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

Electrochemical Characterization Of Dehaloperoxidase Adsorbates On COOH/OH Mixed Self-assembled Monolayers

T. Chen, E. F. Bowden
Published 2013 · Chemistry

Save to my Library
Download PDF
Analyze on Scholarcy
Abstract Electrochemical characterization of Amphitrite ornata dehaloperoxidase, a monomeric hemoglobin, adsorbed on COOH/OH-terminated alkanethiolate mixed self-assembled monolayers (SAMs) is reported. Adsorption was achieved by simple electrode exposure to low ionic strength protein solution at pH 6.0, and cyclic voltammetry (CV) was employed to measure surface concentration, electron transfer rate, and formal potential under anaerobic conditions. Surface concentration values determined by CV were found to be inversely proportional to scan rate, a behavior that is different than that observed for electron transfer proteins such as cytochrome c. We attribute this behavior to a dynamic heterogeneous adsorbate layer that permits some fraction of the molecules to undergo reorientation during a CV scan. A model was proposed that classifies adsorbates among three populations with respect to their most stable orientations, namely, electroactive adsorbates, latent electroinactive adsorbates capable of undergoing reorientation to electroactive states, and electroinactive adsorbates. Electrochemical results and the proposed model are discussed in terms of the tertiary structure and surface properties of dehaloperoxidase and are compared to the docking and electron transfer reactions of the myoglobin/cytochrome b5 system. Examination of the effects of ionic strength and mixed SAM composition provide support for the proposed model.
This paper references
Self-assembled organic monolayers: model systems for studying adsorption of proteins at surfaces
K. L. Prime (1991)
Third-generation biosensors based on the direct electron transfer of proteins.
W. Zhang (2004)
The courtship of proteins: Understanding the encounter complex
M. Ubbink (2009)
pH-Induced changes in adsorbed cytochrome c. voltammetric and surface-enhanced resonance Raman characterization performed simultaneously at chemically modified silver electrodes.
D. Millo (2007)
Direct electron transfer of horse heart myoglobin at an indium oxide electrode
I. Taniguchi (1992)
Electron transfer and interfacial behavior of redox proteins
N. Zhou (2010)
Self-assembled monolayers of thiolates on metals as a form of nanotechnology.
J. Love (2005)
Molecular basis of coupled protein and electron transfer dynamics of cytochrome c in biomimetic complexes.
Damián Alvarez-Paggi (2010)
Voltammetry of dehaloperoxidase on self-assembled monolayers: Reversible adsorptive immobilization of a globin
E. L. D’Antonio (2013)
Electroanalytical Chemistry: A Series of Advances
Allen J. Bard (1974)
Electron transfer from electrodes to myoglobin: facilitated in surfactant films and blocked by adsorbed biomacromolecules.
A. E. Nassar (1995)
Adsorptive immobilization of cytochrome c on indium/tin oxide (ITO): electrochemical evidence for electron transfer-induced conformational changes
A. E. Kasmi (2002)
Protein-protein interaction in insulin signaling and the molecular mechanisms of insulin resistance.
A. Virkamäki (1999)
An electrochemical approach to investigate gated electron transfer using a physiological model system: Cytochrome c immobilized on carboxylic acid-terminated alkanethiol self-assembled monolayers on gold electrodes
A. Avila (2000)
Molecular orientation distributions in protein films. 1. Cytochrome c adsorbed to substrates of variable surface chemistry
P. Edmiston (1997)
An Unusual Dehalogenating Peroxidase from the Marine Terebellid Polychaete Amphitrite ornata(*)
Y. Chen (1996)
Ordered Assembly and Controlled Electron Transfer of the Blue Copper Protein Azurin at Gold (111) Single-Crystal Substrates
Qijin Chi (2001)
Determination of the orientation of adsorbed cytochrome C on carboxyalkanethiol self-assembled monolayers by in situ differential modification.
J. Xu (2006)
Immobilization of bio-macromolecules on self-assembled monolayers: methods and sensor applications.
Debasis Samanta (2011)
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)
Thin-layer spectroelectrochemistry of the Fe(III)/Fe(II) redox reaction of dehaloperoxidase-hemoglobin
E. L. D’Antonio (2012)
Direct observation of the gating step in protein electron transfer: electric-field-controlled protein dynamics.
Anja Kranich (2008)
Template‐Synthesized Protein Macroporous Biofilms: Conformational Related Direct Electron Transfer
Yan-Yan Song (2007)
Electron-transfer reaction of cytochrome c adsorbed on carboxylic acid terminated alkanethiol monolayer electrodes
M. Tarlov (1991)
The distribution of standard rate constants for electron transfer between thiol-modified gold electrodes and adsorbed cytochrome c
T. M. Nahir (1996)
Heme plane orientation dependent direct electron transfer of cytochrome c at SAMs/Au electrodes with different wettability.
G. Wang (2012)
Adsorption and Direct Electron Transfer from Hemoglobin into a Three‐Dimensionally Ordered Macroporous Gold Film
C. Wang (2005)
Electrostatic control of electron transfer between myoglobin and cytochrome b5: Effect of methylating the heme propionates of Zn-myoglobin [16]
Z. Liang (2000)
Interfacial hydration, dynamics and electron transfer: multi-scale ET modeling of the transient [myoglobin, cytochrome b5] complex.
Shahar Keinan (2012)
Electric-field effects on the interfacial electron transfer and protein dynamics of cytochrome c
H. K. Ly (2011)
The Unusual Reactivities of Amphitrite ornata Dehaloperoxidase and Notomastus lobatus Chloroperoxidase Do Not Arise from a Histidine Imidazolate Proximal Heme Iron Ligand
S. Franzén (1998)
The effect of ionic strength on the electron-transfer rate of surface immobilized cytochrome C.
Hongjun Yue (2006)
Characterization of cytochrome c/alkanethiolate structures prepared by self-assembly on gold
Shihua. Song (1993)
Characterization of dehaloperoxidase compound ES and its reactivity with trihalophenols.
Jeremiah A. Feducia (2009)
General expression of the linear potential sweep voltammogram in the case of diffusionless electrochemical systems
E. Laviron (1979)
Dielectric dispersion and dipole moment of myoglobin in water
G. South (1972)
Voltammetric Peak Broadening for Cytochrome c/Alkanethiolate Monolayer Structures: Dispersion of Formal Potentials
Rose A. Clark† and (1997)
Protein-protein interactions studied by EPR relaxation measurements: cytochrome c and cytochrome c oxidase.
Sevdalina Lyubenova (2007)
The asymmetric distribution of charges on the surface of horse cytochrome c. Functional implications.
W. Koppenol (1982)
On the electron transfer mechanism between cytochrome C and metal electrodes. Evidence for dynamic control at short distances.
Hongjun Yue (2006)
Electric-field controle of the pH-dependent redox process of cytochrome c immobilized on gold electrode
B. Jin (2012)
Dynamic docking and electron transfer between myoglobin and cytochrome b5
Zhao-Xun Liang (2001)
27 Heme Protein-Based Electrochemical Biosensors
G. Li (2010)
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)

This paper is referenced by
Semantic Scholar Logo Some data provided by SemanticScholar