Block copolymer assembly via kinetic control.
ABSTRACT Block copolymers consist of two or more chemically different polymer segments, or blocks, connected by a covalent linkage. In solution, amphiphilic blocks can self-assemble as a result of energetic repulsion effects between blocks. The degree of repulsion, the lengths of the block segments, and the selectivity of the solvent primarily control the resultant assembled morphology. In an ideal situation, one would like to be able to alter the morphology that forms without having to change the chemistry of the block copolymer. Through the kinetic manipulation of charged, amphiphilic block copolymers in solution, we are able to generate different nanoscale structures with simple block copolymer chemistry. The technique relies on divalent organic counter ions and solvent mixtures to drive the organization of the block copolymers down specific pathways into complex one-dimensional structures. Block copolymers are increasingly used as templating materials; thus, the ability to control the formation of specific patterns and structures is of growing interest and applicability.
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ABSTRACT: The ladder model of growth of cylindrical micelles gives expressions for the micellar size distribution and for the mean aggregation number, which are in good agreement with the experiment. Here, we consider this model and its extension to the case of disclike micelles. In analogy with the modeling of elongated micelles as sphero-cylinders, the disclike micelles can be modeled as toro-discs. Upon micelle growth, the hemispherical caps of a cylindrical aggregate remain unchanged, whereas the semitoroidal periphery of a disclike micelle expands. This effect can be taken into account in the expression for the size distribution of the disclike micelles, which predicts the dependence of the micelle mean aggregation number on the surfactant concentration. It turns out that disclike micelles could form in a limited range of surfactant concentrations, and that their mean aggregation number cannot exceed a certain maximal value. Large disclike micelles can exist only near the border with the domain of cylindrical micelles. Then, small variations in the experimental conditions could induce a transformation of the disclike micelles into cylindrical ones.Current Opinion in Colloid & Interface Science 12/2013; 18(6):524–531. DOI:10.1016/j.cocis.2013.11.002 · 6.40 Impact Factor
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ABSTRACT: Combining self-consistent-field theory and density-functional theory, we systematically study the deformation of copolymer micelles induced by the presence of amphiphilic dimer particles. Due to the amphiphilic nature, dimer particles tend to accumulate onto the interface of the copolymer micelle. With increasing concentration of the symmetric dimer particles, which are made of two identical spherical particles, the micelle deforms from the initial sphere to ellipse, dumbbell, and finally separates into two micelles. Furthermore, asymmetric dimer particles, composed by two particles with different sizes, are considered to investigate the influence of geometry of dimer particles on the deformation of the micelle. It is found that the micelle inclines to deform into dumbbell due to the additional curvature originating in the gathering of asymmetric dimer particles onto the interface of the micelle. The present study on the deformation of micelles is useful to understand the possible shape variation in the course of cell division/fusion.Chinese Journal of Polymer Science 03/2011; 30(2). DOI:10.1007/s10118-012-1108-4 · 1.42 Impact Factor