Adsorbed layer self-assemblies

A logical division is made for the adsorption of nonelectrolytes according to whether they are in dilute or concentrated solution. In dilute solutions, the treatment is very similar to that for gas adsorption, whereas in concentrated binary mixtures the role of the solvent becomes more explicit. An important class of adsorbed materials, self-assembling monolayers, are briefly reviewed along with an overview of the essential features of polymer adsorption. The adsorption of electrolytes is treated briefly, mainly in terms of the exchange of components in an electrical double layer. 

The structural state of dendritic macromolecules at air-water (Langmuir mono-layers) and air-solid (adsorbed monolayers, self-assembled films and cast films) interfaces have been reviewed by Tsukruk [17]. Although this work summarizes various characterization techniques for dendritic films by AFM techniques, in this chapter, we will present recent progress on the characterization of the dendritic film surface morphologies. 

Fig. 4.13 General scheme of dendritic macromolecules within molecular layers at interfaces (a) compressed Langmuir bilayer at air-water interface (b) adsorbed and self-assembled monolayers of neutral dendrimers (left) and dendrimers with sticky surface groups (right) (c) multilayer self-assembled films obtained by layer-by-layer deposition of dendrimers low molar mass ions (left) and two adjacent dendrimer generations (right). (From ref. [106])...

Light-emitting devices based on sequentially adsorbed layer-by-layer SELF-ASSEMBLED FILMS OF ALIZARIN VIOLET... 

Light-Emitting Devices Based on Sequentially Adsorbed Layer-By-Layer Self-Assembled Films of Alizarin Violet... 

Hodak, J., et al.. Layer-by-layer self-assembly of glucose oxidase with a poly(aUylamine)ferrocene redox mediator. Langmuir, 1997.13(10) p. 2708-2716. Yoo, D., et al.. New electro-active self-assembled multilayer thin films based on alternately adsorbed layers of polyelectrolytes and functional dye molecules. Synthetic Metals, 1997. 85(1-3) p. 1425-1426. 

The power of optical spectroscopies is that they are often much better developed than their electron-, ion- and atom-based counterparts, and therefore provide results that are easier to interpret. Furtlienuore, photon-based teclmiques are uniquely poised to help in the characterization of liquid-liquid, liquid-solid and even solid-solid interfaces generally inaccessible by other means. There has certainly been a renewed interest in the use of optical spectroscopies for the study of more realistic systems such as catalysts, adsorbates, emulsions, surfactants, self-assembled layers, etc. 

Self-assembled monolayers (SAMs) are molecular layers tliat fonn spontaneously upon adsorjDtion by immersing a substrate into a dilute solution of tire surface-active material in an organic solvent [115]. This is probably tire most comprehensive definition and includes compounds tliat adsorb spontaneously but are neither specifically bonded to tire substrate nor have intennolecular interactions which force tire molecules to organize tliemselves in tire sense tliat a defined orientation is adopted. Some polymers, for example, belong to tliis class. They might be attached to tire substrate via weak van der Waals interactions only. 

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 (SAMs) [8] The layers are formed by heterologous interaction between reactive groups, such as thiols, and noble metals, such as gold or silver. Since the molecules are selectively adsorbed on these metals, film growth stops after the first monolayer is completed. The molecular aggregation is enthalpy driven, and the final structure is in thermodynamic equilibrium. 

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