Self-assembly effects

Finally, our group reported on gold nanoparticles decorated with bent-core liquid crystals showing pattern formation on TEM grids after slow solvent evaporation (18 in Fig. 22). These particles showed interesting self-assembly effects in different bent-core liquid crystal hosts (SmCPA and Colr) and slightly improved electro-optic effects such as shorter response time, x, and unaltered spontaneous polarization in the SmCPA host, but no mesophase formation [547]. 

For polymer chemists it is interesting to know how well-known linear polymers can be linked with dendritic architectures and what the supramolecular consequences of this approach might be. Combination of dendrimers with linear polymers in hybrid linear-dendritic block copolymers has been employed to achieve particular self-assembly effects. Block copolymers with a linear polyethylene oxide block and dendritic polybenzylether block form large micellar structures in solution that depend on the size (i.e., the generation) of the dendritic block [10]. Amphiphilic block copolymers have been prepared by the combination of a linear, apolar polystyrene chain with a polar, hydrophilic poly(propylene imine) dendrimer [11] as well as PEO with Boc-substituted poly-a, -L-lysine dendrimers, respectively [12]. Such block copolymers form large spherical and cylindrical micelles in solution and have been described as superamphi-philes and hydra-amphiphiles , respectively. 

Edwin, N. J. Hammer, R. R McCarley, R. L. Russo, P. S. Reversibility of p-amyloid self-assembly Effects of pH and added salts assessed by fluorescence photobleaching recovery. Biomacromolecules 2010,11, 341-347. 

An even coarser description is attempted in Ginzburg-Landau-type models. These continuum models describe the system configuration in temis of one or several, continuous order parameter fields. These fields are thought to describe the spatial variation of the composition. Similar to spin models, the amphiphilic properties are incorporated into the Flamiltonian by construction. The Flamiltonians are motivated by fiindamental synnnetry and stability criteria and offer a unified view on the general features of self-assembly. The universal, generic behaviour—tlie possible morphologies and effects of fluctuations, for instance—rather than the description of a specific material is the subject of these models. 

As reviewed so far, the contact-mechanics-based techniques (JKR and SFA methods) have been effective in the understanding molecular level mechanisms related to the adhesion of elastomers and in measuring the surface and interfacial energies of polymers and self-assembled monolayers. The current work in this area is aimed at understanding contact induced interfacial rearrangements and the role of specific interactions. The recent progress of these studies is discussed in this section. 

Random interface models for ternary systems share the feature with the Widom model and the one-order-parameter Ginzburg-Landau theory (19) that the density of amphiphiles is not allowed to fluctuate independently, but is entirely determined by the distribution of oil and water. However, in contrast to the Ginzburg-Landau approach, they concentrate on the amphiphilic sheets. Self-assembly of amphiphiles into monolayers of given optimal density is premised, and the free energy of the system is reduced to effective free energies of its internal interfaces. In the same spirit, random interface models for binary systems postulate self-assembly into bilayers and intro-... 

Tethering may be a reversible or an irreversible process. Irreversible grafting is typically accomplished by chemical bonding. The number of grafted chains is controlled by the number of grafting sites and their functionality, and then ultimately by the extent of the chemical reaction. The reaction kinetics may reflect the potential barrier confronting reactive chains which try to penetrate the tethered layer. Reversible grafting is accomplished via the self-assembly of polymeric surfactants and end-functionalized polymers [59]. In this case, the surface density and all other characteristic dimensions of the structure are controlled by thermodynamic equilibrium, albeit with possible kinetic effects. In this instance, the equilibrium condition involves the penalties due to the deformation of tethered chains. 

AB diblock copolymers in the presence of a selective surface can form an adsorbed layer, which is a planar form of aggregation or self-assembly. This is very useful in the manipulation of the surface properties of solid surfaces, especially those that are employed in liquid media. Several situations have been studied both theoretically and experimentally, among them the case of a selective surface but a nonselective solvent [75] which results in swelling of both the anchor and the buoy layers. However, we concentrate on the situation most closely related to the micelle conditions just discussed, namely, adsorption from a selective solvent. Our theoretical discussion is adapted and abbreviated from that of Marques et al. [76], who considered many features not discussed here. They began their analysis from the grand canonical free energy of a block copolymer layer in equilibrium with a reservoir containing soluble block copolymer at chemical potential peK. They also considered the possible effects of micellization in solution on the adsorption process [61]. We assume in this presentation that the anchor layer is in a solvent-free, melt state above Tg. The anchor layer is assumed to be thin and smooth, with a sharp interface between it and the solvent swollen buoy layer. 

Self-assembled monolayers are formed spontaneously by the immersion of an appropriate substrate into a solution of active surfactant in an organic solvent. After the substrate is immersed for a time from minutes to hours, it is rinsed with ligroin, methanol, distilled water, and dried in a steam of nitrogen. An apparent effect of the monolayer coating is the drastic change in wettability of the surface so that the measurement of the contact angle can be considered as an effective way to detect the formation of the SAMs. 

Micellar nanocarriers have already been applied successfully for delivery of hydro-phobic drugs [86]. These carriers are usually the product of self-assembled block copolymers, consisting of a hydrophilic block and a hydrophobic block. Generally, an ELP with a transition temperature below body temperature is used as hydrophobic block and the hydrophilic block can be an ELP with a transition temperature above body temperature or another peptide or protein. The EPR effect also directs these types of carriers towards tumor tissue. 

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