Redox bridge

Covalent functionlization of CNTs was employed in a flexible way to modify single-walled carbon nanotubes (SWCNTs) by the corresponding redox mediator prior to their deposition on electrode. R. Bilewicz et al. reported the covalent functionalization of SWCNTs with ferrocene and ABTS [6]. Immobilized ferrocene acts as a redox bridge for the electrical wiring of GOX while at the anode and ABTS-modified SWCNTs serve for the electrical connection of laccase at the cathode. 

Figure 1.9 Examples of functionally important intrinsic metal atoms in proteins, (a) The di-iron center of the enzyme ribonucleotide reductase. Two iron atoms form a redox center that produces a free radical in a nearby tyrosine side chain. The iron atoms are bridged by a glutamic acid residue and a negatively charged oxygen atom called a p-oxo bridge. The coordination of the iron atoms is completed by histidine, aspartic acid, and glutamic acid side chains as well as water molecules, (b) The catalytically active zinc atom in the enzyme alcohol dehydrogenase. The zinc atom is coordinated to the protein by one histidine and two cysteine side chains. During catalysis zinc binds an alcohol molecule in a suitable position for hydride transfer to the coenzyme moiety, a nicotinamide, [(a) Adapted from P. Nordlund et al., Nature 345 593-598, 1990.)...

The thioredoxin domain (see Figure 2.7) has a central (3 sheet surrounded by a helices. The active part of the molecule is a Pa(3 unit comprising p strands 2 and 3 joined by a helix 2. The redox-active disulfide bridge is at the amino end of this a helix and is formed by a Cys-X-X-Cys motif where X is any residue in DsbA, in thioredoxin, and in other members of this family of redox-active proteins. The a-helical domain of DsbA is positioned so that this disulfide bridge is at the center of a relatively extensive hydrophobic protein surface. Since disulfide bonds in proteins are usually buried in a hydrophobic environment, this hydrophobic surface in DsbA could provide an interaction area for exposed hydrophobic patches on partially folded protein substrates. 

The Creutz-Taube anion, [(NH3)5Ru- N(CH=CH)2N Ru(NH3)5] + displays more obvious redox properties, yielding both 4+ and 6- - species, and much interest has focused on the extent to which the pyrazine bridge facilitates electron transfer. A variety of spectroscopic studies supports the view that low-energy electron tunnelling across the bridge delocalizes the charge, making the 5- - ion symmetrical. Other complexes, such as the anion [(CN)5Ru (/z-CN)Ru (CN)5] , are asymmetric... 

Potassium chloride (nitrate) bridge 583, 582 Potassium chromate as indicator, 343, 349 Potassium cyanoferrate(II) D. of, (ti) 384 Potassium cyanoferrate(III) D. of, (ti) 399 Potassium cyanonickelate(II) prepn., 328 Potassium dichromate solution analyses involving, 375 oxidising properties of, 375 internal indicators for, 377 preparation of, 0.02M, 375 redox indicators for, 377 standardisation of, by iron, (cm) 546, (ti) 376... 

Finally, we consider the alternative mechanism for electron transfer reactions -the inner-sphere process in which a bridge is formed between the two metal centers. The J-electron configurations of the metal ions involved have a number of profound consequences for this reaction, both for the mechanism itself and for our investigation of the reaction. The key step involves the formation of a complex in which a ligand bridges the two metal centers involved in the redox process. For this to be a low energy process, at least one of the metal centers must be labile. 

The redox processes responsible for the switching of the bridging redox polymer can also be brought about by redox processes induced by molecular species in solution Alternatively, the switching processes can be designed so that a solution component is essential for, or mediates the redox process. The array electrode can then be used as a sensor for those solution constituents. 

Several demonstrations of this concept have recently been published The first one is based on the pH dependence of redox transitions in oxide semiconductors that are connected with conductivity changes. If the bridging polymer layer in Fig. 6 is WO3 sputtered onto the electrode array or electrochemically deposited Ni(OH)j the transistor amplification is a function of the pH of the... 

The bridging polymer is a conducting poly(3-methyIthiophene) or polyaniline and the solid state redox conduction between all electrodes is accomplished by a common coating with poly(ethyleneoxide)/Li" CF3S03- or poly(vinyl alcohol)/ The polyaniline based molecular transistor proved as a very sensitive moisture detector it works well in a dry argon atmosphere but in water saturated argon the device cuts out... 

Reference electrodes for non-aqueous solvents are always troublesome because the necessary salt bridge may add considerable errors by undefined junction potentials. Leakage of components of the reference compartment, water in particular, into the working electrode compartment is a further problem. Whenever electrochemical cells of very small dimensions have to be designed, the construction of a suitable reference electrode system may be very difficult. Thus, an ideal reference electrode would be a simple wire introduced into the test cell. The usefulness of redox modified electrodes as reference electrodes in this respect has been studied in some detail... 

The lower redox potential in menaquinone-oxidizing be complexes can be attributed to the absence of the hydrogen bond from the Oy of Ser 163 (ISF)/Ser 130 (RFS) to the bridging sulfur S-1 (see Section III,B,2). This serine is completely conserved in Rieske proteins of bci and bef complexes, but in all sequences of Rieske proteins from menaquinone-oxidizing be complexes, alanine or glycine is found in... 

Fig. 4. Representation of the ligand sphere of the [2Fe-2S] cluster of the Rieske protein from spinach and the attribution of g-tensor to moleculEir axes as discussed in the text. Ser 130 has been observed to influence the redox potentiEd of the cluster via hydrogen interactions with the acid-labile bridging sulfur.

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