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

Protein Electronics: Chemical Modulation Of Contacts Control Energy Level Alignment In Gold-Azurin-Gold Junctions.

Jerry A Fereiro, G. Porat, T. Bendikov, I. Pecht, M. Sheves, D. Cahen
Published 2018 · Chemistry, Medicine

Save to my Library
Download PDF
Analyze on Scholarcy
Share
Making biomolecular electronics a reality will require control over charge transport across biomolecules. Here we show that chemical modulation of the coupling between one of the electronic contacts and the biomolecules in a solid-state junction allows controlling electron transport (ETp) across the junction. Employing the protein azurin (Az), we achieve such modulation as follows: Az is covalently bound by Au-S bonding to a lithographically prepared Au electrode (Au-Az). Au nanowires (AuNW) onto which linker molecules, with free carboxylic group, are bound via Au-S bonds serve as top electrode. Current-voltage plots of AuNW-linkerCOOH//Az-Au junctions have been shown earlier to exhibit step-like features, due to resonant tunneling through discrete Az energy levels. Forming an amide bond between the free carboxylic group of the AuNW-bound linker and Az yields AuNW-linkerCO-NH-Az-Au junctions. This Az-linker bond switches the ETp mechanism from resonant to off-resonant tunneling. By varying the extent of this amide bonding, the current-voltage dependence can be controlled between these two mechanisms, thus providing a platform for altering and controlling the ETp mechanism purely by chemical modification in a two-terminal device, i.e., without a gate electrode. Using results from conductance, including the energy barrier and electrode-molecule coupling parameters extracted from current-voltage fitting and normalized differential conductance analysis and from inelastic-electron-tunneling and photoelectron spectroscopies, we determine the Az frontier orbital energies, with respect to the Au Fermi level, for four junction configurations, differing only in electrode-protein coupling. Our approach and findings open the way to both qualitative and quantitative control of biomolecular electronic junctions.
This paper references
10.1073/pnas.1319351111
Solid-state electron transport via cytochrome c depends on electronic coupling to electrodes and across the protein
N. Amdursky (2014)
10.1016/J.EURPOLYMJ.2016.03.028
Electron transfer in nanobiodevices
A. Alessandrini (2016)
10.1016/J.CPLETT.2011.06.050
Filled and empty states of alkanethiol monolayer on Au (1 1 1): Fermi level asymmetry and implications for electron transport
Y. Qi (2011)
10.1103/PhysRevB.69.085403
End group effect on electrical transport through individual molecules: A microscopic study
Yongqiang Xue (2004)
10.1016/S1369-7021(08)70238-4
Inelastic electron tunneling spectroscopy
M. Reed (2008)
10.1103/PhysRevB.68.115406
Microscopic study of electrical transport through individual molecules with metallic contacts. I. Band lineup, voltage drop, and high-field transport
Yongqiang Xue (2003)
10.1002/ADMA.200390065
Electron Energetics at Surfaces and Interfaces: Concepts and Experiments†
D. Cahen (2003)
10.1088/0953-8984/19/10/103201
Molecular transport junctions: vibrational effects
Michael Galperin (2006)
10.1038/nature08639
Observation of molecular orbital gating
Hyunwook Song (2009)
10.1116/1.575407
Theory of the local tunneling spectrum of a vibrating adsorbate
A. Baratoff (1988)
10.1021/ja109989f
Solid-state electron transport across azurin: from a temperature-independent to a temperature-activated mechanism.
Lior Sepunaru (2011)
10.1016/J.EURPOLYMJ.2016.04.030
Electron transfer, conduction and biorecognition properties of the redox metalloprotein Azurin assembled onto inorganic substrates
Chiara Baldacchini (2016)
10.1021/acsnano.5b03950
Insights into Solid-State Electron Transport through Proteins from Inelastic Tunneling Spectroscopy: The Case of Azurin.
X. Yu (2015)
10.1080/05704928.2016.1166435
Investigation of molecular junctions with inelastic electron tunneling spectroscopy
Young-sang Kim (2016)
10.1021/JA972540A
RATES OF INTRAMOLECULAR ELECTRON TRANSFER IN RU(BPY)2(IM)(HIS83)-MODIFIED AZURIN INCREASE BELOW 220 K
L. Skov (1998)
10.1126/SCIENCE.1078675
Vibrationally Resolved Fluorescence Excited with Submolecular Precision
X. H. Qiu (2003)
10.1073/pnas.1719867115
Tunneling explains efficient electron transport via protein junctions
Jerry A Fereiro (2018)
10.1103/PHYSREVLETT.59.339
Inelastic electron tunneling from a metal tip: The contribution from resonant processes.
Persson (1987)
10.1038/nnano.2009.176
Molecular electronics with single molecules in solid-state devices.
K. Moth-Poulsen (2009)
10.1073/pnas.1201557109
Charge transport in molecular electronic junctions: Compression of the molecular tunnel barrier in the strong coupling regime
S. Y. Sayed (2012)
10.1088/0957-4484/15/7/058
Tuning current rectification across molecular junctions
J. Kushmerick (2004)
10.1021/JA00104A032
Raman Spectroscopy as an Indicator of Cu-S Bond Length in Type 1 and Type 2 Copper Cysteinate Proteins
C. Andrew (1994)
10.1063/1.1814076
Inelastic electron tunneling spectroscopy in molecular junctions: peaks and dips.
Michael Galperin (2004)
10.1021/jacs.5b01241
Mechanism of Orientation-Dependent Asymmetric Charge Transport in Tunneling Junctions Comprising Photosystem I
Olga E. Castañeda Ocampo (2015)
10.1073/PNAS.96.4.1379
An approach to long-range electron transfer mechanisms in metalloproteins: in situ scanning tunneling microscopy with submolecular resolution.
E. P. Friis (1999)
10.1103/PHYSREVLETT.93.236802
Control of relative tunneling rates in single molecule bipolar electron transport.
S. Wu (2004)
10.1142/10598
Molecular Electronics: An Introduction to Theory and Experiment
J. Cuevas (2010)
10.1103/PHYSREVLETT.117.126804
Transition from Strong to Weak Electronic Coupling in a Single-Molecule Junction.
R. Frisenda (2016)
10.1016/S0022-0728(97)00178-2
In situ STM and AFM of the copper protein Pseudomonas aeruginosa azurin
E. P. Friis (1997)
10.1103/PHYSREVB.22.848
Theory of intensities in inelastic-electron tunneling spectroscopy orientation of adsorbed molecules
J. Kirtley (1980)
10.1016/S1388-2481(99)00012-0
Electrochemistry of self-assembled monolayers of the blue copper protein Pseudomonas aeruginosa azurin on Au(111)
Qijin Chi (1999)
10.1038/nnano.2010.106
High-yield self-limiting single-nanowire assembly with dielectrophoresis.
E. M. Freer (2010)
10.1039/c4cp03605k
Promising anchoring groups for single-molecule conductance measurements.
Veerabhadrarao Kaliginedi (2014)
10.1002/SMLL.200700001
Electronic coupling between azurin and gold at different protein/substrate orientations.
Anurag Setty Venkat (2007)
10.1103/PhysRevLett.98.206803
Origin of discrepancies in inelastic electron tunneling spectra of molecular junctions.
L. Yu (2007)
10.1063/1.1290272
Electric-field assisted assembly and alignment of metallic nanowires
P. Smith (2000)
10.1021/NL071228O
Electronic transport in single molecule junctions: control of the molecule-electrode coupling through intramolecular tunneling barriers.
A. Danilov (2008)
10.1039/C3PY01638B
Optimising the enzyme response of a porous silicon photonic crystal via the modular design of enzyme sensitive polymers
A. Soeriyadi (2014)
10.1021/JA065864K
Effect of anchoring groups on single-molecule conductance: comparative study of thiol-, amine-, and carboxylic-acid-terminated molecules.
F. Chen (2006)
10.1021/ja207751w
Molecular tunnel junctions based on π-conjugated oligoacene thiols and dithiols between Ag, Au, and Pt contacts: effect of surface linking group and metal work function.
B. Kim (2011)
10.1146/ANNUREV.PHYSCHEM.57.032905.104709
Single-molecule electrical junctions.
Y. Selzer (2006)
10.1039/c7cp05536f
Revealing tunnelling details by normalized differential conductance analysis of transport across molecular junctions.
A. Vilan (2017)
Raman-spectroscopy as an indicator of Cu-S bond lengths and coordination geometries in copper-cysteinate proteins
C. R. Andrew (1994)



This paper is referenced by
10.1039/d0cp01621g
Introducing mesoscopic charge transfer rates into molecular electronics.
A. Santos (2020)
10.1002/smll.202004720
Selective Fabrication of Single-Molecule Junctions by Interface Engineering.
Biao-Feng Zeng (2020)
10.1002/slct.201903024
Tuning Thin Film Properties by Structural Modulations in Red Fluorescent Protein Chromophore Analogues
Ashish Singh (2019)
10.1016/j.isci.2020.101001
Coenzyme Coupling Boosts Charge Transport through Single Bioactive Enzyme Junctions
Xiao-yan Zhuang (2020)
10.1016/j.isci.2020.101099
Solid-State Protein Junctions: Cross-Laboratory Study ShowsPreservationof Mechanism at Varying Electronic Coupling
Sabyasachi Mukhopadhyay (2020)
10.1016/j.jelechem.2019.113472
Modulating the electron transport energy levels of protein by doping with foreign molecule
Wenhui Liang (2019)
10.1016/j.coelec.2020.100643
What can electrochemistry tell us about individual enzymes
Connor Davis (2021)
10.1039/d0cp01556c
Multifaceted aspects of charge transfer.
J. B. Derr (2020)
10.1002/aelm.201901416
Molecular Signature and Activationless Transport in Cobalt‐Terpyridine‐Based Molecular Junctions
Q. T. Nguyen (2020)
10.1002/ANGE.201906032
Solid‐state Protein‐based Reversible Biased‐induced Tunneling Current Switch
D. Cahen (2019)
10.1002/ANIE.201906032
A Solid‐State Protein Junction Serves as a Bias‐Induced Current Switch
Jerry A Fereiro (2019)
Supporting information to “ Photoresponse of Aromatic molecules in molecular Tunnel Junctions: Converting Photons to Charge carriers”
Jerry A Fereiro (2020)
Semantic Scholar Logo Some data provided by SemanticScholar