Cationic surface, electron exchange

Electron transfer can be accomplished by quenching of a micelle trapped chromophore by ions capable of ion pairing with the micelle surface. For example, excited N-methylphenothiazine in sodium dodecylsulfate (SDS) micelles can exchange electrons with Cu(II). The photogenerated Cu(I) is rapidly displaced by Cu(II) from the aqueous phase so that intramicellar recombination is averted, Fig. 5 (266). Similarly, the quantum yield for formation of the pyrene radical cation via electron transfer to Cu(II) increases with micellar complexation from 0.25 at 0.05 M SDS to 0.60 at 0.8 M SDS (267). The electron transfer quenching of triplet thionine by aniline is also accelerated in reverse micelles by this mechanism (268). 

Pomonis and Vickermann used model solid solution catalysts with a-Al203, Ti02, and Sn02 as the host compounds.105 They conclude that vanadium ions have to be present in order to obtain catalysts which are both active and selective. Furthermore a relatively facile electron exchange between the active site cations is necessary in order to give an energetically more stable surface oxygen state than on a localized atomic site. This is important both for the release of 02 and for the reoxidation of the active sites. The host lattice has an important role in the electronic isolation of the active sub-lattice. 

However, our concern is with the cationic surface which promotes a rapid exchange of an electron from dimethylaniline to pyrene, and thereafter maintains a long-lived ion which can react with further solutes added to the system. Hie concept of the experiment is, that dimethylaniline transfers the electron rapidly to pyrene via a diffusion controlled reaction, which occurs by movement of the reactants on the surface of the micelle until they encounter each other. Electron transfer then occurs, and the back reaction of the two ions is prevented by the surface of the micelle, which holds the reactants in an unsuitable configuration for back reaction to occur. However, the repulsive positive force of the micelle on the dimethylaniline cation rapidly drives it away from the micelle, and effective and efficient charge separation is achieved, with a quantum yield Q of unity for the process of charge separation. 

The assumption of the association of Hb in the pores of carboxylic cation exchangers has been advanced in Ref. [47] on the basis of electron microscopy at the maximum filling, almost all the pore surface is filled with Hb associates which are ordered star-shaped structures. Interprotein interaction in the adsorption immobilization of enzymes have been reported in Refs. [74, 75]. 

Electron spin resonance (ESR) is a useful technique for investigating the mobility and orientation of exchange cations at the surface of layer silicate clays in various states of hydration. Using Cu2+ and the charged nitroxide spin probe, TEMPAMINE+... 

Another well-studied electron transfer reaction is the oxidation of aqueous benzidine in the presence of various clays (2, 40, 43, 50, 51). An electron from the colorless benzidine molecule is abstracted by the clay with formation of a blue monovalent radical cation. Upon drying of the blue clay-benzidine system, a yellow color is produced. There is disagreement in the literature with respect to the chemical identity of the yellow product (2, 40, 52) however, in the case of hectorite, the yellow product has been suggested to be the protonated form of the radical cation (divalent radical cation) (2, 52). There is also disagreement about whether the electron-accepting sites of the clay are ferric iron at the planar surfaces, aluminum ions at the edges, or exchangeable cations <2, I). 

---