Self-assembly of molecular and block copolymer amphiphiles represents a well-established route to micelles with a wide variety of shapes and gel-like phases. We demonstrate an analogous process, but ...on a longer length scale, in which amphiphilic P-H-P and H-P-H cylindrical triblock comicelles with hydrophobic (H) or polar (P) segments that are monodisperse in length are able to self-assemble side by side or end to end in nonsolvents for the central or terminal segments, respectively. This allows the formation of cylindrical supermicelles and one-dimensional (1D) or 3D superstructures that persist in both solution and the solid state. These assemblies possess multiple levels of structural hierarchy in combination with existence on a multimicrometer-length scale, features that are generally only found in natural materials.
The creation of shaped, uniform and colloidally stable two-dimensional (2D) assemblies by bottom-up methods represents a challenge of widespread current interest for a variety of applications. ...Herein, we describe the utilization of surface charge to stabilize self-assembled planar structures that are formed from crystallizable polymer precursors by a seeded growth approach. Addition of crystallizable homopolymers with charged end-groups to seeds generated by the sonication of block copolymer micelles with crystalline cores yields uniform platelet micelles with controlled dimensions. Significantly, the seeded growth approach is characterized by a morphological memory effect whereby the origin of the seed, which can involve a quasi-hexagonal or rectangular 2D platelet precursor, dictates the observed 2D platelet shape. This new strategy is illustrated using two different polymer systems, and opens the door to the construction of 2D hierarchical structures with broad utility.
Although solution self-assembly of block copolymers (BCPs) represents one of the most promising approaches to the creation of nanoparticles from soft matter, the formation of non-centrosymmetric ...nanostructures with shape anisotropy remains a major challenge. Through a combination of crystallization-driven self-assembly of crystalline-coil BCPs in solution and selective micelle corona cross-linking, we have created short (about 130 nanometers), monodisperse cylindrical seed micelles that grow unidirectionally. These nanostructures grow to form long, non-centrosymmetric cylindrical A-B and A-B-C block co-micelles upon the addition of further BCPs. We also illustrate the formation of amphiphilic cylindrical A-B-C block co-micelles, which spontaneously self-assemble into hierarchical star-shaped supermicelle architectures with a diameter of about 3 micrometers. The method described enables the rational creation of non-centrosymmetric, high aspect ratio, colloidally stable core-shell nanoparticles in a manner that until now has been restricted to the biological domain.
We report the preparation of a series of fiber-like micelles of narrow length distribution with an oligo(p-phenylenevinylene) (OPV)-core and a poly(N-isopropylacrylamide) (PNIPAM) corona via two ...different crystallization-driven self-assembly (CDSA) strategies. The average length L n of these micelles can be varied up to 870 nm by varying the temperature in self-seeding experiments. In addition, seeded growth was employed not only to prepare uniform micelles of controlled length, but also to form fiber-like A-B-A triblock comicelles with an OPV-core.
Recent advances in the self-assembly of block copolymers have enabled the precise fabrication of hierarchical nanostructures using low-cost solution-phase protocols. However, the preparation of ...well-defined and complex planar nanostructures in which the size is controlled in two dimensions (2D) has remained a challenge. Using a series of platelet-forming block copolymers, we have demonstrated through quantitative experiments that the living crystallization-driven self-assembly (CDSA) approach can be extended to growth in 2D. We used 2D CDSA to prepare uniform lenticular platelet micelles of controlled size and to construct precisely concentric lenticular micelles composed of spatially distinct functional regions, as well as complex structures analogous to nanoscale single- and double-headed arrows and spears. These methods represent a route to hierarchical nanostructures that can be tailored in 2D, with potential applications as diverse as liquid crystals, diagnostic technology and composite reinforcement.
Fiber-like (1D) core-crystalline micelles of uniform length can be obtained in protocols involving multiple steps from block copolymers (BCPs) in which crystallization of the core-forming polymer ...drives the self-assembly. Here we report a systematic study that shows that adding small amounts (<5 w/w%) of a homopolymer corresponding to the core-forming block of the BCP enables uniform 1D micelles (mean lengths L n = 0.6 to 9.7 μm) to be obtained in a single step, simply by heating the mixture in a selective solvent followed by slow cooling. A series of poly(ferrocenyldimethylsilane) (PFS) BCPs with different corona-forming blocks and different compositions as well as PFS homopolymers of different lengths were examined. Dye labeling and confocal fluorescence microscopy showed that the homopolymer ends up in the center of the micelle, signaling that it served as the initial seed for epitaxial micelle growth. The rate of unimer addition was strongly enhanced by the length of the PFS block, and this enabled more complex structures to be formed in one-pot self-assembly experiments from mixtures of two or three BCPs with different PFS block lengths. Furthermore, BCP mixtures that included PFS-b-PI (PI = polyisoprene) and PFS-b-PDMS with similar PFS block lengths resulted in simultaneous addition to growing micelles, resulting in a patchy block that could be visualized by staining the vinyl groups of the PI with Pt nanoparticles. This approach also enabled scale up, so that uniform 1D micelles of controlled architecture can be obtained at concentrations of 10 w/w % solids or more.
In the late 1970s and 1980s, Professor Herbert Morawetz pioneered the use of dye-labeled polymers and fluorescence resonance energy transfer measurements for the study of miscibility of polymer ...blends. This work had its largest impact on scientists who use fluorescence techniques to study polymer systems.
The preparation of colloidally stable, self-assembled materials with tailorable solid or hollow two-dimensional (2D) structures represents a major challenge. We describe the formation of uniform, ...monodisperse rectangular platelet micelles of controlled size by means of seeded-growth methods that involve the addition of blends of crystalline-coil block copolymers and the corresponding crystalline homopolymer to cylindrical micelle seeds. Sequential addition of different blends yields solid platelet block comicelles with concentric rectangular patches with distinct coronal chemistries. These complex nano-objects can be subject to spatially selective processing that allows their disassembly to form perforated platelets, such as well-defined hollow rectangular rings. The solid and hollow 2D micelles provide a tunable platform for further functionalization and potential for a variety of applications.
Emerging strategies based on the self-assembly of block copolymers have recently enabled the bottom-up fabrication of nanostructured materials with spatially distinct functional regions. ...Concurrently, a drive for further miniaturization in applications such as optics, electronics and diagnostic technology has led to intense interest in nanomaterials with well-defined patterns of emission colour. Using a series of fluorescent block copolymers and the crystallization-driven living self-assembly approach, we herein describe the synthesis of multicompartment micelles in which the emission of each segment can be controlled to produce colours throughout the visible spectrum. This represents a bottom-up synthetic route to objects analogous to nanoscale pixels, into which complex patterns may be written. Because of their small size and high density of encoded information, these findings could lead to the development of new materials for applications in, for example, biological diagnostics, miniaturized display technology and the preparation of encoded nanomaterials with high data density.
Block copolymers consist of two or more chemically different polymers connected by covalent linkages. In solution, repulsion between the blocks leads to a variety of morphologies, which are ...thermodynamically driven. Polyferrocenyldimethylsilane block copolymers show an unusual propensity to forming cylindrical micelles in solution. We found that the micelle structure grows epitaxially through the addition of more polymer, producing micelles with a narrow size dispersity, in a process analogous to the growth of living polymer. By adding a different block copolymer, we could form co-micelles. We were also able to selectively functionalize different parts of the micelle. Potential applications for these materials include their use in lithographic etch resists, in redox-active templates, and as catalytically active metal nanoparticle precursors.
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