Online citations, reference lists, and bibliographies.
Please confirm you are human
(Sign Up for free to never see this)
← Back to Search

Electron Transfer With Myoglobin In Free And Strongly Confined Regimes: Disclosing Diverse Mechanistic Role Of The Fe-coordinated Water By Temperature- And Pressure-assisted Voltammetric Studies

Tinatin D. Dolidze, Mikhael Shushanyan, D. Khoshtariya
Published 2015 · Chemistry

Save to my Library
Download PDF
Analyze on Scholarcy
Share
The naturally occurring electron-transfer (ET) event for myoglobin (Mb) can be mimicked through its functionalization at diversely modified metal platforms to allow for the electron exchange either in freely diffusing or immobilized regimes. In this work, horse muscle Mb was involved in the electron exchange with Au electrodes modified by dissimilar, thin or thick alkanethiol SAMs, terminated either by unicomponent (–OH) or 1 : 1 mixed (–OH/–COOH) functional (externally exposed) entities, respectively. The systematic, temperature- and pressure-supported cyclic voltammetry studies perfectly confirmed certainty of two kinds of ET patterns for Mb, embodying: (a) different operational kinetic regimes (including protein’s freely diffusing and strongly confined motifs) and (b) different intrinsic physical mechanisms (including dynamically controlled and non-adiabatic modes). Our analysis of obtained and published data for Mb and the reference redox-active protein, cytochrome c, specified further the central mechanistic role of the Fe-(heme-)coordinated water whose displacement is directly coupled to ET, and can be, in turn, controlled by the conformational organization and intrinsic fluctuational mobility of the Mb macromolecule. Graphical Abstract
This paper references
10.1021/JP0105140
The Nature of Electronic Coupling between Ferrocene and Gold through Alkanethiolate Monolayers on Electrodes: The Importance of Chain Composition, Interchain Coupling, and Quantum Interference
Andrew M. Napper (2001)
10.1021/JA034719T
Charge-transfer mechanism for cytochrome c adsorbed on nanometer thick films. Distinguishing frictional control from conformational gating.
D. Khoshtariya (2003)
R
D. E. Khoshtariya (2006)
Z
L. D. Zusman (1994)
10.1016/J.CCR.2015.02.016
Kinetics, mechanism and equilibrium studies on the substitution reactions of Pd(II) in reference to Pt(II) complexes with bio-molecules
Ž. Bugarčić (2015)
Biochim
R. A. Marcus (1985)
Biopolymers
T. D. Dolidze (2007)
10.1016/J.JELECHEM.2013.05.023
Electrochemical characterization of dehaloperoxidase adsorbates on COOH/OH mixed self-assembled monolayers
T. Chen (2013)
R
T. Tretyakova (2013)
R
A. Franke (2012)
Eur
N. G. Goguadze (1991)
10.1007/s00249-002-0255-x
A water network within a protein: temperature-dependent water ligation in H64V-metmyoglobin and relaxation to deoxymyoglobin
N. Engler (2002)
10.1016/j.bbapap.2008.08.006
Application of high pressure laser flash photolysis in studies on selected hemoprotein reactions.
M. Brindell (2008)
10.1021/ja909822d
Heme proteins: the role of solvent in the dynamics of gates and portals.
M. A. Scorciapino (2010)
R
M. Brindell (2008)
Biophys
V. E. Prusakov (1995)
10.1021/IC00099A027
Mechanistic Information from the First Volume Profile Analysis for a Reversible Intermolecular Electron-Transfer Reaction Involving Pentaammine(isonicotinamide)ruthenium and Cytochrome c
B. Baensch (1994)
10.1021/AC60230A016
Theory and Application of Cyclic Voltammetry for Measurement of Electrode Reaction Kinetics.
R. S. Nicholson (1965)
R
T. D. Dolidze (2008)
10.1016/j.bpc.2013.02.006
Simplicity within the complexity: bilateral impact of DMSO on the functional and unfolding patterns of α-chymotrypsin.
T. Tretyakova (2013)
10.1021/JA00185A021
Pressure tuning spectroscopic study of electron-tunneling processes in solution
N. Lewis (1989)
10.1007/s00775-011-0867-7
A complete volume profile for the reversible binding of camphor to cytochrome P450cam
A. Franke (2011)
10.1016/j.bpj.2009.12.4318
Protein collective motions coupled to ligand migration in myoglobin.
Y. Nishihara (2010)
10.1021/BI00230A026
Ligand binding to heme proteins: connection between dynamics and function.
P. J. Steinbach (1991)
Electron Transfer in Chemistry and Biology: An Introduction to the Theory
A. Kuznetsov (1999)
10.1006/JMBI.1993.1491
Investigations of ligand association and dissociation rates in the "open" and "closed" states of myoglobin.
W. D. Tian (1993)
10.1007/s007750050316
Kinetic, structural and electrostatic aspects of the reduction of pentacyanoferrate(III) complexes by myoglobin
E. Ilkowska (1999)
10.1021/CR050571F
Introduction: Inorganic and Bioinorganic Mechanisms
R. Eldik (2005)
Coord
M. Fedurco (2000)
10.1021/JA9915504
The Role of the Distal and Proximal Protein Environments in Controlling the Ferric Spin State and in Stabilizing Thiolate Ligation in Heme Systems: Thiolate Adducts of the Myoglobin H93G Cavity Mutant
M. Roach (1999)
10.1126/science.1197054
Faster Interprotein Electron Transfer in a [Myoglobin, b5] Complex with a Redesigned Interface
P. Xiong (2010)
10.1021/JP9717103
Long-Range Electronic Coupling between Ferrocene and Gold in Alkanethiolate-based Monolayers on Electrodes
K. Weber (1997)
Biochim
Z. Amini-Bayat (2012)
10.1021/AC00091A028
Cyclic Voltammetric Analysis of Ferrocene Alkanethiol Monolayer Electrode Kinetics Based on Marcus Theory
L. Tender (1994)
10.1136/bmj.1.4959.155-a
Biochemistry
F. G. Young (1955)
R
A. Drljaca (1998)
10.1039/c3cp51896e
Electron transfer with azurin at Au-SAM junctions in contact with a protic ionic melt: impact of glassy dynamics.
D. Khoshtariya (2013)
10.1021/JP991813G
Pressure Dependence of the Intramolecular Electron Transfer Reaction in Myoglobin Reinvestigated
Y. Furukawa (2000)
Adv
M. Bixon (1999)
10.1016/0304-4173(85)90014-X
Electron transfers in chemistry and biology
R. Marcus (1985)
10.1021/JP035184T
Positive Activation Volume for a Cytochrome C Electrode Process: Evidence for a “Protein Friction” Mechanism from High-Pressure Studies
Tina D. Dolidze‡ and (2003)
Biochim
K. Teilum (2011)
10.1016/0003-2670(95)90239-2
Modern Aspects Of Electrochemistry
W. Ziegler (2016)
10.1007/s00894-013-1864-2
Effects of local protein environment on the binding of diatomic molecules to heme in myoglobins. DFT and dispersion-corrected DFT studies
M. Liao (2013)
R
E. Ilkowska (1997)
10.1007/978-1-4614-0347-0_2
Fundamental Studies of Long- and Short-Range Electron Exchange Mechanisms between Electrodes and Proteins
D. Waldeck (2011)
10.1021/JA9923179
Solvent Dynamics and Pressure Effects in the Kinetics of the Tris(bipyridine)cobalt(III/II) Electrode Reaction in Various Solvents
Y. Fu (1999)
Eur
N. Engler (2003)
R
D. E. Khoshtariya (2009)
10.1002/9780470141656.CH3
Electron transfer : from isolated molecules to biomolecules
M. Bixon (2007)
R
Z. D. Bugarčić (2015)
Biochim
D. Dantsker (2005)
10.1016/s0021-9258(18)50397-5
Metmyoglobin reductase. Identification and purification of a reduced nicotinamide adenine dinucleotide-dependent enzyme from bovine heart which reduces metmyoglobin.
L. Hagler (1979)
10.1103/PHYSREVE.80.065101
Unusual mechanism for the short-range electron transfer within gold-alkanethiol-ionic-liquid films of subnanometer thickness.
D. Khoshtariya (2009)
Eur
D. C. Lamb (1998)
R
T. D. Dolidze (2003)
10.1021/JA973781L
PHOTODISSOCIATION AND REBINDING OF H2O TO FERROUS SPERM WHALE MYOGLOBIN
D. Lamb (1998)
R
D. E. Khoshtariya (2014)
10.1021/JA038163L
Dynamic docking and electron-transfer between cytochrome b5 and a suite of myoglobin surface-charge mutants. Introduction of a functional-docking algorithm for protein-protein complexes.
Zhao-Xun Liang (2004)
10.1016/0301-0104(87)85021-8
Outer-sphere electron transfer reactions at an electrode
L. Zusman (1987)
10.1016/S0010-8545(00)00292-7
Redox reactions of heme-containing metalloproteins: dynamic effects of self-assembled monolayers on thermodynamics and kinetics of cytochrome c electron-transfer reactions
M. Fedurco (2000)
10.1063/1.453184
Dynamic solvent effects on outer‐sphere electron transfer
I. Rips (1987)
10.1021/J100126A037
Characterization of cytochrome c/alkanethiolate structures prepared by self-assembly on gold
Shihua. Song (1993)
10.1021/BI9908888
Hydrogen bonding modulates binding of exogenous ligands in a myoglobin proximal cavity mutant.
S. Decatur (1999)
R
E. Ilkowska (1999)
C
A.E.D. Beckit (2005)
R
R. Puchta (2009)
Anal
L. Tender (1994)
Chem
A. Kumar (2012)
10.1177/001452469000101110
"J."
G.G. Stokes (1890)
Chem
H.-X. Zhou (2009)
10.1016/J.BBAPAP.2005.04.002
A hierarchy of functionally important relaxations within myoglobin based on solvent effects, mutations and kinetic model.
D. Dantsker (2005)
10.1016/S0006-3495(95)80435-2
Mössbauer spectroscopy on nonequilibrium states of myoglobin: a study of r-t relaxation.
V. Prusakov (1995)
10.1073/pnas.0910837107
Fundamental signatures of short- and long-range electron transfer for the blue copper protein azurin at Au/SAM junctions
D. Khoshtariya (2010)
10.1021/IC9413528
Comparative Kinetic Analysis of Reversible Intermolecular Electron-Transfer Reactions between a Series of Pentaammineruthenium Complexes and Cytochrome c.
M. Meier (1996)
Anal
R. S. Nicholson (1964)
10.1021/J100640A025
Pressure dependence of weak acid ionization in aqueous buffers
J. C. Neuman (1973)
R
D. E. Khoshtariya (2006)
Biophys
Y. Nishihara (2010)
10.1021/JP064091J
Spin-forbidden ligand binding to the ferrous-heme group: ab initio and DFT studies.
N. Strickland (2007)
10.1016/s0021-9258(17)43201-7
Water coordination by heme iron in metmyoglobin.
J. Peisach (1984)
10.1149/1.2403817
Modern Aspects of Electrochemistry
B. E. Conway (1971)
R
M. Meier (1996)
10.1021/jp077734j
High-pressure testing of heterogeneous charge transfer in a room-temperature ionic liquid: evidence for solvent dynamic control.
T. Dolidze (2008)
R
M. Meier (1996)
10.1021/JP0041095
Observation of the Turnover between the Solvent Friction (Overdamped) and Tunneling (Nonadiabatic) Charge-Transfer Mechanisms for a Au/Fe(CN)63-/4- Electrode Process and Evidence for a Freezing Out of the Marcus Barrier
†‡ and Dimitri E. Khoshtariya (2001)
10.1007/s007750050175
Kinetics and mechanism of the reduction of hexacyanoferrate(III) by myoglobin in aqueous solution
E. Ilkowska (1997)
R
M. Shushanyan (2011)
Anal
K. Weber (1994)
R
D. E. Khoshtariya (2013)
10.1016/S0898-8838(09)00209-8
Ligand exchange processes on the smallest solvated alkali and alkaline earth metal cations: An experimental and theoretical approach
R. Puchta (2009)
10.1021/cr2003773
Overview of the stability of α-chymotrypsin in different solvent media.
A. Kumar (2012)
10.1021/JA00021A010
1H NMR Hyperfine Shift Pattern as a Probe for Ligation State in High-Spin Ferric Hemoproteins: Water Binding in Metmyoglobin Mutants
K. Rajarathnam (1991)
10.1021/JP0620670
On the electron transfer mechanism between cytochrome C and metal electrodes. Evidence for dynamic control at short distances.
Hongjun Yue (2006)
10.1016/S0065-3160(06)41001-7
The interpretation and mechanistic significance of activation volumes for organometallic reactions
R. Eldik (2006)
10.1021/jp4101569
Long-range electron transfer with myoglobin immobilized at Au/mixed-SAM junctions: mechanistic impact of the strong protein confinement.
D. Khoshtariya (2014)
10.1007/s002490050117
From metmyoglobin to deoxy myoglobin: relaxations of an intermediate state
D. Lamb (1998)
10.1021/BI010067E
Water penetration and binding to ferric myoglobin.
W. Cao (2001)
R
D. E. Khoshtariya (2010)
10.1021/cr800551w
Theory of free energy and entropy in noncovalent binding.
H. Zhou (2009)
10.1002/9780470145180.CH131
By Electrochemical methods
T. Brown (2007)
Chem
T. W. Swaddle (2005)
10.1021/AC60210A007
Theory of Stationary Electrode Polarography. Single Scan and Cyclic Methods Applied to Reversible, Irreversible, and Kinetic Systems.
R. S. Nicholson (1964)
10.1016/0020-1693(95)04865-0
Volume of activation for the self-exchange reaction of cytochrome c1
M. Meier (1996)
10.1021/JP9052659
A Unified Model for the Electrochemical Rate Constant That Incorporates Solvent Dynamics
Ambuj Mishra (2009)
10.1021/jp204047b
Elucidating the energetics of entropically driven protein-ligand association: calculations of absolute binding free energy and entropy.
Nan-Jie Deng (2011)
10.1016/j.bbapap.2010.11.005
Protein stability, flexibility and function.
K. Teilum (2011)
R
D. E. Khoshtariya (1995)
10.1524/zpch.1994.186.Part_1.001
Dynamical Solvent Effects in Electron Transfer Reactions
L. D. Zusman (1994)
10.1016/j.bbapap.2011.11.003
Relationship between stability and flexibility in the most flexible region of Photinus pyralis luciferase.
Z. Amini-bayat (2012)
10.1063/1.1696792
On the Theory of Electron-Transfer Reactions. VI. Unified Treatment for Homogeneous and Electrode Reactions
R. Marcus (1965)
Chem
L. D. Zusman (1987)
Anal
R. S. Nicholson (1965)
10.1016/j.meatsci.2005.04.032
Metmyoglobin reducing activity.
A. Bekhit (2005)
10.1021/CR970461B
Activation and Reaction Volumes in Solution. 3.
A. Drljača (1978)
R
B. Baensch (1994)
10.1016/J.CCR.2007.02.004
Fascinating inorganic/bioinorganic reaction mechanisms☆
R. Eldik (2007)
10.1039/FT9959101625
Temperature, pressure and solvent isotope effects on the precursor formation constant and reorganization dynamics in outer-sphere charge transfer between free mobile [Fe(CN)6]3– and [Fe(CN)6]4– ions
D. Khoshtariya (1995)
10.1016/0079-6816(75)90008-8
Theory of charge transfer kinetics at solid-polar liquid interfaces
R. R. Dogonadze (1975)
10.1021/JA067598G
Dynamic docking of cytochrome b5 with myoglobin and alpha-hemoglobin: heme-neutralization "squares" and the binding of electron-transfer-reactive configurations.
Korin E Wheeler (2007)
10.1021/ja902131d
Electrostatic redesign of the [myoglobin, cytochrome b5] interface to create a well-defined docked complex with rapid interprotein electron transfer.
Peng Xiong (2009)
10.1039/A605567B
Long-range electron-transfer reaction rates to cytochromec across long- and short-chain alkanethiol self-assembledmonolayers: Electroreflectancestudies
Z. Q. Feng (1997)
10.1001/jama.1967.03120070166075
Science in Washington
P. Ludovice (2010)
10.1021/AC00091A027
Voltammetry of Redox-Active Groups Irreversibly Adsorbed onto Electrodes. Treatment Using the Marcus Relation between Rate and Overpotential
K. Weber (1994)
R
N. A. Lewis (1989)
10.1021/CR030727G
Homogeneous versus heterogeneous self-exchange electron transfer reactions of metal complexes: insights from pressure effects.
T. Swaddle (2005)
Progr
R. R. Dogonadze (1975)



Semantic Scholar Logo Some data provided by SemanticScholar