Structural electrochemical study of hemoglobin by in situ circular dichroism thin layer spectroelectrochemistry |
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Authors: | Zhu Yongchun Cheng Guangjin Dong Shaojun |
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Affiliation: | State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin 130022, PR China. |
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Abstract: | Secondary and tertiary or quaternary structural changes in hemoglobin (HB) during an electroreduction process were studied by in situ circular dichroism (CD) spectroelectrochemistry with a long optical path thin-layer cell. By means of singular value decomposition least-squares analysis, CD spectra in the far-UV region give two similar alpha components with different CD intensity, indicating slight denaturation in the secondary structures due to the electric field effect. CD spectra in the Soret band show a R-->T transition of two quaternary structural components induced by electroreduction of the heme, which changes the redox states of the center ion from Fe3+ to Fe2+ and the co-ordination number from 6 to 5. The double logarithmic analysis shows that electroreduction of hemoglobin follows a chemical reaction with R-->T transition. Some parameters in the electrochemical process were obtained: formal potential, E0'=-0.167 V; electrochemical kinetic overpotential, deltaE0=-0.32 V; standard electrochemical reaction rate constant, k0=1.79 x 10(-5) cm s(-1); product of electron transfer coefficient and electron number, alphan=0.14; and the equilibrium constant of R-->T transition, Kc=9.0. |
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