Self-assembled monolayers reactions

A second class of monolayers based on van der Waal s interactions within the monolayer and chemisorption (in contrast with physisorption in the case of LB films) on a soHd substrate are self-assembled monolayers (SAMs). SAMs are well-ordered layers, one molecule thick, that form spontaneously by the reaction of molecules, typically substituted-alkyl chains, with the surface of soHd materials (193—195). A wide variety of SAM-based supramolecular stmctures have been generated and used as functional components of materials systems in a wide range of technological appHcations ranging from nanoHthography (196,197) to chemical sensing (198—201). 

L. Haussling, H. Ringsdorf, F.J. Schimitt, and W. Knoll, Biotin-functionalized self-assembled monolayers on gold-surface-plasmon optical studies of specific recognition reactions. Langmuir 7, 1837-184 (1991). 

L. Jiang, C.J. McNeil, and J.M. Cooper, Direct electron transfer reaction of glucose oxidase immobilized at a self-assembled monolayer. J. Chem. Soc. Chem. Commun. 1293-1295 (1995). 

Hou et al. developed a method that controlled the generation of a nanomolar amount of NO [173]. A self-assembled monolayer of N-nitroso-N-oxy-p-thiomethyl-benzeamine ammonium salt bound to a gold electrode via a thiol linkage was used for the reaction. When an electric potential was applied, one-electron electrochemical oxidation led to the release of NO (Scheme 3.20). There was a linear relationship between the amount of NO generated and the area of the electrode, indicating that the amount of NO release could be controlled by selecting an appropriately sized... 

Komatsu K (2005) The Mechanochemical Solid-State Reaction of Fullerenes. 254 185-206 Kriegisch V, Lambert C (2005) Self-Assembled Monolayers of Chromophores on Gold Surfaces. 258 257-313... 

Fig. 9.24 Reaction scheme for the surface-in- rigid self-assembled monolayer of 4 -lithio-4-itiated living anionic polymerization using the mercaptobiphenyl [194].

Gray HB, Winkler JR (1996) Electron transfer in proteins. Annu Rev Biochem 65 537 Fedurco M (2000) Redox reactions of heme-containing metalloproteins dynamic effects of self-assembled monolayers on thermodynamics and kinetics of cytochrome c electron-transfer reactions. Coord Chem Rev 209 263... 

The first surface-initiated enzymatic polymerization reported was the synthesis of amylose brushes on planar and spherical surfaces [145]. For this, silica or silicone surfaces were modified with self-assembled monolayers of (3 amino-propyl)trimethoxysilane or chlorodimethylsilane, respectively. To these functionalities, oligosaccharides were added via (a) reductive amidation of the oligosaccharides to surface-bound amines, (b) conversion of the oiigosaccharide to the according aldonic acid lactone and reaction with surface bound amines, and (c) incorporation... 

Mass spectrum from V. J. Angelico, S. A. Mitchell, and V. H. Wysocki, "Low-Energy Ion-Surface Reactions of Pyrazine with Two Classes of Self-Assembled Monolayers, Anal. Chem. 2000, 72, 2603. 

Finally, self-assembled monolayers (SAMs) on gold electrodes constitute electrochemical interfaces of supramolecular structures that efficiently connect catalytic reactions, substrate and product diffusion and heterogeneous electron transfer step when enzymes are immobilised on them. Resulting enzyme-SAM electrodes have demonstrated to exhibit good performance and long-term enzyme stability. 

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