Mechanistic Insights for Block Copolymer Morphologies: How Do Worms Form Vesicles?

Blanazs, Adam; Madsen, Jeppe; Battaglia, Giuseppe; Ryan, Anthony J.; Armes, Steven P.

doi:10.1021/ja206301a

Cited by 726 publications

(1,376 citation statements)

References 45 publications

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“…[186] Sequential formation of PEGA/MMA macro-RAFT agent (by solution polymerization) and low dispersity poly(PEGA-co-MMA)-b-poly(St) (by emulsion polymerization) in a one-pot process. [354,360] The same macro-RAFT agent was also used in non-aqueous emulsion or dispersion polymerization of BzMA.…”

Section: Raft Polymerization In Heterogeneous Mediamentioning

confidence: 99%

“…It has been reported that the extent of branching is higher 289 [186,187,229,577] 290 [175,203,305] 291 [211] 295 [308] 301 [165] 306 CSSQMA [389] 302 [164] 303 [209] 304 [305] 307 [578,579] 308 [579] 305 [212] 297 [188] 298 [201] 299 [201] 300 [387] 292 [189] 293 [173] 294 [210] Glycerol monomethacrylate Solketal methacrylate 296 [197,390] for conventional radical polymerization than for RDRP (ATRP, RAFT, and NMP). [443] A qualitative explanation was proposed in terms of the differences in the concentrations of short-chain radicals between RDRP and conventional radical polymerization.…”

Section: Acrylatesmentioning

confidence: 99%

“…S S * BzMA [161] MMA [162] PEGMA [163] 302 [164] 301 [165] 312 [166] 396 [167] MA [168] PFPVB [169] PVS [169] St [132,162] 359 [170] St [171] BA [122] MMA/BDSMA [172] (MAA/TPMMA) [173] (MAA/293) [173] DEGMA/PEGMA [174] tBMA/DMAEMA/290 [175] MMA/LMA [163] 396-b-PEGMA [167] St/AcS [176] 4VP/EGDMA [177] (St-b-DMAEMA) [171] BzMA-b-HPMAm [161] DEGMA/PEGMA-b-DMAPMAm [174] PEGMA-b-MMA [163] LMA/MMA-b-PEGMA [163] 12 S S CN D* [178] MMA [178][179][180][181][182][183][184] PEGMA [111,185] GMA [186] 289 [186,187] 297 [188] 324 [189] 453 [190] iPOx [191] St [132,…”

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Living Radical Polymerization by the RAFT Process – A Third Update

2012

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This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(¼S)SR) by a mechanism of reversible addition-fragmentation chain transfer ( Chem. 2009Chem. , 62, 1402. This review cites over 700 publications that appeared during the period mid 2009 to early 2012 covering various aspects of RAFT polymerization which include reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses, and a diverse range of applications. This period has witnessed further significant developments, particularly in the areas of novel RAFT agents, techniques for end-group transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.

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Section: Raft Polymerization In Heterogeneous Mediamentioning

confidence: 99%

Section: Acrylatesmentioning

confidence: 99%

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Living Radical Polymerization by the RAFT Process – A Third Update

2012

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“…36 For example, the binary cooperative effect 37,38 of the hydrophilic segments and hydrophobic segments cause the polymer chains to assemble into aggregates in aqueous solutions, with the hydrophobic segments twisting and coiling to entangle each other via hydrophobic interactions as the core. 39 Under certain conditions, the aggregates are able to transform among various morphologies, [39][40][41][42] including spheres, rods, 43 vesicles, 44 tubules 45 and cubosomes 46 similar to actuators. Therefore, it seems feasible to combine a hydrogel with an organogel to fabricate a covalently connected macro-scale 'amphiphilic diblock copolymer aggregate,' whereby the two subunits of diverse physical and chemical properties realize macroscopical motion.…”

Section: Introductionmentioning

confidence: 99%

A monolithic hydro/organo macro copolymer actuator synthesized via interfacial copolymerization

et al. 2017

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Synthetic polymer actuators have attracted increasing attention for their potential applications in artificial muscles, soft robotics and sensors. The majority of previous efforts have focused on smart hydrogels with bilayer structures that can change their shape in response to environmental stimuli, such as temperature, light and certain chemicals. However, the practical application of hydrogels is limited because of their low modulus and weak mechanical strength. Here we synthesized a robust monolithic actuator of a macro-scale hydro/organo binary cooperative Janus copolymer film. The process involves direct, one-step interfacial polymerization of immiscible hydrophilic and hydrophobic vinyl monomer solutions, and the resultant product exhibited binary cooperative shape transformation to multiple external stimuli. The Janus copolymer film can work in both aqueous solutions and organic solvents, with bidirectional and site-specific bending arising from cooperative asymmetric swelling/shrinking of the hydrogel and organogel networks. In addition, the as-prepared Janus copolymer film can act as a sensor element for solvent leakage detection. This binary cooperative strategy is applicable to most immiscible monomer systems and provides a general approach to developing novel functional copolymer materials. NPG Asia Materials (2017) 9, e380; doi:10.1038/am.2017.61; published online 19 May 2017 INTRODUCTIONThe shape transformations of biological organisms [1][2][3][4][5][6] have been the inspiration for many products in the field of artificial muscles, 7-13 soft robotics, 14-19 sensors 20 and complex shape engineering. 21,22 For example, the leaves of the Venus flytrap snap together to capture insects by virtue of the synergy between the hydroelastic instability and asymmetric expansion of the inner and outer surfaces at the cellular level. 2 The layered anisotropic orientated cellulose fibrils induce hygroscopic movements of pine cones, 1 wheat awns, 3 orchid tree seedpods 6 and other plants. By mimicking the sophisticated hierarchical structures present in nature, the motion of polymer films has been successfully demonstrated in several cases. [23][24][25][26][27][28][29][30] For example, hydrogel bilayers embedded with intersecting inorganic platelets or cellulose fibrils have exhibited pine-cone-like bending and pod-like twisting motions. 24,31 However, the practical applications of these actuators were limited because of the low modulus and weak mechanical strength of the hydrogels. 32 Elastomer single layer films, such as azobenzene polymer films synthesized using an elaborate molecular design, 13,27 can achieve smart responsive curving. However, these films require a unidirectional stimulus to generate anisotropic contraction/expansion of their two sides; this factor limits the film thickness to the micrometer or sub-millimeter level. 27,[33][34][35] Therefore,

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“…[13] In particular, polymerization-induced selfassembly (PISA) of poly(glycerol monomethacrylate)-block-poly(2-hydroxypropyl methacrylate) (PGMA-PHPMA) diblock copolymers enables well-defined spheres, worms or vesicles to be produced at high solids, simply by targeting the appropriate diblock composition. [14,15] The worm morphology is of particular interest, because these highly anisotropic particles form soft, free-standing aqueous gels. [15,16] These worm gels are thermoresponsive: upon cooling to 5 °C, the hydrophobic core-forming PHPMA block becomes more plasticized by water, which induces a worm-to-sphere transition and causes de-gelling (i.e., separation of fused spheres).…”

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Disulfide-Based Diblock Copolymer Worm Gels: A Wholly-Synthetic Thermoreversible 3D Matrix for Sheet-Based Cultures

et al. 2015

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It is well-known that 3D in vitro cell cultures provide a much better model than 2D cell cultures for understanding the in vivo microenvironment of cells. However, significant technical challenges in handling and analyzing 3D cell cultures remain, which currently limits their widespread application. Herein, we demonstrate the application of wholly synthetic thermoresponsive block copolymer worms in sheet-based 3D cell culture. These worms form a soft, free-standing gel reversibly at 20–37 °C, which can be rapidly converted into a free-flowing dispersion of spheres on cooling to 5 °C. Functionalization of the worms with disulfide groups was found to be essential for ensuring sufficient mechanical stability of these hydrogels to enable long-term cell culture. These disulfide groups are conveniently introduced via statistical copolymerization of a disulfide-based dimethacrylate under conditions that favor intramolecular cyclization and subsequent thiol/disulfide exchange leads to the formation of reversible covalent bonds between adjacent worms within the gel. This new approach enables cells to be embedded within micrometer-thick slabs of gel with good viability, permits cell culture for at least 12 days, and facilitates recovery of viable cells from the gel simply by incubating the culture in buffer at 4 °C (thus, avoiding the enzymatic degradation required for cell harvesting when using commercial protein-based gels, such as Matrigel).

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Mechanistic Insights for Block Copolymer Morphologies: How Do Worms Form Vesicles?

Cited by 726 publications

References 45 publications

Living Radical Polymerization by the RAFT Process – A Third Update

Living Radical Polymerization by the RAFT Process – A Third Update

A monolithic hydro/organo macro copolymer actuator synthesized via interfacial copolymerization

Disulfide-Based Diblock Copolymer Worm Gels: A Wholly-Synthetic Thermoreversible 3D Matrix for Sheet-Based Cultures

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