Protein Method Em (mV) vs SHE Escherichia coli Spectroelectrochemistry -20 (lsa), -108 (hsa), -153 (ls), -206 (ls), -292 (ls) NrfA (15) (MCD) PFE +22 (ls), -56 (hs), -117 (hs), -189 (hs), -275 (ls) (SnO2 electrode) Spectroelectrochemistry -62, -140, -250, -283, -342 Shewanella oneidensis MR1 (electronic absorbance) NrfA (8) PFE -36, -105, -166, -230, -295 (graphite electrode) Desulfovibrio Spectroelectrochemistry -50 (hs) vulgaris NrfHA (resonance Raman) (17) Desulfovibrio Potentiometry b +150 (ls), -50 (ls), -80 (hs), -480 (ls, 2 hemes) desulfuricans (EPR and Mössbauer) NrfHA (14,16) PFE -220 (active site CO binding heme) (graphite electrode) Thioalkalivibrio Spectroelectrochemistry +100 (ls), -80 (ls), -200 (3, ls) -370 (2, ls) nitratireducens (electronic absorbance, MCD) TvNiR (this work) a ls low-spin, hs high-spin b Dithionite or Zn as reductant Fig. 1. The active of two nitrite ammonifying enzymes that contain CxxCK coordinated active site hemes NrfA (A) and (B). Ec TvNiR The catalytic of Tyr, His and Arg in the distal pocket are illustrated together with the Cys modification of the active site Tyr in In NrfA Phe218 (blue) is the equivalent residue to TvNiR. Ec
Protein Method Em (mV) vs SHE Escherichia coli NrfA (15) Spectroelectrochemistry (MCD) -20 (lsa), -108 (hsa), -153 (ls), -206 (ls), -292 (ls) PFE (SnO2 electrode) +22 (ls), -56 (hs), -117 (hs), -189 (hs), -275 (ls) Shewanella oneidensis MR1 NrfA (8) Spectroelectrochemistry (electronic absorbance) -62, -140, -250, -283, -342 PFE (graphite electrode) -36, -105, -166, -230, -295 Desulfovibrio vulgaris NrfHA (17) Spectroelectrochemistry (resonance Raman) -50 (hs) Desulfovibrio desulfuricans NrfHA (14,16) Potentiometry b (EPR and Mössbauer) +150 (ls), -50 (ls), -80 (hs), -480 (ls, 2 hemes) PFE (graphite electrode) -220 (active site CO binding heme) Thioalkalivibrio nitratireducens TvNiR (this work) Spectroelectrochemistry (electronic absorbance, MCD) +100 (ls), -80 (ls), -200 (3, ls) -370 (2, ls) a ls low-spin, hs high-spin b Dithionite or Zn as reductant Fig. 1. The active of two nitrite ammonifying enzymes that contain CxxCK coordinated active site hemes Ec NrfA (A) and TvNiR (B). The catalytic of Tyr, His and Arg in the distal pocket are illustrated together with the Cys modification of the active site Tyr in TvNiR. In Ec NrfA Phe218 (blue) is the equivalent residue to
Doyle_et_al_for_JBIC_REVISION_2_FINAL.docx