Polystyrene-Dendrimer Amphiphilic Block Copolymers with a Generation-Dependent Aggregation

Hest, Jan C. M. van; Delnoye, D.A.P.; Baars, Maurice W. P. L.; Genderen, Marcel H. P. van; Meijer, E. W.

doi:10.1126/science.268.5217.1592

Cited by 503 publications

(347 citation statements)

References 25 publications

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“…A distinct class of amphiphilic macromolecules capable of vesicle formation has been synthesized by coupling of PS to poly(propylene imine) dendrimers [25]. The shape of these PS-dendrimer diblock copolymers is comparable with that of small-molecule surfactants, and not with the more traditional block copolymers described earlier.…”

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confidence: 97%

Block copolymer vesicles

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Cornelissen

Hest

2004

Pure and Applied Chemistry

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Amphiphilic block copolymers have the ability to assemble into multiple morphologies in solution. Depending on the length of the hydrophilic block, the morphology can vary from spherical micelles, rods, and vesicles to large compound micelles (LCMs). Vesicle formation is favored upon an increase in total molecular weight of the block copolymer, that is, an increasing bending modulus (K). Owing to the polymeric character of this type of vesicle (also called polymersomes), they possess remarkable properties. The diffusion of (polymeric) amphiphiles in these vesicles is very low compared to liposomes and for high-molecular-weight chain entanglements even lead to reptation-type motions, which make it possible to trap near-equilibrium and metastable morphologies. Additionally, in contrast to liposomes, membrane thicknesses can exceed 200 nm. As a consequence, this increased membrane thickness, in combination with the conformational freedom of the polymer chains, leads to a much lower permeability for water of block copolymer vesicles compared to liposomes. The enhanced toughness and reduced permeability of polymersomes makes them, therefore, very suitable as stable nanocontainers, which can be used, for example, as reactors or drug delivery vehicles.Self-assembly of amphiphilic block copolymers in solution has been a topic of active research for more than 30 years. The most commonly observed morphology in these systems is the star-micelle. "Star" refers to the fundamental core-corona structure, which consists of a small core and a large corona. These star-micelles can be divided into regular and reversed micelles, which are formed in polar and apolar solvents, respectively.Over the past few years, the ability of highly asymmetric, amphiphilic block copolymers to assemble into aggregates of multiple morphologies in solution has attracted much attention. For these "crew-cut" aggregates, a term proposed by Halperin et al. [1], the longer block forms the core of the aggregate, while the corona is composed of the short segment. Manipulation of the relative block lengths and environmental parameters, such as solvent composition, the presence of additives, and temperature, has resulted in a variety of morphologies, including spheres, rods, vesicles, lamellae, tubules, large compound micelles (LCMs), large compound vesicles (LCVs), and hexagonally packed hollow hoops (HHHs).Several of these block copolymer morphologies are classified as vesicles because they all have hollow-spherical structures containing walls composed of bilayers of polymer molecules. The field of block copolymer vesicles (polymersomes) has only recently been explored. The earliest reports on polymersomes focused on vesicles prepared from bulk copolymer systems [2] and block copolymer/homo-

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confidence: 97%

Block copolymer vesicles

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Cornelissen

Hest

2004

Pure and Applied Chemistry

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“…Since the first reports, 208,209 a large number of examples describing the formation of polymersomes have been published. [210][211][212][213] The structure of vesicle-forming block copolymers can vary from simple coil-coil diblock copolymers and further to rod-coil diblock copolymers to coil-coil and rod-coil multiblock copolymers with and without additional cross-linkable groups ( Figure 19).…”

Section: Polymersomes As Nanoreactorsmentioning

confidence: 99%

Self-Assembled Nanoreactors

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“…In the early stage, the aim was focused on the construction of the dendron-coil molecular architecture by using diverse synthetic strategies [15][16][17] or the study of the self-assemblies in solution. [18][19][20] However, the recent interest has shifted to the bulk assemblies of dendron-coil molecules. Many dendron-coil assembling systems were reported, but they mostly addressed the solid state.…”

Section: Amphiphilic Dendron-coils Based Upon Aliphatic Polyether Denmentioning

confidence: 99%

Spontaneous bulk organization of molecular assemblers based on aliphatic polyether and/or poly(benzyl ether) dendrons

Cho

2012

Polym J

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This paper reviews our recent research with regard to bulk self-assemblers based on well-defined branched building blocks. Branched molecules/polymers have been known to show different physical properties from conventional linear-shaped polymers. As well as thermal and solution properties, structural modification into branched building blocks also has a significant influence on self-assembling behavior in the bulk states, including solid and liquid crystalline (LC) phases. As a branched component, dendrons/dendrimers with well-defined structures can be ideal candidates for the construction of advanced self-assemblers. Recently, we worked on new assembling systems such as dendron-coils, block codendrimers and discotic LC molecules. In the design, we used aliphatic polyether dendrons in most cases and poly(benzyl ether) dendrons in part. Their bulk assembling and thermal properties were found to be distinct from conventional linear block copolymers and they were dependent upon their chain architectures. To self-assemble into ordered nanostructures, the hybrid assembers were designed to have incompatible blocks, for example, hydrophilic and hydrophobic parts. Furthermore, in some cases an ionic complexation was carried out to maximize the immiscibility between the two different blocks. This review describes the molecular manipulations to engineer the nanoassemblies in bulk and also the ionic transportation properties depending on the assembling morphology.

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Polystyrene-Dendrimer Amphiphilic Block Copolymers with a Generation-Dependent Aggregation

Cited by 503 publications

References 25 publications

Block copolymer vesicles

Block copolymer vesicles

Self-Assembled Nanoreactors

Spontaneous bulk organization of molecular assemblers based on aliphatic polyether and/or poly(benzyl ether) dendrons

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