By Reinhard Renneberg, Dorothea Pfeiffer, Fred Lisdat (auth.), Reinhard Renneberg, Fred Lisdat (eds.)
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The authors proposed an interaction of the graphite surface with positively charged Arg-72, Arg-112, Arg-364 and Lys-344 residues on the protein surface. The formal potential of camphor free CYP101 was –526 mV Protein Electrodes with Direct Electrochemical Communication 37 (versus SCE). Addition of camphor caused a positive shift of the potential. Later the same group showed for mutant enzymes where cysteins were replaced by inert alanins that electron transfer is not affected by these cystein residues .
The overall hydroxylation reaction of the monooxygenases is insertion of one atom of an oxygen molecule into a substrate RH, the second atom of oxygen being reduced to water while consuming two reducing equivalents under formation of ROH: RH + O2 + 2e– + 2H+ → ROH + H2 O . (2) The single reaction steps have been investigated in detail [105, 106]. The resting enzyme is in the hexa-coordinated low-spin ferric enzyme with water beeing the sixth ligand. Substrate binding excludes water from the active site, which causes a change to the 5-coordinated high-spin state.
In addition, studies on His64 mutants of sperm whale Mb allowed the conclusion that a partly hydrophobic environment of a surfactant can disrupt the hydrogen bonding network of His64 and thus lower the reorganisation energy for the electron transfer . Mb on electrodes possesses pseudo-enzymatic activity towards O2 , H2 O2 , nitrite and organohalides. Under aerobic conditions, oxymyoglobin (MbO2 ) is also active in oxygenation reactions. Thus peroxide reduction, styrene oxygenation and dehalogenation of pollutants were followed electrocatalytically on Mb-modiﬁed electrodes.
Biosensing for the 21st Century by Reinhard Renneberg, Dorothea Pfeiffer, Fred Lisdat (auth.), Reinhard Renneberg, Fred Lisdat (eds.)