Heme Attachment Motif Mobility Tunes Cytochrome c Redox Potential
Lea Vacca Michel,Tao Ye,Sarah E. J. Bowman,Benjamin D. Levin,Megan A. Hahn,Brandy S. Russell,Sean Elliott,Kara L. Bren +7 more
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TLDR
The mobility of the CXXCH pentapeptide is found to impact the His-Fe(III) interaction and therefore the heme redox potential of Pseudomonas aeruginosa and Hydrogenobacter thermophilus.Abstract:
Hydrogen exchange (HX) rates and midpoint potentials (Em) of variants of cytochrome c from Pseudomonas aeruginosa (Pa cyt c551) and Hydrogenobacter thermophilus (Ht cyt c552) have been characterized in an effort to develop an understanding of the impact of properties of the Cys-X-X-Cys-His pentapeptide c-heme attachment (CXXCH) motif on heme redox potential. Despite structural conservation of the CXXCH motif, Ht cyt c552 exhibits a low level of protection from HX for amide protons within this motif relative to Pa cyt c551. Site-directed mutants have been prepared to determine the structural basis for and functional implications of these variations on HX behavior. The double mutant Ht-M13V/K22M displays suppressed HX within the CXXCH motif as well as a decreased Em (by 81 mV), whereas the corresponding double mutant of Pa cyt c551 (V13M/M22K) exhibits enhanced HX within the CXXCH pentapeptide and a modest increase in Em (by 30 mV). The changes in Em correlate with changes in axial His chemical shifts in th...read more
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Direct Electrochemistry of Redox Enzymes as a Tool for Mechanistic Studies
TL;DR: This review regards the use of dynamic electrochemistry to study the mechanism of redox enzymes, with exclusive emphasis on the configuration where the protein is adsorbed onto an electrode and electron tranfer is direct.
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Multifunctional Cytochrome c: Learning New Tricks from an Old Dog.
Damián Alvarez-Paggi,Luciana Hannibal,Luciana Hannibal,María A. Castro,Santiago Oviedo-Rouco,Verónica Demicheli,Verónica Tórtora,Florencia Tomasina,Rafael Radi,Daniel H. Murgida +9 more
TL;DR: Current knowledge and recent advances in understanding the different structural, dynamic, and thermodynamic factors that regulate the primary electron transfer function, as well as alternative functions and conformations of cyt c are summarized.
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The Chemistry and Biochemistry of Heme c: Functional Bases for Covalent Attachment
Sarah E. J. Bowman,Kara L. Bren +1 more
TL;DR: It is proposed that heme attachment influences both heme reduction potential and ligand-iron interactions, which is expected to be similar to heme b.
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Multi-heme proteins: nature's electronic multi-purpose tool.
TL;DR: Recent advances in the field of multi-heme proteins are reviewed, focusing on emergent properties of these complex redox proteins, and strategies found in Nature where such proteins appear to be modular and essential components of larger biochemical pathways.
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NMR and DFT investigation of heme ruffling: functional implications for cytochrome c.
TL;DR: In this paper, the authors demonstrate correlations between the heme ruffling OOP deformation and the 13C and 1H nuclear magnetic resonance (NMR) hyperfine shifts of heme aided by density functional theory (DFT) calculations.
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