11 days. Plots of (E) area versus aging time and (F) aspect ratio versus aging time.
Figure 3.
Figure 3.
(A) Illustration of platelet fragmentation of PCL61-b-PCoAEMA58 caused by charge repulsion and preservation by charge screening in accordance with ionic strength. TEM micrographs: (B) fragmented hexagon in methanol and water (v/v, 50/50) and (C) preserved hexagons by methanol and 2.0 M NaCl aq. solution (v/v, 50/50).
Figure 4.
Figure 4.
Schematic of (A, B) lower aspect ratio hexagonal platelet from PCL61-b-PCoAEMA244 and diamond-shaped platelet from PCL61-b-PCoAEMA344. TEM micrographs of platelets formed by (C) PCL61-b-PCoAEMA244 with an area dispersity of 1.05, (D) PCL61-b-PCoAEMA344 with an area dispersity of 1.11, and (E) PCL61-b-PCoAEMA58 in methanol and (F) plot of aspect ratio versus block ratio.
Scheme 1.
Scheme 1.
Illustration of CDSA of PCL-b-PCoAEMA Block Copolymer to Form Hexagonal Platelet Nanostructures
See this image and copyright information in PMC

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