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• W2016205740 endingPage "7046" @default.
• W2016205740 startingPage "7042" @default.
• W2016205740 abstract "The nature of bonding interactions between Fe(III) and NO in the ferric nitrosyl complexes of myoglobin (Mb), hemoglobin A (HbA), and horseradish peroxidase (HRP) is investigated by Soret-excited resonance Raman spectroscopy. On the basis of 15NO and N18O isotope shifts, we clearly identified the Fe(III)--NO bond stretching frequencies at 595 cm-1 (ferric Mb X NO), 594 cm-1 (ferric HbA X NO), and 604 cm-1 (ferric HRP X NO). The Fe(III)--N--O bending vibrations are located at 573 cm-1 (ferric Mb X NO) and 574 cm-1 (ferric HRP X NO), which are very similar to the Fe(II)--C--O bending modes at 578 cm-1 in Mb X CO and HbA X CO. However, the Fe(III)--NO and Fe(II)--CO stretching frequencies differ by approximately equal to 90 cm-1, indicating a much stronger iron-axial ligand bond for the [Fe(III) + NO] system, which is isoelectronic with the [Fe(II) + CO] system and, hence, presumably also has a linear Fe(III)--N--O linkage (in the absence of distal steric effect). The unusually strong Fe(III)--NO bond may be attributed to the pi bonding involving the unpaired electron in the pi (NO) orbital. The N18O isotope shift data indicate that the widely accepted assignment of the Fe(II)--NO stretching vibration at approximately equal to 554 cm-1 in ferrous nitrosyl Mb/HbA is incorrect; instead, we assign it to the Fe(II)--N--O bending mode. The validity of the assignment of Fe(II)--O2 stretch at 567 cm-1 in oxy-HbA by Brunner [Brunner, H. (1974) Naturwissenschaften 61, 129-130] is now in doubt. Literature data are presented to suggest that it is the Fe(II)--O--O bending vibration." @default.
• W2016205740 created "2016-06-24" @default.
• W2016205740 creator A5054271415 @default.
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• W2016205740 date "1983-11-01" @default.
• W2016205740 modified "2023-10-16" @default.
• W2016205740 title "Resonance Raman studies of nitric oxide binding to ferric and ferrous hemoproteins: detection of Fe(III)--NO stretching, Fe(III)--N--O bending, and Fe(II)--N--O bending vibrations." @default.
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• W2016205740 doi "https://doi.org/10.1073/pnas.80.22.7042" @default.
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