Dynamic assembly, block copolymers

Keywords Block copolymer Dynamic assembly Nanostructure... 

The impenetrability of assemblies of tethered chains has broad implications. Some of these are discussed in more detail in the sections on interactions, on dynamics and on block copolymer melts. Examples of phenomena that have been... 

Recently, we have also prepared nanosized polymersomes through self-assembly of star-shaped PEG-b-PLLA block copolymers (eight-arm PEG-b-PLLA) using a film hydration technique [233]. The polymersomes can encapsulate FITC-labeled Dex, as model of a water-soluble macromolecular (bug, into the hydrophilic interior space. The eight-arm PEG-b-PLLA polymersomes showed relatively high stability compared to that of polymersomes of linear PEG-b-PLLA copolymers with the equal volume fraction. Furthermore, we have developed a novel type of polymersome of amphiphilic polyrotaxane (PRX) composed of PLLA-b-PEG-b-PLLA triblock copolymer and a-cyclodextrin (a-CD) [234]. These polymersomes possess unique structures the surface is covered by PRX structures with multiple a-CDs threaded onto the PEG chain. Since the a-CDs are not covalently bound to the PEG chain, they can slide and rotate along the PEG chain, which forms the outer shell of the polymersomes [235,236]. Thus, the polymersomes could be a novel functional biomedical nanomaterial having a dynamic surface. 

By covalent linkage of different types of molecules it is possible to obtain materials with novel properties that are different from those of the parent compounds. Examples of such materials are block-copolymers, soaps, or lipids which can self-assemble into periodic geometries with long-range order. Due to their amphiphilic character, these molecules tend to micellize and to phase-separate on the nanometer scale. By this self-assembly process the fabrication of new na-noscopic devices is possible, such as the micellization of diblock-co-polymers for the organization of nanometer-sized particles of metals or semiconductors [72 - 74]. The micelle formation is a dynamic process, which depends on a number of factors like solvent, temperature, and concentration. Synthesis of micelles which are independent of all of these factors via appropriately functionalized dendrimers which form unimolecular micelles is a straightforward strategy. In... 

From a theoretical standpoint, block copolymers are ideal systems for studying many fundamental issues in the thermodynamics and dynamics of self-assembly of soft materials. This is so because of the relatively large length scale of macromolecules, the slow dynamics associated with the relevant structural relaxations, and the ease of control of the molecular characteristics, such as the molecular weight, compositions, and architecture. 

Block copolymers in selective solvents exhibit a remarkable capacity to self-assemble into a great variety of micellar structures. The final morphology depends on the molecular architecture, tlie block composition, and the affinity of the solvent for the different blocks. The solvophobic blocks constitute the core of the micelles, while the soluble blocks form a soft and deformable corona (Fig. Id). Because of this architecture, micelles are partially Impenetrable, just like colloids, but at the same time inherently soft and deformable like polymers. Most of their properties result from this subtle interplay between colloid-like and polymer-like features. In applications, micelles are used to solubilize in solvents otherwise insoluble compounds, to compatibilize polymer blends, to stabilize colloidal particles, and to control tire rheology of complex fluids in various formulations. A rich literature describes the phase behavior, the structure, the dynamics, and the applications of block-copolymer micelles both in aqueous and organic solvents [65-67],... 

These are stable micelles that are formed with polymeric surfactants. Amphiphilic block copolymers such as the pluronics (polyoxyethylene-polyoxypropylene block copolymers) are able to self-assemble into polymeric micelles and hydrophobic drugs may be solubilized within the core of the micelle or, alternatively, conjugated to the micelle-forming polymer. Although micelles are rather dynamic systems that continuously exchange units between the micelle structure and the free units in solution, those composed of polyoxyethylene - poly(aspartic acid) have been found sufficiently... 

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