Block copolymers self-assembly structure formation

The literature is abundant in describing the formation of spherical micelles from block copolymer self-assembly. From the classical diblock copolymer AB, two types of micelles could be prepared as a function of their structural parameters (Fig. 5). 

Structure Formation via Block Copolymer Self-Assembly. 102... 

Figure 1 depicts structures of nanotubes that have so far been derived from block copolymer self-assembly. While the nanotubes are drawn as being rigid and straight, they, in reality, can bend or contain kinks. The top scheme depicts a nanotube formed from either an AB diblock copolymer [15,16] or an ABA triblock copolymer [17], where the gray B block forms a dense intermediate shell and the dark A block or A blocks stretch into the solvent phase from both the inner and outer surfaces of the gray tubular sheU. Such tubes have been prepared so far from the direct self-assembly or tubular micelle formation of a few block copolymers in block-selective solvents, which solubilize only the dark A block or blocks. Nanotubes with structures depicted in the middle and bottom schemes have been prepared from precursory ABC triblock copolymer nanofibers, which consist of an A corona, a cross-linked intermediate B shell, and a C core [18] A fully empty tubular core was ob-... 

Finally, it needs to be mentioned that the mechanisms of supramolecular self-assembly apply to many systems more complex than simple surfactants and amphiphilic block copolymers. Supramolecular self-assembly and pattern formation is one of the crucial principles in nature and gives rise to hierarchical structure ranging from the length scale of a few nanometers to the macroscopic domain. The generation of intricate and very regular structures by templating supramolecularly self-assembled structures in the shape of LLC phases has proven extremely successful. Therefore, the utilization of the more complex systems found in nature (e.g. protein assemblies in viruses) is at the hands of mod-... 

One particular asset of structured self-assemblies is their ability to create nano- to microsized domains, snch as cavities, that could be exploited for chemical synthesis and catalysis. Many kinds of organized self-assemblies have been proved to act as efficient nanoreactors, and several chapters of this book discnss some of them such as small discrete supramolecular vessels (Chapter Reactivity In Nanoscale Vessels, Supramolecular Reactivity), dendrimers (Chapter Supramolecular Dendrlmer Chemistry, Soft Matter), or protein cages and virus capsids (Chapter Viruses as Self-Assembled Templates, Self-Processes). In this chapter, we focus on larger and softer self-assembled structures such as micelles, vesicles, liquid crystals (LCs), or gels, which are made of surfactants, block copolymers, or amphiphilic peptides. In addition, only the systems that present a high kinetic lability (i.e., dynamic) of their aggregated building blocks are considered more static objects such as most of polymersomes and molecularly imprinted polymers are discussed elsewhere (Chapters Assembly of Block Copolymers and Molecularly Imprinted Polymers, Soft Matter, respectively). Finally, for each of these dynamic systems, we describe their functional properties with respect to their potential for the promotion and catalysis of molecular and biomolecu-lar transformations, polymerization, self-replication, metal colloid formation, and mineralization processes. 

As biological systems have always been an inspiration for scientists, intracellular compartments (such as lysosomes or mitochondria) also have their artificial equivalents in polymer vesicles, called polymersomes. Polymersomes are spherical compartments with a bi- or monolayer membrane, generated by self-assembly of di- or triamphiphilic block copolymers in diluted aqueous conditions. To favor the formation of structures such as polymersomes, it is necessary to have a hydrophilic fraction of the copolymer mass of 25-40%, and polymer concentration above the critical micellar concentration. Other parameters that affect the self-assembly process, and therefore the final architecture of the polymer supramolecular assemblies, are the molecular weight of the copolymer (Af ), block lengths, solubility, and glass transition temperature (Tg) [21,22], The relative mass or volume fraction of each block is a key parameter in the formation of a self-assembled structure with a certain membrane curvature, and ultimately, with a specific architecture. The of the copolymer (and thus the block lengths) dictates the membrane thickness and polymersome properties, such as membrane fluidity, stabihty, and permeabihty [21,74],... 

One approach to the self-assembly of polymers into tube-like structures is the use of block copolymers. They enable the formation of structures with amphiphilic behavior, which tend to assemble into helices or vesicles. 

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