Redox potential control

Shifman JM, Gibney BR, Sharp RE et al (2000) Heme redox potential control in de novo designed four-a-helix bundle proteins. Biochemistry 39 14813-14821... 

Important consequences result from the increase of the redox potential of metal clusters with their nuclearity. Indeed, independently of the metal, the smaller clusters are more sensitive to oxidation and can undergo corrosion even by mild oxidizing agents. Moreover, size-dependent redox properties explain the catalytic efficiency of colloidal particles during electron transfer processes. Their redox potentials control their role as electron relays the required potential being intermediate between the thresholds of the potentials of the donor (more negative) and of the acceptor (more positive). Catalytic properties of the nanoparticles are thus size-dependent. Haruta and co-workers reported that gold nanoparticles smaller than 5 nm have potential applications in catalysis as they are very active in... 

For metals, the primary factors affecting immobilization are pH control, chemical speciation, and redox potential control. For organics, immobilization of constituents can be broken down into two primary classifications (1) reactions that destroy or alter organic compounds and (2) physical processes such as adsorption and encapsulation (Conner and Hoeffner 1998b). 

Das A, Grinkova YV, Sligar SG (2007) Redox potential control by drug binding to cytochrome P450 3A4. J Am Chem Soc 129 13778-13779... 

AK Churg, A Warshel. Control of the redox potential of cytochrome c and microscopic dielectric effects m proteins. Biochemistry 25 1675, 1986. 

PJ Stephens, DR Jollie, A Warshel. Protein control of redox potentials of iron-sulfur proteins. Chem Rev 96 2491-2513, 1996. 

J-C Marchon, T Mashiko, CA Reed. How does nature control cytochrome redox potentials In C Ho, ed. Electron Transport and Oxygen Utilization. New York Elsevier North-Holland, 1982, pp 67-72. 

R Langen, GM Jensen, U Jacob, PJ Stephens, A Warshel. Protein control of iron-sulfur cluster redox potentials. J Biol Chem 267 25625-25627, 1992. 

It follows from the electrochemical mechanism of corrosion that the rates of the anodic and cathodic reactions are interdependent, and that either or both may control the rate of the corrosion reaction. It is also evident from thermodynamic considerations (Tables 1.9 and 1.10) that for a species in solution to act as an electron acceptor its redox potential must be more positive than that of the M /M equilibrium or of any other equilibrium involving an oxidised form of the metal. 

It is usual to choose a container metal for fused salts sufficiently noble for the displacement reaction (2.16) to be negligible, and the most important aspects of corrosion are, as in aqueous solutions, those which involve reducible impurities, although in a salt melt there is also the additional possibility of a reducible anion (see above). All such factors can be described as controlling the oxidising power of the melt, which can be defined in terms of a redox potential just as in aqueous solutions The redox potential is expressed by relationships of the form... 

Under certain conditions, it will be impossible for the metal and the melt to come to equilibrium and continuous corrosion will occur (case 2) this is often the case when metals are in contact with molten salts in practice. There are two main possibilities first, the redox potential of the melt may be prevented from falling, either because it is in contact with an external oxidising environment (such as an air atmosphere) or because the conditions cause the products of its reduction to be continually removed (e.g. distillation of metallic sodium and condensation on to a colder part of the system) second, the electrode potential of the metal may be prevented from rising (for instance, if the corrosion product of the metal is volatile). In addition, equilibrium may not be possible when there is a temperature gradient in the system or when alloys are involved, but these cases will be considered in detail later. Rates of corrosion under conditions where equilibrium cannot be reached are controlled by diffusion and interphase mass transfer of oxidising species and/or corrosion products geometry of the system will be a determining factor. 

Figure 26 shows the redox potential of 40 monolayers of cytochrome P450scc on ITO glass plate in 0.1 KCl containing 10 mM phosphate buffer. It can be seen that when the cholesterol dissolved in X-triton 100 was added 50 pi at a time, the redox peaks were well distinguishable, and the cathodic peak at -90 mV was developed in addition to the anodic peak at 16 mV. When the potential was scanned from 400 to 400 mV, there could have been reaction of cholesterol. It is possible that the electrochemical process donated electrons to the cytochrome P450scc that reacted with the cholesterol. The kinetics of adsorption and the reduction process could have been the ion-diffusion-controlled process. 

In order to realize the precise control of core/shell structures of small bimetallic nanoparticles, some problems have to be overcome. For example, one problem is that the oxidation of the preformed metal core often takes place by the metal ions for making the shell when the metal ions have a high-redox potential, and large islands of shell metal are produced on the preformed metal core. Therefore, we previously developed a so-called hydrogen-sacrificial protective strategy to prepare the bimetallic nanoparticles in the size range 1.5-5.5nm with controllable core/shell structures [132]. The strategy can be extended to other systems of bi- or multimetallic nanoparticles. 

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