Bump-Surface Multicompartment Micelles from a Linear ABC Triblock Copolymer: A Combination Study by Experiment and Computer Simulation

Ma, Zengwei; Yu, Haizhou; Jiang, Wei

doi:10.1021/jp8089775

Cited by 36 publications

(39 citation statements)

References 29 publications

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“…The PB phase (dark) was selectively stained with OsO 4 to enhance contrast. This sphere-on-sphere configuration or ‘patchy spherical micelle' has been observed before whenever a voluminous corona was present to stabilize the spherical shape of the solvophobic core 19 20 21 34 . Applying our generalized parameter, N C / N A 2/3 ( Supplementary equation (10) ), to these literature examples, both literature and our own values suggest a stability region for spheres-on-spheres of N C / N A 2/3 >1.…”

Section: Resultssupporting

confidence: 63%

“…Applying our generalized parameter, N C / N A 2/3 ( Supplementary equation (10) ), to these literature examples, both literature and our own values suggest a stability region for spheres-on-spheres of N C / N A 2/3 >1. For instance, a N C / N A 2/3 of 1.9 and 6.4 led to the formation of spherical multicompartment micelles in case of polystyrene- b -polybutadiene- b -poly(2-vinyl pyridine) 34 and polybutadiene- b -poly(2-vinyl pyridine)- b -poly( tert -butyl methacrylate) 20 . Also in a previous publication, we examined a large set of terpolymers without observing structural evolution to patchy cylinder micelles, which we now can explain given their N C / N A 2/3 of 4–10 (ref.…”

Section: Resultsmentioning

confidence: 99%

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Rational design of ABC triblock terpolymer solution nanostructures with controlled patch morphology

et al. 2016

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Block copolymers self-assemble into a variety of nanostructures that are relevant for science and technology. While the assembly of diblock copolymers is largely understood, predicting the solution assembly of triblock terpolymers remains challenging due to complex interplay of block/block and block/solvent interactions. Here we provide guidelines for the self-assembly of linear ABC triblock terpolymers into a large variety of multicompartment nanostructures with C corona and A/B cores. The ratio of block lengths NC/NA thereby controls micelle geometry to spheres, cylinders, bilayer sheets and vesicles. The insoluble blocks then microphase separate to core A and surface patch B, where NB controls the patch morphology to spherical, cylindrical, bicontinuous and lamellar. The independent control over both parameters allows constructing combinatorial libraries of unprecedented solution nanostructures, including spheres-on-cylinders/sheets/vesicles, cylinders-on-sheets/vesicles, and sheets/vesicles with bicontinuous or lamellar membrane morphology (patchy polymersomes). The derived parameters provide a logical toolbox towards complex self-assemblies for soft matter nanotechnologies.

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Section: Resultssupporting

confidence: 63%

Section: Resultsmentioning

confidence: 99%

Rational design of ABC triblock terpolymer solution nanostructures with controlled patch morphology

et al. 2016

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“…8b). 221 The patch number and patch location almost corresponds to geometrically arranged clusters. In another example, MCNs with Janus distribution of the core as well as the corona were fabricated by direct dispersion of bishydrophilic poly(ethylene oxide)-block-poly(ε-caprolactone)-block-poly(2aminoethyl methacrylate hydrochloride) (PEO-b-PCL-b-PAMA) in water at temperatures close to the T g of the hydrophobic PCL segment to give thermodynamically equilibrated PCL cores and a mixed PEO/PAMA corona.…”

Section: One-step Self-assembly Of Abc Triblock Terpolymersmentioning

confidence: 98%

Self-assembly concepts for multicompartment nanostructures

2015

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Compartmentalization is ubiquitous to many biological and artificial systems, be it for the separate storage of incompatible matter or to isolate transport processes. Advancements in the synthesis of sequential block copolymers offer a variety of tools to replicate natural design principles with tailor-made soft matter for the precise spatial separation of functionalities on multiple length scales. Here, we review recent trends in the self-assembly of amphiphilic block copolymers to multicompartment nanostructures (MCNs) under (semi-)dilute conditions, with special emphasis on ABC triblock terpolymers. The intrinsic immiscibility of connected blocks induces short-range repulsion into discrete nano-domains stabilized by a third, soluble block or molecular additive. Polymer blocks can be synthesized from an arsenal of functional monomers directing self-assembly through packing frustration or response to various fields. The mobility in solution further allows the manipulation of self-assembly processes into specific directions by clever choice of environmental conditions. This review focuses on practical concepts that direct self-assembly into predictable nanostructures, while narrowing particle dispersity with respect to size, shape and internal morphology. The growing understanding of underlying self-assembly mechanisms expands the number of experimental concepts providing the means to target and manipulate progressively complex superstructures.

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“…41 The phenomenon may be ascribed that the rigid characteristic of rod HAPEK segment was conducive to maintaining the metastable state. 44 –46 Thus, similar quadrilateral-shaped micelles were formed when a small quantity of CHCl 3 (66.7 vol.%) was added to the copolymer solution of THF.…”

Section: Resultsmentioning

confidence: 98%

Influence of selective solvents on self-assembly behaviors of amphiphilic hyperbranched poly(aryl ether ketone)-graft-poly(ethylene glycol) rod–coil copolymer

Luan

Lü

Guo

et al. 2016

High Performance Polymers

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An amphiphilic hyperbranched poly(aryl ether ketone)- graft-poly(ethylene glycol) (HPAEK- graft-PEG) rod–coil copolymer was synthesized by grafting linear PEG onto hydroxyl-terminated HPAEK (OH-HPAEK). The molecular structure, the number-average molecular weight and the thermal properties of HPAEK- graft-PEG were characterized by proton nuclear magnetic resonance and Fourier transform infrared spectroscopies, gel permeation chromatography, differential scanning calorimetry, and thermogravimetric analysis, respectively. The self-assembly behaviors of HPAEK- graft-PEG in the mixed solvents were investigated by transmission electron microscopy and scanning electron microscopy. The results demonstrated that the selective solvent in the used mixed solvents exerted remarkable influence on the morphology of the resulting micelles. When the mixed solvents were water/tetrahydrofuran (THF), trichloromethane/THF, and toluene/THF, that is, with the decrease of the selective solvents in polarity, HPAEK- graft-PEG could self-assemble into the regular microspheres with obvious core–shell structure, the similar quadrilateral-shaped micelles with the dimension of about 20 nm and the large complicated clew-shaped micelles, as well as the irregular large compound micelles, respectively. It is worth mentioning that the similar quadrilateral-shaped micelles were different from the toroidal micelles reported already, which had relatively obvious “angle”. The phenomenon may be ascribed that the rigid characteristic of rod HAPEK segment was conducive to the maintenance of the metastable state.

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Bump-Surface Multicompartment Micelles from a Linear ABC Triblock Copolymer: A Combination Study by Experiment and Computer Simulation

Cited by 36 publications

References 29 publications

Rational design of ABC triblock terpolymer solution nanostructures with controlled patch morphology

Rational design of ABC triblock terpolymer solution nanostructures with controlled patch morphology

Self-assembly concepts for multicompartment nanostructures

Influence of selective solvents on self-assembly behaviors of amphiphilic hyperbranched poly(aryl ether ketone)-graft-poly(ethylene glycol) rod–coil copolymer

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