Non-covalent synthesis of supermicelles with complex architectures using spatially confined hydrogen-bonding interactions

Li, Xiaoyu; Gao, Yang; Boott, Charlotte E.; Winnik, Mitchell A.; Manners, Ian

doi:10.1038/ncomms9127

Cited by 99 publications

(114 citation statements)

References 59 publications

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“…381 Amphiphilic block comicelles with a very short hydrophobic PFDMS-b-PMVS central block and long hydrophilic PFDMS-b-P2VP end blocks could self-assemble into cross-type structures after dialysing into a selective solvent for the terminal coronal blocks. 381 Amphiphilic block comicelles with a very short hydrophobic PFDMS-b-PMVS central block and long hydrophilic PFDMS-b-P2VP end blocks could self-assemble into cross-type structures after dialysing into a selective solvent for the terminal coronal blocks.…”

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confidence: 99%

Polyferrocenylsilanes: synthesis, properties, and applications

et al. 2016

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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.

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Section: View Article Onlinementioning

confidence: 99%

Polyferrocenylsilanes: synthesis, properties, and applications

et al. 2016

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“…[32][33][34][35] Over the past decade, we and our collaborators have used CDSA and the "living" characteristics of this process to control micelle dimensions [36][37][38] and to construct complex PFDMS BCP micellar architectures. 39,40 However, as a result of the presence of crystalline cores, CDSA gives rise to micelles that with high-aspect-ratios that exhibit high stiffness. Consequently, CDSA does not normally favor the formation of vesicles or toroids that possess curved shapes, although limited examples of hollow nanostructures have been reported.…”

Section: Introductionmentioning

confidence: 99%

Uniform Toroidal Micelles via the Solution Self-Assembly of Block Copolymer–Homopolymer Blends Using a “Frustrated Crystallization” Approach

et al. 2018

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Toroidal nanostructures are of growing importance due to their unique geometry and potential utility in materials fabrication. Although a variety of amphiphilic block copolymers have been shown to selfassemble into toroidal micelles, the conventional methods used are often very slow with little control over the size of the resulting nanostructures. Here, we report a rapid and efficient synthetic route to prepare toroidal micelles of near uniform diameter through the cooperative co-assembly of amorphous blends of polyferrocenylsilane block copolymer and homopolymer, where the degree of polymerization of the core-forming metalloblock in the former is greater than for the latter. The selfassembly process is accomplished within a few minutes and the ring size of the toroids can be varied between 30 and 90 nm by adjusting the mass ratio of the block copolymer and homopolymer. The kinetic stability of the resulting toroidal micelles can be enhanced by frustrating core crystallization through solvent modulation and the toroids can also be readily used as templates to fabricate circular arrays of metal nanoparticles.

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“…[11,12] These techniques have been used to create hierarchical self-assembled structures and superstructures in solution. [13][14][15] Previous work on the liquid crystalline phase behaviour of PFS-based cylindrical micelles dispersed in decane revealed the existence of nematic and hexagonal phases, however discussion of the results was focussed predominantly on the isotropic and nematic phases. [7] Indeed where the phase behaviour of semi-flexible rods has been reported elsewhere, [16][17][18][19][20][21][22][23] there has been little discussion of what occurs at high concentrations.…”

Section: Introductionmentioning

confidence: 99%

An investigation into the hexagonal phases formed in high-concentration dispersions of well-defined cylindrical block copolymer micelles

et al. 2016

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This paper presents a detailed analysis of the structure of the hexagonal phase of poly(ferrocenylsilane) (PFS)-based cylindrical micelles found at concentrations above ca. 5 wt. % in non-polar solvents such as decane. Small angle X-ray scattering indicated that the hexagonal order is not long-range. In all samples, deviations in the lower order peak positions were observed with respect to those expected for a perfect hexagonal lattice, with the degree of deviation correlating with the micelle length. Furthermore, analysis of the peak shapes and peak widths suggest that the phase possesses intermediate translational order similar to the hexatic phase. The observed features can be reproduced by amending Hosemann's paracrystal theory to include a distribution of lattice parameters to model well and poorly condensed regions. It is proposed that this distribution arises due to the bending and intertwining of individual micelles in a hexagonal lattice resulting in a kinetically-trapped phase that is initially neither perfectly hexagonal nor canonically hexatic but which anneals over time towards a perfect hexagonal lattice.

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Non-covalent synthesis of supermicelles with complex architectures using spatially confined hydrogen-bonding interactions

Cited by 99 publications

References 59 publications

Polyferrocenylsilanes: synthesis, properties, and applications

Polyferrocenylsilanes: synthesis, properties, and applications

Uniform Toroidal Micelles via the Solution Self-Assembly of Block Copolymer–Homopolymer Blends Using a “Frustrated Crystallization” Approach

An investigation into the hexagonal phases formed in high-concentration dispersions of well-defined cylindrical block copolymer micelles

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