Fluorous Cylindrical Micelles of Controlled Length by Crystallization-Driven Self-Assembly of Block Copolymers in Fluorinated Media

Hudson, Zachary M.; Qian, Jieshu; Boott, Charlotte E.; Winnik, Mitchell A.; Manners, Ian

doi:10.1021/mz500764n

Cited by 19 publications

(17 citation statements)

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“…356,[362][363][364][365][366] Branched micelles have been prepared by adding BCP unimer with a short PFS block to a preformed cylindrical micelle with a core composed of a longer PFS block. 356,[362][363][364][365][366] Branched micelles have been prepared by adding BCP unimer with a short PFS block to a preformed cylindrical micelle with a core composed of a longer PFS block.…”

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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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“…46,47 This has been achieved by sonication of the long polydisperse cylinders prepared by spontaneous nucleation in a selective solvent to form small seed micelles. Addition of molecularly dissolved BCP (unimer) then leads to growth from the seed termini.…”

Section: Introductionmentioning

confidence: 99%

Monodisperse Cylindrical Micelles and Block Comicelles of Controlled Length in Aqueous Media

et al. 2016

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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.

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“…Recently, BCP micelles with a crystalline core-forming block, such as polyferrocenyldimethylsilane (PFDMS), [1][2][3][4] polyethylene (PE), [5][6][7][8][9][10][11][12] poly(ethylene oxide) (PEO), [13][14][15][16] poly(e-caprolactone) (PCL), [17][18][19][20][21][22][23][24] poly(L-lactide) (PLLA), [25][26][27][28][29] polyacrylonitrile (PAN), 30 poly( p-dioxanone), 31,32 and polythiophene, 33,34 have received considerable attention. Recently, BCP micelles with a crystalline core-forming block, such as polyferrocenyldimethylsilane (PFDMS), [1][2][3][4] polyethylene (PE), [5][6][7][8][9][10][11][12] poly(ethylene oxide) (PEO), [13][14]…”

Section: Introductionmentioning

confidence: 99%

Crystallization-driven one-dimensional self-assembly of polyethylene-b-poly(tert-butylacrylate) diblock copolymers in DMF: effects of crystallization temperature and the corona-forming block

Fan

Liu

et al. 2016

Soft Matter

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Crystallization-driven self-assembly of polyethylene-b-poly(tert-butylacrylate) (PE-b-PtBA) block copolymers (BCPs) in N,N-dimethyl formamide (DMF) was studied. It is found that all three PE-b-PtBA BCPs used in this work can self-assemble into one-dimensional crystalline cylindrical micelles. When the BCP solution is cooled to crystallization temperature (Tc) from 130 °C, the seed micelles may be produced via two competitive processes in the initial period: stepwise micellization/crystallization and simultaneous crystallization/micellization. Subsequently, the seed micelles can undergo growth driven by the epitaxial crystallization of the unimers. The lengths of both the seed micelles and the grown micelles are longer for the BCP with a longer PtBA block at a higher Tc. Quasi-living growth of the PE-b-PtBA crystalline cylindrical micelles is achieved at a higher Tc. A longer PtBA block evidently retards the attachment of unimers to the crystalline micelles, leading to a slower growth rate.

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Fluorous Cylindrical Micelles of Controlled Length by Crystallization-Driven Self-Assembly of Block Copolymers in Fluorinated Media

Cited by 19 publications

References 50 publications

Polyferrocenylsilanes: synthesis, properties, and applications

Polyferrocenylsilanes: synthesis, properties, and applications

Monodisperse Cylindrical Micelles and Block Comicelles of Controlled Length in Aqueous Media

Crystallization-driven one-dimensional self-assembly of polyethylene-b-poly(tert-butylacrylate) diblock copolymers in DMF: effects of crystallization temperature and the corona-forming block

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