Issue 6, 2017

1D vs. 2D shape selectivity in the crystallization-driven self-assembly of polylactide block copolymers

Abstract

2D materials such as graphene, LAPONITE® clays or molybdenum disulfide nanosheets are of extremely high interest to the materials community as a result of their high surface area and controllable surface properties. While several methods to access 2D inorganic materials are known, the investigation of 2D organic nanomaterials is less well developed on account of the lack of ready synthetic accessibility. Crystallization-driven self-assembly (CDSA) has become a powerful method to access a wide range of complex but precisely-defined nanostructures. The preparation of 2D structures, however, particularly those aimed towards biomedical applications, is limited, with few offering biocompatible and biodegradable characteristics as well as control over self-assembly in two dimensions. Herein, in contrast to conventional self-assembly rules, we show that the solubility of polylactide (PLLA)-based amphiphiles in alcohols results in unprecedented shape selectivity based on unimer solubility. We use log Poct analysis to drive solvent selection for the formation of large uniform 2D diamond-shaped platelets, up to several microns in size, using long, soluble coronal blocks. By contrast, less soluble PLLA-containing block copolymers yield cylindrical micelles and mixed morphologies. The methods developed in this work provide a simple and consistently reproducible protocol for the preparation of well-defined 2D organic nanomaterials, whose size and morphology are expected to facilitate potential applications in drug delivery, tissue engineering and in nanocomposites.

Graphical abstract: 1D vs. 2D shape selectivity in the crystallization-driven self-assembly of polylactide block copolymers

Supplementary files

Article information

Article type
Edge Article
Submitted
10 Feb 2017
Accepted
24 Mar 2017
First published
13 Apr 2017
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2017,8, 4223-4230

1D vs. 2D shape selectivity in the crystallization-driven self-assembly of polylactide block copolymers

M. Inam, G. Cambridge, A. Pitto-Barry, Z. P. L. Laker, N. R. Wilson, R. T. Mathers, A. P. Dove and R. K. O'Reilly, Chem. Sci., 2017, 8, 4223 DOI: 10.1039/C7SC00641A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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