Well-Defined Amphiphilic Block Copolymer Nanoobjects via Nitroxide-Mediated Emulsion Polymerization

Groison, Emilie; Brusseau, Ségolène; D’Agosto, Franck; Magnet, Stéphanie; Inoubli, Rabi; Couvreur, Laurence; Charleux, Bernadette

doi:10.1021/mz200035b

Cited by 110 publications

(121 citation statements)

References 32 publications

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“…[6][7][8][9] Recently, substantial processes have been made by virtue of polymerisation-induced self-assembly (PISA) [3][4][5] via combination of reversible addition-fragmentation chain transfer (RAFT) 10,11 with aqueous emulsion/dispersion polymerisation. [15][16][17] In each case, a macromolecular chain transfer agent (macro-CTA) acts as a steric stabilizer, and hydrophobic growing block drives in situ self-assembly. [15][16][17] In each case, a macromolecular chain transfer agent (macro-CTA) acts as a steric stabilizer, and hydrophobic growing block drives in situ self-assembly.…”

Section: Introductionmentioning

confidence: 99%

The direct synthesis of interface-decorated reactive block copolymer nanoparticles via polymerisation-induced self-assembly

et al. 2015

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Self-assembly of amphiphilic block copolymer in water suffers from the undesired encapsulation of hydrophobic reactive motifs in core-forming block, which deteriorates the performance as aqueous catalysts. This problem can be circumvented by polymerisation-induced self-assembly (PISA). Herein, we report a new strategy for one-pot synthesis of reactive block copolymer nanoparticles whose hydrophobic reactive motifs decorate surrounding core-shell interfaces. We demonstrate fast RAFT aqueous dispersion polymerisation of a commercial available specialty monomer, diacetone acrylamide (DAAM), under visible light irradiation at 25 o C. PISA is induced by polymerisation via sequentially dehydration, phase separation and reaction acceleration, and thus complete conversion in 30 min. Replacement of minimal DAAM by NH3 + -monomer induces slight hydration of the core-forming block, and thus a low polydispersity of resultant statistic-block copolymer. Moreover, simultaneous in situ self-assembly and chain growth favours adjustment of newly-added NH3 + -units outward to core-shell interfaces while the major DAAM units collapse to hydrophobic PISA-cores. Both lead to timely and selective self-assembly into the new reactive nanoparticles whose NH3 + -motifs decorate surrounding core-shell interfaces. These nanoparticles well suit fabrication of advanced nanoreactors whose hydrophobic dative metal centres decorate surrounding interfaces via simultaneous imine conversion and Zn(II)-coordination. Such PISA-nanostructures endow hydrophobic metal centres with huge and accessible specific surface area and are stabilized by water-soluble shells. Therefore, this strategy holds fascinating potentials for the fabrication of metalloenzyme-inspired aqueous catalysts.Enzyme inspired interface-decorated media-accessible reactive nanoparticles are now available via PISA by aqueous dispersion RAFT of commodity-DAAM with minimal NH 3 + -monomer.

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Section: Introductionmentioning

confidence: 99%

The direct synthesis of interface-decorated reactive block copolymer nanoparticles via polymerisation-induced self-assembly

et al. 2015

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“…[17][18][19][20][21][22][23][24][25][26][27][28] PISA facilitates the formation of a myriad of macromolecular nano-architectures depending on the solvophilic/solvophobic volume ratio at much higher concentrations (up to 50 wt%) by using living radical polymerization techniques, such as atom transfer radical polymerization (ATRP), 29,30 nitroxide mediated polymerization (NMP) [31][32][33] and reversible addition-fragmentation chain transfer (RAFT) polymerization. [17][18][19][20][21][22][23][24][25][26][27][28] PISA facilitates the formation of a myriad of macromolecular nano-architectures depending on the solvophilic/solvophobic volume ratio at much higher concentrations (up to 50 wt%) by using living radical polymerization techniques, such as atom transfer radical polymerization (ATRP), 29,30 nitroxide mediated polymerization (NMP) [31][32][33] and reversible addition-fragmentation chain transfer (RAFT) polymerization.…”

Section: Introductionmentioning

confidence: 99%

Polymerization-induced self-assembly driving chiral nanostructured materials

et al. 2015

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To prepare chiral nanostructures coated with bioactive molecules, a side-chain amino acid containing macromolecular chain transfer agent (macroCTA), poly(Boc-L-alanine methacryloyloxyethyl ester) (PBLAEMA), has been used as the steric stabilizer for the reversible addition-fragmentation chain transfer (RAFT) mediated dispersion polymerization of benzyl methacrylate (BzMA) in methanol at 65°C. Gel permeation chromatography (GPC) analysis confirmed an efficient and well-controlled block copolymerization. A full spectrum of morphologies spanning spherical micelles, worm like micelles, fibres and vesicles could be attained by tuning (i) the length of the solvophobic block and (ii) the total solid content at which the block copolymerization is performed. Interestingly, a purely fibre phase morphology formed a thermoresponsive gel at room temperature above a critical fibre entanglement concentration, which underwent degelation upon heating because of the morphological transformation from anisotropic fibre to isotropic sphere. In actual fact, twisted nano-fibres have been formed through the hierarchical selfassembling of polymerization induced self-assembly (PISA) generated macromolecules in the gel state.Circular dichroism (CD) spectroscopy was used to elucidate chiroptical properties. Additionally, a high demanding wrinkle surface has been constructed preliminarily from this copolymer dispersion solution.Successful Boc-group expulsion facilitates the disassembly of vesicles to either worms or spheres with an appreciable cationic character below pH 7.0 as revealed by aqueous electrophoresis studies. Though the creation of nano-objects through PISA is well-known, fabricating chiral nanostructures with reactive handles and their hierarchical self-organization to have functional architectures is a less explored area. In this present work we were able to hybridize PISA, chirality and hierarchical self-assembling. † Electronic supplementary information (ESI) available: GPC chromatograms, CD spectra, 1 H NMR spectrum and DLS size distributions of various block copolymers. See

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“…Another strategy to prepare block copolymer nano‐objects is the so‐called polymerization‐induced self‐assembly through the macro‐RAFT agent mediated emulsion polymerization or dispersion polymerization . The strategy involves the in situ synthesis of the amphiphilic block copolymer nano‐objects by the growth of the solvatophobic block from a solvatophilic living polymer in the living radical polymerization such as atom transfer radical polymerization (ATRP), nitroxide mediated polymerization, and reversible addition fragmentation chain transfer (RAFT) polymerization . Compared with the self‐assembly of block copolymers in the block‐selective solvent, the polymerization‐induced self‐assembly to prepare block copolymer nano‐objects can be achieved with the block copolymer concentration as high as 25 wt % …”

Section: Introductionmentioning

confidence: 99%

Brush macro‐RAFT agent mediated dispersion polymerization of styrene in the alcohol/water mixture

Xiao

Dan

et al. 2013

J. Polym. Sci. Part A: Polym. Chem.

109

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Dispersion RAFT polymerization of styrene in the alcohol/water mixture mediated with the brush macro‐RAFT agent of poly[poly(ethylene oxide) methyl ether vinylphenyl‐co‐styrene] trithiocarbonate [P(mPEGV‐co‐St)‐TTC] with similar molecular weight but different chemical composition is investigated. Well‐controlled RAFT polymerization including an initial slow homogeneous polymerization and a subsequent fast heterogeneous polymerization at almost complete monomer conversion is achieved. The molecular weight of the synthesized block copolymer increases linearly with the monomer conversion, and the polydispersity is relatively narrow (PDI < 1.3). The RAFT polymerization kinetics is dependent on the chemical composition in the brush macro‐RAFT agents, and those with high content of hydrophobic segment lead to fast RAFT polymerization. The growth of the block copolymer nano‐objects during the RAFT polymerization is explored, and various block copolymer nano‐objects such as nanospheres, worms, vesicles and large‐compound‐micelle‐like particles are prepared. The parameters such as the chemical composition in the brush macro‐RAFT agent, the chain length of the solvatophobic block, the concentration of the feeding monomer and the solvent character affecting the size and morphology of the block copolymer nano‐objects are investigated. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3177–3190

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Well-Defined Amphiphilic Block Copolymer Nanoobjects via Nitroxide-Mediated Emulsion Polymerization

Cited by 110 publications

References 32 publications

The direct synthesis of interface-decorated reactive block copolymer nanoparticles via polymerisation-induced self-assembly

The direct synthesis of interface-decorated reactive block copolymer nanoparticles via polymerisation-induced self-assembly

Polymerization-induced self-assembly driving chiral nanostructured materials

Brush macro‐RAFT agent mediated dispersion polymerization of styrene in the alcohol/water mixture

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