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note
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, gas-phase proton affinity; PCA, protocatechuate; 3,4-PCD, protocatechuate 3,4-dioxygenase; PDB, protein data bank; PIPES, piperazine-N,N′-bis(2-ethanesulfonic acid); RR, resonance Raman; SOD, superoxide dismutase; TACN, triazocyclononane; VTVH, variable-temperature, variable-field; WT, wild type; ZFS, zero-field splitting.
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Note that the abbreviation NO-FeSOD does not imply that nitric oxide binds to the iron ion through the oxygen atom; rather this ligand coordinates the iron ion through the nitrogen atom.
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We thank one of the reviewers for suggesting that nitrite may be present in our samples of NO-FeSOD.
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Low-temperature absorption data collected for NO-FeSOD were not suitable for quantitative analysis as these data were complicated by glass strain and were not as intense as the corresponding room-temperature data as the addition of glycerol reduced the concentration of NO-FeSOD.
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note
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Despite intensive investigation, no other peaks were observed.
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79
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In the case of the NO adducts of deoxyhemerythrin, for example, no high-energy peak was ever observed, and only one low-energy peak was observed in the presence of fluoride (see ref 79).
-
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83
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0038362990
-
-
note
-
3-FeSOD probably arises from the restricted motion of the His ligands in the actual protein. However, the fact that DFT computations predict that the opening of this angle is energetically favorable when substrate analogues are bound is significant.
-
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84
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0038362991
-
-
note
-
H2O and thereby underestimate the magnitude of the ΔpK.
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85
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0038024936
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note
-
While INDO/S-CISD computations proved useful in the calculation of ground-state properties for our model of NO-FeSOD, this computational method preferentially stabilizes the ground state relative to excited states and thus predicts electronic transition energies that are unrealistically large Because of this, INDO/S-CIS computations are typically used to predict electronic transition energies. For our model of NO-FeSOD, however, the S = 3/2 ground state calculated by the inclusion of only single electron excitations is different in composition than the S = 3/2 ground state calculated by the inclusion of both single and double electron excitations. Therefore, we have chosen to use DFT calculations in order to obtain excited-state properties.
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86
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0037686972
-
-
note
-
s = 3/2 mixed spin states. However, as these differences are expected to be small compared to LMCT energies, application of the Slater method to estimate transition energies for NO-FeSOD is reasonable.
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