Abstract
The use of crystallization as a tool to control the self-assembly of polymeric and molecular amphiphiles in solution is attracting growing attention for the creation of non-spherical nanoparticles and more complex, hierarchical assemblies. In particular, the seeded growth method termed living crystallization-driven self-assembly (CDSA) has been established as an ambient temperature and potentially scalable platform for the preparation of low dispersity samples of core–shell fiber-like or platelet micellar nanoparticles. Significantly, this method permits predictable control of size, and access to branched and segmented structures where functionality is spatially-defined. Living CDSA operates under kinetic control and shows many analogies with living chain-growth polymerizations of molecular organic monomers that afford well-defined covalent polymers of controlled length except that it covers a much longer length scale (ca. 20 nm to 10 μm). The method has been applied to a rapidly expanding range of crystallizable polymeric amphiphiles, which includes block copolymers and charge-capped homopolymers, to form assemblies with crystalline cores and solvated coronas. Living CDSA seeded growth methods have also been transposed to a wide variety of π-stacking and hydrogen-bonding molecular species that form supramolecular polymers in processes termed “living supramolecular polymerizations”. In this article we outline the main features of the living CDSA method and then survey the promising emerging applications for the resulting nanoparticles in fields such as nanomedicine, colloid stabilization, catalysis, optoelectronics, information storage, and surface functionalization.
Highlights
Molecular and macromolecular synthesis has evolved to an advanced state, the ability to prepare materials in the 10 nm to 100 micron size regime with controlled shape, dimensions, functionality, and structural hierarchy is still in its relative infancy and currently remains the near-exclusive domain of biology
Living crystallization-driven selfassembly (CDSA) seeded growth methods have been transposed to a wide variety of p-stacking and hydrogen-bonding molecular species that form supramolecular polymers in processes termed “living supramolecular polymerizations”
The rst syntheses of well-de ned Block copolymers (BCPs) were achieved via living anionic polymerization in the mid-to-late 1950s and studies of their solution self-assembly behavior were initiated over the following decade.[9]
Summary
Molecular and macromolecular synthesis has evolved to an advanced state, the ability to prepare materials in the 10 nm to 100 micron size regime with controlled shape, dimensions, functionality, and structural hierarchy is still in its relative infancy and currently remains the near-exclusive domain of biology. Ian Manners' group at University of Victoria as a postdoctoral fellow, his research interest is currently on fabrication functional materials through living crystallizationdriven self-assembly of block polymers. He joined the University of Toronto, Canada as an Assistant Professor in 1990 and was promoted to Full Professor in 1995 and was made a Canada Research Chair in 2001. Over the past 15 years extensive studies of the self-assembly of polymeric amphiphiles with crystallizable rather than amorphous core-forming blocks have established promising solutions to the aforementioned issues.[6,9,23,24] These investigations have enabled the development of a wide range of 1D, 2D and complex polymer-based nanoparticles with promising scalability and potential functions that complement those available with spherical and vesicular micellar morphologies. In this perspective we describe the development and main features of this seeded growth approach, and survey the promising emerging applications for the resulting micellar assemblies
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