Self-Assembly in General

In principle, we can distinguish (for surfactant self-assemblies in general) between a microstructure in which either oil or water forms discrete domains (droplets, micelles) and one in which both form domains that extend over macroscopic distances (Fig. 7a). It appears that there are few techniques that can distinguish between the two principal cases uni- and bicontinuous. The first technique to prove bicontinuity was self-diffusion studies in which oil and water diffusion were monitored over macroscopic distances [35]. It appears that for most surfactant systems, microemulsions can be found where both oil and water diffusion are uninhibited and are only moderately reduced compared to the neat liquids. Quantitative agreement between experimental self-diffusion behavior and Scriven s suggestion of zero mean curvature surfactant monolayers has been demonstrated [36]. Independent experimental proof of bicontinuity has been obtained by cryo-electron microscopy, and neutron diffraction by contrast variation has demonstrated a low mean curvature surfactant film under balanced conditions. The bicontinuous microemulsion structure (Fig. 7b) has attracted considerable interest and has stimulated theoretical work strongly. 

We have noted that micellization (and surfactant self-assembly in general) is some intermediate between phase separation and simple complex formation and this is illustrated in the ways that micellization has been modelled in thermodynamic analyses. Micelle formation is generally discussed in terms of one of the following models. 

The way that Pn peptides self-assemble is important for polypeptides and proteins amyloid-type structures are believed to have the same core stmcture, and in fact the propensity to self-assemble in this manner is hypothesized to be a general property of polypeptides [52]. It is therefore unsurprising that systems featuring this motif are common. In recent years, a push towards the use of peptide-based self-assembled materials has led to increasing interest in extending their functionality by derivatising them. 

Thus, it is herein that we now describe the results of this analysis which we regard as the development of a general strategy for the construction of spherical molecular hosts. [11] We will begin by presenting the idea of self-assembly in the context of spherical hosts and then, after summarizing the Platonic and Archimedean solids, we will provide examples of cubic symmetry-based hosts, from both the laboratory and nature, with structures that conform to these polyhedra. 

There is now a solid body of available knowledge to indicate that the general features of biopolymer self-assembly in bulk aqueous solutions can account for various detailed aspects of the stability, rheology and microstructure of oil-in-water emulsions (and foams) stabilized by the same kinds of biopolymers (Dickinson, 1997, 1998 Casanova and Dickinson, 1998 Dickinson et al., 1997, 1998 Semenova et al., 1999, 2006 van der Linden, 2006 Semenova, 2007 Ruis et al., 2007). In particular, the richness of the self-assembly and surface-active properties of the... 

Generally, the mechanism proposed for structure direction and self-assembly in the synthesis of Si-ZSM-5 involves the formation of an ordered, hydrophobic hydration sphere around the TPA cation [11]. The assembly process of MCM-41 is controlled by electrostatic interaction between silicate species and charged surfactant head groups [12]. 

As described in the Introduction, Pasteur showed beautifully that racemic molecules resolve spontaneously into chiral forms when they crystallize. We call them conglomerates, in which molecules form condensates comprised of only one enantiomer. The condensation into conglomerates can now be observed not only in crystals but in monolayers, fibers, and supramolecules self-assembled in solution [35]. The researches became possible because of the development of microscopic observation techniques at the nanometer scale. However, in crystals we still do not know what kinds of molecules show spontaneous resolution. Hence, observation of chiral resolution in soft matter may provide important information on the general question. 

We have already dealt with some general aspects of biochemical self-assembly in Section 2.10 including the remarkable formation of viral capsids. There are some biochemical examples, however, that translate readily into supramolecular chemical concepts and have been pivotal in defining the field. One such system is the tobacco mosaic virus, a virus that is very harmful to a variety of crops including tobacco, tomato, pepper, cucumbers and species such as ornamental flowers. This system consists of a helical virus particle measuring some 300 X 18 nm (Figure 10.6). A central strand of RNA is sheathed by 2130 identical protein subunits, each of which contains 158 amino acids. What is remarkable about... 

Self-assembling in liquid media results from decreased system free energy. A general mechanism of self-organization was introduced by Onzager.11 This mechanism is based on a dependence of the change in a system s entropy AS of... 

CONTROL OF lONOPHILIC-IONOPHOBIC INTERACTIONS AND GENERALIZATION OF MOLECULAR SELF-ASSEMBLIES IN IONIC LIQUIDS... 

In summary, the formation of self-assemblies in ionic liquids is a general phenomenon that depends on the molecular structures of amphiphUes, ionic liquids, and their combinations. The ether-introduced ionic liquids facilitate the formation of molecular self-assemblies. However, stable self-assemblies can form also in conventional ionic liquids if the intermolecular interactions are suitably tuned. 

A noteworthy feature in the transformations of ID and 2D structures is that we readily obtain single crystals of the 3D structures as products, although we start with powders of the 1D/2D compounds, generally in solution. The ready crystallization of the 3D structures and the formation of single crystals is likely to be related to the process of self-assembly in these systems. We can represent the different steps as follows ... 

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