Academic Journal

Articles How Cytochromes with Different Folds Control Heme Redox Potentials†

التفاصيل البيبلوغرافية
العنوان: Articles How Cytochromes with Different Folds Control Heme Redox Potentials†
المؤلفون: Junjun Mao, Karin Hauser, M. R. Gunner
المساهمون: The Pennsylvania State University CiteSeerX Archives
المصدر: http://www.sci.ccny.cuny.edu/~gunner/Pages-lab/papers/bi03.mao.cyt.pdf.
سنة النشر: 2002
المجموعة: CiteSeerX
الوصف: The electrochemical midpoint potentials (Em’s) of 13 cytochromes, in globin (c, c2, c551, c553), four-helix bundle (c′, b562), Râ roll (b5), and â sandwich (f) motifs, with Em’s spanning 450 mV were calculated with multiconformation continuum electrostatics (MCCE). MCCE calculates changes in oxidation free energy when a heme-axial ligand complex is moved from water into protein. Calculated and experimental Em’s are in good agreement for cytochromes with His-Met and bis-His ligated hemes, where microperoxidases provide reference Em’s. In all cytochromes, Em’s are raised by 130-260 mV relative to solvated hemes by the loss of reaction field (solvation) energy. However, there is no correlation between Em and heme surface exposure. Backbone amide dipoles in loops or helix termini near the axial ligands raise Em’s, but amides in helix bundles contribute little. Heme propionates lower Em’s. If the propionic acids are partially protonated in the reduced cytochrome, protons are released on heme oxidation, contributing to the pH dependence of the Em. In all cytochromes studied except b5’s and low potential globins, buried side chains raise Em’s. MCCE samples ionizable group protonation states, heme redox states, and side chain rotamers simultaneously. Globins show the largest structural changes on heme oxidation and four-helix bundles the least. Given the calculated protein-induced Em shift and measured cytochrome Em the five-coordinate, His heme in c ′ is predicted to have a solution Em between that of
نوع الوثيقة: text
وصف الملف: application/pdf
اللغة: English
Relation: http://citeseerx.ist.psu.edu/viewdoc/summary?doi=10.1.1.553.8193; http://www.sci.ccny.cuny.edu/~gunner/Pages-lab/papers/bi03.mao.cyt.pdf
الاتاحة: http://citeseerx.ist.psu.edu/viewdoc/summary?doi=10.1.1.553.8193
http://www.sci.ccny.cuny.edu/~gunner/Pages-lab/papers/bi03.mao.cyt.pdf
Rights: Metadata may be used without restrictions as long as the oai identifier remains attached to it.
رقم الانضمام: edsbas.BFB513A0
قاعدة البيانات: BASE