Self-adsorbed monolayer

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. 

Freunscht P, Van Duyne R P and Schneider S 1997 Surface-enhanced Raman spectroscopy of trans-stilbene adsorbed on platinum- or self-assembled monolayer-modified silver film over nanosphere surfaces Chem. Phys. Lett. 281 372-8... 

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. 

Adsorption phenomena from solutions onto sohd surfaces have been one of the important subjects in colloid and surface chemistry. Sophisticated application of adsorption has been demonstrated recently in the formation of self-assembhng monolayers and multilayers on various substrates [4,7], However, only a limited number of researchers have been devoted to the study of adsorption in binary hquid systems. The adsorption isotherm and colloidal stabihty measmement have been the main tools for these studies. The molecular level of characterization is needed to elucidate the phenomenon. We have employed the combination of smface forces measmement and Fomier transform infrared spectroscopy in attenuated total reflection (FTIR-ATR) to study the preferential (selective) adsorption of alcohol (methanol, ethanol, and propanol) onto glass surfaces from their binary mixtures with cyclohexane. Om studies have demonstrated the cluster formation of alcohol adsorbed on the surfaces and the long-range attraction associated with such adsorption. We may call these clusters macroclusters, because the thickness of the adsorbed alcohol layer is about 15 mn, which is quite large compared to the size of the alcohol. The following describes the results for the ethanol-cycohexane mixtures [10],... 

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. 

Interest in the adsorption of sulfur-containing molecules at metal surfaces been stimulated by a desire to elucidate the decomposition mechanisms of thiols during the catalytic removal of sulfur from feedstocks and the position of thiols as the favoured head groups for adsorbates used to construct self-assembled monolayers. We shall not survey the extensive self-assembled film literature but restrict our discussion to the simpler thiols. 

Strong L, Whitesides GM (1988) Structures of self-assembled monolayer films of organosulfur compounds adsorbed on gold single crystals electron diffraction studies. Langmuir 4 546-558... 

J. M. Tour, L. Jones II, D. L. Pearson, J. S. Lamba, T. P. Bur-gin, G. W. Whitesides, D. L Allara, A. N. Parikh, S. Atre, Self-Assembled Monolayers and Multilayers of Conjugated Thiols, a,co-Dithiols, and Thioacetyl-Containing Adsorbates. Understanding Attachments Between Potential Molecular Wires and Gold Surfaces, J. Am Chem Soc. 1995,112 9529-9534. 

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. 

A large number of examples of redox polyelectrolyte monolayers have been reported [42[. Anson described the adsorption of poly(acrylic acid) onto glassy carbon with electrostatic binding of Ru(NH3)6 and Co(NH3)6 ions from solution [43]. Finklea [44] adsorbed poly(4-vinyl-I-methyl-pyridinium methylsulfate) on self-assembled mercapto-undecanoic self-assembled monolayer (SAM) on gold electrodes to... 

Fe2(III,III)2+ states. By considering that organometallic dendrimers based on conjugated ferrocene units are of special importance since mixed-valence states have interesting electrical, redox, and magnetic properties, recently three generations of polypropylene amine) dendrimers, decorated at their periphery with 4, 8, and 16 (compound 6, Fig. 6.6a) BFc units, respectively, have been synthesized and the electrochemical behavior of the dendrimers complexed with (3-cyclodextrins ([3-CD) and adsorbed at self-assembled monolayers (SAMs) of heptathioether-functionalized [3-CD on gold (molecular printboard) has been studied.40... 

A recent study by DePalma and Tillman [ 10] also demonstrates the potential of surface modification by self-assembled monolayers of low surface energy fiuoroalkyl-containing silanes. Fatty acids, amines and alcohols have long been known to adsorb as monomolecular films on metals. Silane coupling agents have featured strongly in new studies to develop more robust films, covalently bound together and to the metal substrate. 

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