This Perspective outlines recent advances concerning the formation and potential uses of block copolymer micelles, a class of soft matter-based nanoparticles of growing importance. As a result of rapidly expanding interest since the mid 1990s, substantial advances have been reported in terms of the development of morphological diversity and complexity, control over micelle dimensions, scale up, and applications in a range of areas from nanocomposites to nanomedicine.

This in-depth review covers progress in the area of polyferrocenylsilanes (PFS), a well-established, readily accessible class of main chain organosilicon metallopolymer consisting of alternating ferrocene and organosilane units. Soluble, high molar mass samples of these materials were first prepared in the early 1990s by ring-opening polymerisation (ROP) of silicon-bridged [1]ferrocenophanes (sila[1]ferrocenophanes). Thermal, transition metal-catalysed, and also two different living anionic ROP methodologies have been developed: the latter permit access to controlled polymer architectures, such as monodisperse PFS homopolymers and block copolymers. Depending on the substituents, PFS homopolymers can be amorphous or crystalline, and soluble in organic solvents or aqueous media. PFS materials have attracted widespread attention as high refractive index materials, electroactuated redox-active gels, fibres, films, and nanoporous membranes, as precursors to nanostructured magnetic ceramics, and as etch resists to plasmas and other radiation. PFS block copolymers form phase-separated iron-rich, redox-active and preceramic nanodomains in the solid state with applications in nanolithography, nanotemplating, and nanocatalysis. In selective solvents functional micelles with core-shell structures are formed. Block copolymers with a crystallisable PFS core-forming block were the first to be found to undergo "living crystallisation-driven self-assembly" in solution, a controlled method of assembling block copolymers into 1D or 2D structures that resembles a living covalent polymerisation, but on a longer length scale of 10 nm-10 μm.

Monodisperse fiber-like micelles with a crystalline π-conjugated polythiophene core with lengths up to ca. 700 nm were successfully prepared from the diblock copolymer poly(3-hexylthiophene)-block-polystyrene using a one-dimensional self-seeding technique. Addition of a polythiophene block copolymer with a different corona-forming block to the resulting nanofibers led to the formation of segmented B-A-B triblock co-micelles by crystallization-driven seeded growth. The key to these advances appears to be the formation of a relatively defect-free crystalline micelle core under the self-seeding conditions.

The preparation of well-defined nanoparticles based on soft matter, using solution-processing techniques on a commercially viable scale, is a major challenge of widespread importance. Self-assembly of block copolymers in solvents that selectively solvate one of the segments provides a promising route to core-corona nanoparticles (micelles) with a wide range of potential uses. Nevertheless, significant limitations to this approach also exist. For example, the solution processing of block copolymers generally follows a separate synthesis step and is normally performed at high dilution. Moreover, non-spherical micelles-which are promising for many applications-are generally difficult to access, samples are polydisperse and precise dimensional control is not possible. Here we demonstrate the formation of platelet and cylindrical micelles at concentrations up to 25% solids via a one-pot approach-starting from monomers-that combines polymerization-induced and crystallization-driven self-assembly. We also show that performing the procedure in the presence of small seed micelles allows the scalable formation of low dispersity samples of cylindrical micelles of controlled length up to three micrometres.

With the aim of accessing colloidally stable, fiberlike, π-conjugated nanostructures of controlled length, we have studied the solution self-assembly of two asymmetric crystalline-coil, regioregular poly(3-hexylthiophene)-b-poly(2-vinylpyridine) (P3HT-b-P2VP) diblock copolymers, P3HT23-b-P2VP115 (block ratio=1:5) and P3HT44-b-P2VP115 (block ratio=ca. 1:3). The self-assembly studies were performed under a variety of solvent conditions that were selective for the P2VP block. The block copolymers were prepared by using Cu-catalyzed azide-alkyne cycloaddition reactions of azide-terminated P2VP and alkyne end-functionalized P3HT homopolymers. When the block copolymers were self-assembled in a solution of a 50% (v/v) mixture of THF (a good solvent for both blocks) and an alcohol (a selective solvent for the P2VP block) by means of the slow evaporation of the common solvent; fiberlike micelles with a P3HT core and a P2VP corona were observed by transmission electron microscopy (TEM). The average lengths of the micelles were found to increase as the length of the hydrocarbon chain increased in the P2VP-selective alcoholic solvent (MeOH3 μm) fiberlike micelles were prepared by the dialysis of solutions of the block copolymers in THF against iPrOH. Furthermore the widths of the fibers were dependent on the degree of polymerization of the chain-extended P3HT blocks. The crystallinity and π-conjugated nature of the P3HT core in the fiberlike micelles was confirmed by a combination of UV/Vis spectroscopy, photoluminescence (PL) measurements, and wide-angle X-ray scattering (WAXS). Intense sonication (iPrOH, 1 h, 0 °C) of the fiberlike micelles formed by P3HT23-b-P2VP115 resulted in small (ca. 25 nm long) stublike fragments that were subsequently used as initiators in seeded growth experiments. Addition of P3HT23-b-P2VP115 unimers to the seeds allowed the preparation of fiberlike micelles with narrow length distributions (L(w)/L(n) < 1.11) and lengths from about 100-300 nm, that were dependent on the unimer-to-seed micelle ratio.

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Self-assembly provides the ability to create well-controlled nanostructures with electronic or chemical functionality and enables the synthesis of a wide range of useful devices. Diblock copolymers self-assemble into periodic arrays of microdomains with feature sizes of typically 10-50 nm, and have been used to make a wide range of devices such as silicon capacitors and transistors, photonic crystals, and patterned magnetic media(1-3). However, the cylindrical or spherical microdomains in diblock copolymers generally form close-packed structures with hexagonal symmetry, limiting their device applications. Here we demonstrate self-assembly of square-symmetry patterns from a triblock terpolymer in which one organometallic block imparts high etch selectivity and etch resistance. Long-range order is imposed on the microdomain arrays by self-assembly on topographical substrates, and the orientation of both square lattices and in-plane cylinders is controlled by the substrate chemistry. Pattern transfer is demonstrated by making an array of square-packed 30 nm tall, 20 nm diameter silica pillars. Templated self-assembly of triblock terpolymers can generate nanostructures with geometries that are unattainable from diblock copolymers, significantly enhancing the capabilities of block copolymer lithography.

Cylindrical block copolymer micelles have shown considerable promise in various fields of biomedical research. However, unlike spherical micelles and vesicles, control over their dimensions in biologically-relevant solvents has posed a key challenge that potentially limits in depth studies and their optimisation for applications. Here, we report the preparation of cylindrical micelles of length in the wide range of 40 nm -1.10 µm in aqueous media with narrow length distributions (length polydispersities < 1.10). In our approach, an amphiphilic linear-brush block copolymer, with high potential for functionalization, was synthesized based on poly(ferrocenyldimethylsilane)-b-poly(allyl glycidyl ether) (PFS-b-PAGE) decorated with triethylene glycol (TEG), abbreviated as PFS-b-(PEO-g-TEG). PFS-b-(PEO-g-TEG) cylindrical micelles of controlled length with low polydispersities were prepared in N,N-dimethylformamide using small seed initiators via living crystallization-driven self-assembly. Successful dispersion of these micelles into aqueous media was achieved by dialysis against deionized water. Furthermore, B-A-B amphiphilic triblock comicelles with PFS-b-poly(2-vinylpyridine) (P2VP) as hydrophobic "B" blocks and hydrophilic PFS-b-(PEO-g-TEG) "A" segments were prepared and their hierarchical self-assembly in aqueous media studied. It was found that superstructures formed depend on the length of the hydrophobic blocks. Quaternization of P2VP was shown to cause the disassembly of the superstructures, resulting in the first examples of water-soluble cylindrical multi-block comicelles. We also demonstrate the ability of the triblock comicelles with quaternized terminal segments to complex DNA and, thus, to potentially function as gene vectors.