Monolayers electrochemistry

Porter M D, Bright T B, Allara D L and Chidsey C E D 1987 Spontaneously organized molecular assemblies. 4. Structural characterization of normal-alkyl thiol monolayers on gold by optical ellipsometry, infrared-spectroscopy, and electrochemistry J. Am. Chem. Soc. 109 3559-68... 

RAIRS is routinely used for the analysis of chemically modified surfaces - surface systems in electrochemistry [4.277], polymer research [4.266, 4.278], catalysis [4.265, 4.271], selfassembling monolayers [4.267, 4.268], and protein adsorption [4.268, 4.279] have been investigated. 

To date, numerous radical-induced hydrosilylations of terminal olefins or acetylenes have been reported for the H-terminated Si(l 11) surfaces. These reactions are mainly performed by using thermal conditions, UV irradiation, or electrochemistry. More recently, a very mild method was developed for the attachment of high-quality organic monolayers on crystalline silicon surfaces. 

From this discussion it is clear, that, independently of their redox properties, suitably modified electrodes offer themselves for the introduction of diastereo- or enantioselectivity into electrochemistry. Early reports of chiral inductions at modified electrodes include reactions at graphite and SnO surfaces derivatized with monolayers of (S)-(—)-phenylalanine. Asymmetric inductions at the chiral graphite electrode could, however, not be verified in other laboratories even after great efforts... 

Numerous works have been implemented on tellurium electrochemistry and its adsorption at metal surfaces. The morphological structures of electrodeposited Te layers at various stages of deposition (first UPD, second UPD, and bulk deposition) are now well known [88-93]. As discussed in the previous paragraphs, Stickney and co-workers have carried out detailed characterizations of the first Te monolayer on Au single-crystal surfaces in order to establish the method of electrochemical atomic layer epitaxy of CdTe. 

Hosier H, Richter B, Behm RJ. 2004. Catalytic influence of Pt monolayer islands on the hydrogen electrochemistry of Ru(OOOl) studied by ultrahigh vacuum scanning tunneling microscopy and cychc voltammetry. J Phys Chem B 108 14780. 

Perhaps the most important experimental progress made recently in electrochemistry was the introduction of a scanning electrochemical microscope (SECM). Tsionsky et al. have used SECM to study also the rate of ET across a lipid monolayer at the water-benzene interface [48,49]. The presence of the monolayer decreased the rate of ET, being the decrease more significant for longer hydrocarbon chains and larger lipid concentration in solution. It was thus concluded that the ET reaction does not occur at defect sites in the lipid monolayer. 

Ion A, Partali V, Sliwka HR, and Banica FG. 2002. Electrochemistry of a carotenoid self-assembled monolayer. Electrochemistry Communications 4(9) 674-678. 

Under potential deposition is a much-studied phenomenon in electrochemistry and is the electrochemical reduction of a metal cation to form a monolayer or submonolayer of the corresponding metal at the surface of an electrode. The critical point is that deposition occurs at a potential higher than that dictated by the reversible potential of the metal/metal cation couple, suggesting that such a upd layer is energetically quite different from the bulk metal. However, subsequent deposition on a upd monolayer occurs at the expected potential, and the resulting surface is typical of the bulk metal. 

Y. Tian, L. Mao, T. Okajima, and T. Ohsaka, Electrochemistry and electrocatalytic activities of superoxide dismutases at gold electrodes modified with a self-assembled monolayer. Anal. Chem. 76, 4162-4168 (2004). 

Kolb, D. M., Physical and Electrochemical Properties of Metal Monolayers on Metallic Substrates, in Advances in Electrochemistry and Electrochemical Engineering, H. Gerischer and C. W. Tobias, Editors. 1978, Wiley New York. p. 125. 

Photosystem I, Monolayers, Langmuir-Blodgett films, Absorbance, Electrochemistry. 

We have recently modified U7) one of the several radiochemical methods (U5) which have been used for surface electrochemistry investigations in order to characterize adsorption on well-defined, single crystal electrodes. Below, we will describe the technique and identify some challenging issues which we will be able to address. The proposed method is sensitive to a few percent of a monolayer at smooth surfaces, is nondestructive and simple to use. The radiochemical measurements can be made with all compounds which can be labelled with reasonably long-lived, preferably g- emitting radioisotopes. We believe this technique will fulfill the quantitative function in in situ surface analysis as Auger spectroscopy currently does in vacuum, ex situ characterization of electrodes. 

Structure, Electrochemistry and Applications of Self-Assembled Monolayers of Thiols... 

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