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http://dx.doi.org/10.5012/bkcs.2009.30.1.177

Dynamics of CO Rebinding to Protoheme in Viscous Solutions  

Lee, Tae-Gon (Department of Chemistry and Chemistry Institute for Functional Materials, Pusan National University)
Park, Jae-Heung (Department of Chemistry and Chemistry Institute for Functional Materials, Pusan National University)
Kim, Joo-Young (Department of Chemistry and Chemistry Institute for Functional Materials, Pusan National University)
Joo, Sang-Woo (Department of Chemistry, Soongsil University)
Lim, Man-Ho (Department of Chemistry and Chemistry Institute for Functional Materials, Pusan National University)
Publication Information
Bulletin of the Korean Chemical Society / v.30, no.1, 2009 , pp. 177-182 More about this Journal
Abstract
We present the geminate rebinding kinetics measurements of CO to 2-methylimidazole (2-MeIm) bound ferrous protoporphyrin- IX (FePPIX) in alkaline glycerol/water mixtures at 293 K after photolysis. The kinetics was probed by monitoring the CO stretching mode using femtosecond vibrational spectroscopy. When 2-MeIm is used in excess, heme dimers that typically form in low viscosity solutions disappear as the viscosity of the solvent increases. Heme aggregates formed in low viscosity solutions turn monomeric as more 2-MeIm is added, suggesting that 6-coordinated heme, including a strong proximal histidine tends to be in the monomeric form. The vibrational band of CO in the 2-MeIM-FePPIX-CO is well described by a single Gaussian function centered at 1958 $cm^-1$ and 28 $cm^-1$ full width at half maximum. The efficiency and rate of the geminate rebinding of CO to the heme increase with viscosity of the solvent, suggesting that retention of the dissociated CO near the heme, for a longer period by the viscous solvent media, accelerates rebinding.
Keywords
CO Rebinding; Protoheme; Fs vibrational spectroscopy; Viscous solution;
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