Terminal oxidases

Ferguson-Miller S, Bahcock GT. 1996. Heme/copper terminal oxidases. Chem Rev 7 2889-2907. 

Collman JP, Sunderland CJ, Boulatov R. 2002c. Biomimetic studies of terminal oxidases Trisimidazole picket metalloporphyrins. Inorg Chem 41 2282. 

Collman JP, Boulatov R, Sunderland CJ. 2003a. Functional and structural analogs of the dioxygen reduction site in terminal oxidases. In Kadish KM, Smith KM, Guilard R, editors. The Porphyrin Handbook. Boston Academic Press, p. 1. 

Junemarm S. 1997. C3dochrome bd terminal oxidase. Biochim Biophys Acta 1321 107. 

To provide a model for nitrite reductases72 Karlin and co-workers characterized a nitrite-bound complex (226) (r = 0.05)214 In an endeavor to model nitrite reductase activity, Tanaka and co-workers prepared a few mononuclear complexes (227) (r = 0.74)215 (228) (r = 0.82),216 (229) (r = 0.97),217 (230) (r = 0.16),217 (231) (r = 0.07),217 and (232) (r = 0.43 and r = 0.53)217 and studied the electrochemical reduction of N02A As a part of their activity on modeling heme-copper terminal oxidases, Holm and co-workers prepared complex (233) (r = 0.96).218 Using a sterically hindered tris(pyridylmethyl)amine, Canary et al. prepared a complex (234) (r=1.00), studied its redox behavior, and discussed various factors that may contribute to the difference (higher potential for the new complex) in the redox potential of a Cu Cu1 couple between substituted and unsubstituted ligands.2 9... 

We have already discussed the terminal oxidase of the respiratory chain, CcOx, in the previous chapter. Here we focus on the role of copper in this key metabolic enzyme. 

Sensitivity. Since terminal oxidases have high affinities for oxygen, low-level pCL measurements are important. The signal-to-noise ratio may be unacceptable in some situations. 

Gomes CM, Silva G, Oliviera S, et al. 1997. Studies on redox centers of the terminal oxidase from Desulfovibio gigas and evidence for its interaction with rubredoxin. J Biol Chem 272 22502-8. 

The other copper-only binuclear centre to be considered is the CuA or purple copper complex. It is part of the terminal oxidase in mitochondrial respiration, cytochrome c oxidase (COX). Its EPR signature, a seven-line spectrum, has since long been known to be different from the classes type 1 to 3 and arises from two copper ions in a 1.5 valence (or mixed valence) state, first proposed from EPR-analysis of a similar center in nitrous oxide (N20) reductase. There is a close correspondence between the blue and purple states of copper since each of the two copper ions in CuA can be considered as being structurally related to the mononuclear blue site coordination. 

The expression and characterization of a recombinant subunit II of the archaebacterial terminal oxidase complex in Sulfolobus acidocaldarius was achieved. The binuclear CuA centre was shown to be correctly inserted. A protonation of one of the coordinating histidines was suggested from the pH-profile.109 The subunit is part of a supercomplex SoxM which also has been isolated in a catalytically competent form for the first time.110 Nitrous oxide reductase (NOR) was prepared from Hyphomicrobium denitrificans and charac-... 

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