Encapsulation of Nanoparticles in Block Copolymer Micellar Aggregates by Directed Supramolecular Assembly

Li, Weikun; Liu, Shanqin; Deng, Renhua; Zhu, Jintao

doi:10.1002/anie.201008224

Cited by 112 publications

(135 citation statements)

References 31 publications

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“…1−5 Up to now, a number of strategies have been developed to fabricate the hybrid BCPs/NPs nanomaterials, including coprecipitation method, 6,7 heating−cooling processing, 8 electrostatic interaction approach, 9 directed supramolecular assembly, 10 interfacial instabilities of emulsion droplets, 11,12 and so forth. On the other hand, it has been reported that the neat BCPs can self-assemble into unique microphaseseparated nanostructures confined in emulsion droplets because the confinement effect can effectively break the symmetry of the structure, thus resulting in the nanostructures that are not available in the free systems.…”

Section: Introductionmentioning

confidence: 99%

Entropy-Driven Hierarchical Nanostructures from Cooperative Self-Assembly of Gold Nanoparticles/Block Copolymers under Three-Dimensional Confinement

et al. 2015

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The cooperative self-assembly of polystyrene-b-poly(4-vinylpyridine) block copolymers (BCPs) and gold nanoparticles (AuNPs) confined within the emulsion droplets is studied by combining both the experiments and Monte Carlo simulations. The results indicate that the entropic interaction between the AuNPs and BCP domain is a critical parameter to dominate the spatial arrangement of AuNPs and the nanostructure of the hybrid nanoparticles, which can be utilized to design novel hierarchical hybrid nanoparticles. Based on this theoretical observation, a large number of unique Janus hybrid nanoparticles, including pupa-like nanoparticles with AuNPs concentrated at one pole of the particles, spherical nanoparticles with AuNPs enriched in a bulge on the sphere surface, and the gourd-like, clover-like, and four-leaf-clover-like nanoparticles from the further hierarchical assembly of small hybrid Janus nanoparticles, are fabricated via threedimensional (3D) confined self-assembly.

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Section: Introductionmentioning

confidence: 99%

Entropy-Driven Hierarchical Nanostructures from Cooperative Self-Assembly of Gold Nanoparticles/Block Copolymers under Three-Dimensional Confinement

et al. 2015

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“…Micelles are used in diverse fields including drug delivery, oil recovery, extraction etc, and to control order or porosity in inorganic materials 6,7 . Due to their colloidal size, they undergo random Brownian motion in liquids.…”

mentioning

confidence: 99%

Dynamically arrested micelles in a supercooled sugar urea melt

et al. 2018

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Micelles are nanoscopic, dynamic, equilibrium structures formed by the association of amphiphiles in a liquid. To date, freezing of disordered micelles typically requires cryogenic quenching. This avoids crystallization of the solvent or surfactant, mitigating against micelle destruction. Here we describe a method to create disordered, dynamically arrested waterfree micelles, trapped in a glass-forming solvent at ambient temperature. The micelles are formed by dissolving a surfactant in a molten mixture of sugar (fructose or glucose) and urea. These micelles are trapped in a supercooled state upon cooling the mixture, forming an amorphous micro-heterogeneous material driven by hydrogen bonding interactions. Since all components used in this formulation are solid at room temperature, the supercooled micelle formation is analogous to biphasic alloy formation in metals. This method may provide a way to prepare microphase separated organic solids and to control diffusion-limited aggregation of nanoparticles.

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“…The cationic segment is normally composed of pyridine or amino groups which are readily protonated under acid condition and thus can interact with anionic POMs through electrostatic force. Based on this method, a series of POM clusters including [SiMo 12 9− have been coassembled with BCPs, which leads to various hybrid assemblies such as spherical micelles, worm-like micelles, vesicles, and nanostructured inverse hexagonal films. 31−35 Although the electrostatic assembly method has made fruitful progresses, it is only suitable for special BCPs containing cationic segments; besides, a certain pH value is required to maintain the positively charged state of polymer segment, which may change the structure of some unstable POMs.…”

Section: Introductionmentioning

confidence: 99%

Controllable Nanostructure Formation through Enthalpy-Driven Assembly of Polyoxometalate Clusters and Block Copolymers

Jia

Cao

et al. 2015

Macromolecules

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The coassembly of block copolymers (BCPs) with nanoscale inorganic objects is an important route to fabricate nanostructured polymer composites. However, the immiscibility of inorganic/polymeric interface is a recurring challenge to overcome, particularly for inorganic clusters, such as the polyoxometalates (POMs)/BCPs system. In this paper, we present a general method to incorporate POMs into BCP matrices, in which a POM cluster is embedded as a core in a supramolecular star polymer (SSP) whose arms possess the same chemical composition as a BCP segment. Because of the enthalpic interaction between SSP arms and BCP segments, the SSP can carry POM into BCP matrices to realize their coassembly. By this way, we successfully localize a Keggin-type POM cluster [CoW 12 O 40 ] 6− modified with polystyrene (PS) arms into the PS domain of poly(styrene-b-ethylene oxide) micelles, which induces the formation of a series of hybrid micelles with spherical, toroidal, and bicontinuous structures. The morphological transition of micelles can be adjusted by the length of PS arms and the content of cluster cores. The mechanism is studied by both experimental methods and simulations. An unconventional mechanism for toroid formation is disclosed for the first time, which follows a sphere− rosary−toroid pathway. Furthermore, the electrostatically bonded structure of SSP is found to play a crucial role on this pathway. These results not only pave the way for fabricating cluster−polymer nanocomposites with controllable structures but also provide new insights into comprehending the self-assembly behavior of complex polymer systems.

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Encapsulation of Nanoparticles in Block Copolymer Micellar Aggregates by Directed Supramolecular Assembly

Cited by 112 publications

References 31 publications

Entropy-Driven Hierarchical Nanostructures from Cooperative Self-Assembly of Gold Nanoparticles/Block Copolymers under Three-Dimensional Confinement

Entropy-Driven Hierarchical Nanostructures from Cooperative Self-Assembly of Gold Nanoparticles/Block Copolymers under Three-Dimensional Confinement

Dynamically arrested micelles in a supercooled sugar urea melt

Controllable Nanostructure Formation through Enthalpy-Driven Assembly of Polyoxometalate Clusters and Block Copolymers

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