What Can We Learn from Protein-Based Electron Transport Junctions?
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ABSTRACT:
SUBMITTER: Cahen D
PROVIDER: S-EPMC8647078 | biostudies-literature | 2021 Dec
REPOSITORIES: biostudies-literature
Publications
What Can We Learn from Protein-Based Electron Transport Junctions?
Cahen David D Pecht Israel I Sheves Mordechai M
The journal of physical chemistry letters 20211201 47
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Project description:The fundamental question of "what is the transport path of electrons through proteins?" initially introduced while studying long-range electron transfer between localized redox centers in proteins in vivo is also highly relevant to the transport properties of solid-state, dry metal-protein-metal junctions. Here, we report conductance measurements of such junctions, Au-(Azurin monolayer ensemble)-Bismuth (Bi) ones, with well-defined nanopore geometry and ~103 proteins/pore. Our results can be understood as follows. (1) Transport is via two interacting conducting channels, characterized by different spatial and time scales. The slow and spatially localized channel is associated with the Cu center of Azurin and the fast delocalized one with the protein's polypeptide matrix. Transport via the slow channel is by a sequential (noncoherent) process and in the second one by direct, off-resonant tunneling. (2) The two channels are capacitively coupled. Thus, with a change in charge occupation of the weakly coupled (metal center) channel, the broad energy level manifold, responsible for off-resonance tunneling, shifts, relative to the electrodes' Fermi levels. In this process, the off-resonance (fast) channel dominates transport, and the slow (redox) channel, while contributing only negligibly directly, significantly affects transport by intramolecular gating.
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Project description:In this article, we have investigated the influence of the nitro side-group on the single molecular conductance of pyridine-based molecules by scanning tunneling microscopy break junction. Single molecular conductance of 4,4'-bipyridine (BPY), 3-nitro-4-(pyridin-4-yl)pyridine (BPY-N), and 3-nitro-4-(3-nitropyridin-4-yl)pyridine (BPY-2N) were measured by contact with Au electrodes. For the BPY molecular junction, two sets of conductance were found with values around 10-3.1 G₀ (high G) and 10-3.7 G₀ (low G). The addition of nitro side-group(s) onto the pyridine ring resulted in lower conductance of 10-3.8 G₀ for BPY-N and 10-3.9 G₀ for BPY-2N, respectively, which can be attributed to the twist angle of two pyridine rings. Moreover, the steric hindrance of nitro group(s) also affects the contacting configuration of electrode-molecule-electrode. As a consequence, only one set of conductance value was observed for BPY-N and BPY-2N. Our work clearly shows the important role of side-groups on the electron transport of single-molecule junctions.
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Project description:Molecular junctions hold great potential for future microelectronics and attract people's attention. Here, we used density functional theory calculations (DFT) to investigate the surface-enhanced Raman spectroscopy (SERS) and electron transport properties of fully π-conjugated oligomers (phenylacetylene)-3 (OPE-3) trapped in gold junctions. The effects of charge injection, an applied electric field, and molecular deformation are considered. We found that a new Raman peak located at around 1400 cm-1 appears after the injection of a charge, which agrees well with the experiment. The external electric field and configurational deformation hardly affect the Raman spectra, indicating that the electronic rather than the geometrical structure determines the Raman response. Nonequilibrium Green's function (NEGF) calculations show that both the rotation of the benzene groups and an increased electrode distance largely reduced the conductivity of the studied molecular junctions. The present investigations provide valuable information on the effect of charging, electric field, and deformation on the SERS and conductivity of molecular junctions, helping the development of molecular devices.
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