Electron transfers within

Electron Transfer Within the Cytochrome fig/Cytochrome/ Complex... 

Hoffman BM, Natan MJ, Nocek JM, Wallin SA (1991) Long-Range Electron Transfer Within Metal-Substituted Protein Complexes. 75 85-108 Hoffmann BM, see Ibers JA (1982) 50 1-55... 

The subunits of CODH/ACS have been isolated (see earlier discussion). The isolated a subunit contains one Ni and four Fe and has spectroscopic properties (186) similar to those of Cluster A, the active site of acetyl-CoA synthesis (212). Unfortunately, it has no ACS activity. Therefore, ACS activity may reside in the a subunit or it may require both the a and the fi subunits. If Clusters B and/or C of the B subunit are involved in acetyl-CoA synthesis, one possible role could be in electron transfer. Although acetyl-CoA synthesis and the CO/ exchange reactions do not involve net electron transfer, both of these reactions are stimulated by ferredoxin, indicating that internal electron transfer within CODH/ACS may be required during the reaction (121). Further studies with the isolated subunits and the reconstitu-... 

The transfer of electrons in proteins by a quantum mechanical tunnelling mechanism is now firmly established. Electron transfer within proteins... 

The cobalt(II)15 and zinc(II)16 complexes of phthalocyanine(Pc), octcyano-Pc, and tetrasulfon-ato-Pc incorporated in poly(4-vinylpyridine-co-styrene) or Nafion films coated on graphite have also been examined as catalytic devices for dihydrogen electrogeneration in phosphate buffer. These catalytic systems were strongly suggested to be dominated by the electron transfer within the polymer matrix. The best catalytic film is that constituted of the nonsubstituted Con-Pc complex in poly(4-vinylpyridine-co-styrene), giving a turnover number of 2 x 10s h-1 at an applied potential of —0.90 V vs. Ag Ag Cl. 

The D/A complexation in equation (41) is further substantiated by infrared and NMR studies. These observations suggest that an initial thermal electron transfer within the D/A charge-transfer complex generates an ion-radical pair, and a rapid methyl transfer subsequently completes the 1,4-addition (equation 42). 

This system illustrates the importance of both the thermodynamic and intrinsic barriers in determining the direction of electron transfer within a given reactant pair. In addition, systems such as the one considered here in which the oxidative and reductive pathways possess comparable rate constants afford an opportunity of controlling or switching the direction of electron transfer by modifying one of the barriers. 

Corma, A., Fornes, V., Garcia, H., Miranda, M.A., Primo, J. and Sabater, M.-J. (1994). Photoinduced electron transfer within zeolite cavities eiv-Stilbcnc isomerization photosensitized by 2,4,6-triphenylpyrylium cation imprisoned inside zeolite Y. J. Am. Chem. Soc. 116, 2276-2280... 

Electron transfer within the [M(HA)(02)](re 1)+ complex was envisioned as a two-stage process in which first, a 2p electron of the ascorbate oxygen is transferred to a t2g non-bonding or an eg antibonding orbital of the metal ion. The subsequent step is the transfer of an electron to the 7i 2p or 7ij2p orbital of the oxygen molecule. 

In abroad sense, the model developed for the cobaloxime(II)-catalyzed reactions seems to be valid also for the autoxidation of the alkyl mercaptan to disulfides in the presence of cobalt(II) phthalocyanine tetra-sodium sulfonate in reverse micelles (142). It was assumed that the rate-determining electron transfer within the catalyst-substrate-dioxygen complex leads to the formation of the final products via the RS and O - radicals. The yield of the disulfide product was higher in water-oil microemulsions prepared from a cationic surfactant than in the presence of an anionic surfactant. This difference is probably due to the stabilization of the monomeric form of the catalyst in the former environment. 

Of more apparent significance in the aquatic environment are redox processes induced or enhanced on absorbance of light by chromophores at metal oxide surfaces in which the metal of the oxide lattice constitutes the cationic partner. Light induced electron transfer within such a chromophore often results in disruption of the oxide lattice. The photoredox-induced dissolution of iron and manganese oxides by such a mechanism has been proposed as a possible means of supply of essential trace-metal nutrients to plants and aquatic organisms (29-31). ... 

Rates of reductive dissolution of transition metal oxide/hydroxide minerals are controlled by rates of surface chemical reactions under most conditions of environmental and geochemical interest. This paper examines the mechanisms of reductive dissolution through a discussion of relevant elementary reaction processes. Reductive dissolution occurs via (i) surface precursor complex formation between reductant molecules and oxide surface sites, (ii) electron transfer within this surface complex, and (iii) breakdown of the successor complex and release of dissolved metal ions. Surface speciation is an important determinant of rates of individual surface chemical reactions and overall rates of reductive dissolution. 

Few studies have systematically examined how chemical characteristics of organic reductants influence rates of reductive dissolution. Oxidation of aliphatic alcohols and amines by iron, cobalt, and nickel oxide-coated electrodes was examined by Fleischman et al. (38). Experiments revealed that reductant molecules adsorb to the oxide surface, and that electron transfer within the surface complex is the rate-limiting step. It was also found that (i) amines are oxidized more quickly than corresponding alcohols, (ii) primary alcohols and amines are oxidized more quickly than secondary and tertiary analogs, and (iii) increased chain length and branching inhibit the reaction (38). The three different transition metal oxide surfaces exhibited different behavior as well. Rates of amine oxidation by the oxides considered decreased in the order Ni > Co >... 

Long-Range Electron Transfer Within Metal-Substituted Protein Complexes... 

The second issue is global is the quaternary structure of a mixed-metal hybrid significantly different from that of T-state Hb Here, the answer again is no, as indicated by an X-ray structure of the [a(FeCO), P(Mn)] hybrid [13]. Thus, the distances and geometric relation of the heme groups involved in electron transfer within the [aj, P2] ET complex are preserved in the metal-substituted species (Fig. 1). 

Reversible electron transfer within Mg and Zn-substituted hemoglobin hybrids is initiated by flash photoproduction of the long-lived triplet state ( MP). According to Scheme I, the triplet return to the ground state involves two pathways, intrinsic triplet decay (with rate constant kp) and electron transfer quenching (with rate constant k,). 

Metal-substituted hemoglobin hybrids, [MP, Fe " (H20)P] are particularly attractive for the study of long-range electron transfer within protein complexes. Both photoinitiated and thermally activated electron transfer can be studied by flash excitation of Zn- or Mg-substituted complexes. Direct spectroscopic observation of the charge-separated intermediate, [(MP), Fe " P], unambiguously demonstrates photoinitiated ET, and the time course of this ET process indicates the presence of thermal ET. Replacement of the coordinated H2O in the protein containing the ferric heme with anionic ligands (CN , F , Nj ) dramatically lowers the photoinitiated rate constant, k(, but has a relatively minor effect on the thermal rate, kg. 

Redox reactions usually lead, however, to a marked change in the species, as reactions 4-6 indicate. Important reactions involve the oxidation of organic and metalloprotein substrates (reactions 5 and 6) by oxidizing complex ions. Here the substrate often has ligand properties, and the first step in the overall process appears to be complex formation between the metal and substrate species. Redox reactions will often then be phenomenologically associated with substitution. After complex formation, the redox reaction can occur in a variety of ways, of which a direct intramolecular electron transfer within the adduct is the most obvious. 

The product of intramolecular electron transfer within the precursor complex is the successor complex... 

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