Electronic Properties of Functional Biomolecules at Metal/Aqueous Solution Interfaces

Jingdong Zhang, Qijin Chi, A.M. Kuznetsov, Allan Glargaard Hansen, Hainer Wackerbarth, Hans Erik Mølager Christensen, Jens Enevold Thaulov Andersen, Jens Ulstrup

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

Monolayers of molecules, which retain their function in the adsorbed state on solid surfaces, are important in materials science, analytical detection, and other technology approaching the nanoscale. Molecular monolayers, including layers of functional biological macromolecules, offer new insight in electronic properties and stochastic single-molecule features and can be probed by new methods which approach the single-molecule level. Olle of these is in situ scanning tunneling microscopy (STM) in which single-molecule electronic properties directly in aqueous solution are probed. In situ STM combined with physical electrochemistry, single-crystal electrodes, and spectroscopic methods is now a new dimension in interfacial bioelectrochemistry. We overview first same approaches to spectroscopic single-molecule imaging, including fluorescence spectroscopy, chemical reaction dynamics, atomic force microscopy, and electrochemical single-electron transfer. We then focus on in situ STM. In addition to high structural resolution, in situ STM offers a singlemolecule spectroscopic perspective. This emerges most clearly when adsorbate molecules contain accessible redox leveis, and the tunneling current decomposes into successive single-molecule interfacial electron transfer (ET) steps. Theories of electrochemical ET and in situ STM of redox molecules as well as specific cases are addressed. Two-step in situ STM represents different molecular mechanisms and even new ET phenomena, related to coherent many-electron transfer. A number of systems are noted to accord with these views. The discussion is concluded by attention to Olle of the still very few redox protein s addressed by in situ STM, the bine copper protein Pseudomonas aeruginosa azurin. Use of comprehensive electrochemical techniques has ascertained that well-defined protein monolayers in two opposite orientations can be formed and interfacial tunneling patterns disclosed. P. aeruginosa azurin emerges as by far the most convincing case where in situ STM of functional metalloproteins to single-molecule resolution has been achieved. This comprehensive approach holds promise for broader lise of in situ STM as a single-molecule spectroscopy of metalloproteins and illuminates prerequisites and limitations of in situ STM of biological macromolecules.
Original languageEnglish
JournalJournal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical
Volume106
Issue number6
Pages (from-to)1131-1152
ISSN1520-6106
DOIs
Publication statusPublished - 2002

Cite this

Zhang, Jingdong ; Chi, Qijin ; Kuznetsov, A.M. ; Hansen, Allan Glargaard ; Wackerbarth, Hainer ; Christensen, Hans Erik Mølager ; Andersen, Jens Enevold Thaulov ; Ulstrup, Jens. / Electronic Properties of Functional Biomolecules at Metal/Aqueous Solution Interfaces. In: Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical. 2002 ; Vol. 106, No. 6. pp. 1131-1152.
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title = "Electronic Properties of Functional Biomolecules at Metal/Aqueous Solution Interfaces",
abstract = "Monolayers of molecules, which retain their function in the adsorbed state on solid surfaces, are important in materials science, analytical detection, and other technology approaching the nanoscale. Molecular monolayers, including layers of functional biological macromolecules, offer new insight in electronic properties and stochastic single-molecule features and can be probed by new methods which approach the single-molecule level. Olle of these is in situ scanning tunneling microscopy (STM) in which single-molecule electronic properties directly in aqueous solution are probed. In situ STM combined with physical electrochemistry, single-crystal electrodes, and spectroscopic methods is now a new dimension in interfacial bioelectrochemistry. We overview first same approaches to spectroscopic single-molecule imaging, including fluorescence spectroscopy, chemical reaction dynamics, atomic force microscopy, and electrochemical single-electron transfer. We then focus on in situ STM. In addition to high structural resolution, in situ STM offers a singlemolecule spectroscopic perspective. This emerges most clearly when adsorbate molecules contain accessible redox leveis, and the tunneling current decomposes into successive single-molecule interfacial electron transfer (ET) steps. Theories of electrochemical ET and in situ STM of redox molecules as well as specific cases are addressed. Two-step in situ STM represents different molecular mechanisms and even new ET phenomena, related to coherent many-electron transfer. A number of systems are noted to accord with these views. The discussion is concluded by attention to Olle of the still very few redox protein s addressed by in situ STM, the bine copper protein Pseudomonas aeruginosa azurin. Use of comprehensive electrochemical techniques has ascertained that well-defined protein monolayers in two opposite orientations can be formed and interfacial tunneling patterns disclosed. P. aeruginosa azurin emerges as by far the most convincing case where in situ STM of functional metalloproteins to single-molecule resolution has been achieved. This comprehensive approach holds promise for broader lise of in situ STM as a single-molecule spectroscopy of metalloproteins and illuminates prerequisites and limitations of in situ STM of biological macromolecules.",
author = "Jingdong Zhang and Qijin Chi and A.M. Kuznetsov and Hansen, {Allan Glargaard} and Hainer Wackerbarth and Christensen, {Hans Erik M{\o}lager} and Andersen, {Jens Enevold Thaulov} and Jens Ulstrup",
year = "2002",
doi = "10.1021/jp0129941",
language = "English",
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pages = "1131--1152",
journal = "Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical",
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Electronic Properties of Functional Biomolecules at Metal/Aqueous Solution Interfaces. / Zhang, Jingdong; Chi, Qijin; Kuznetsov, A.M.; Hansen, Allan Glargaard; Wackerbarth, Hainer; Christensen, Hans Erik Mølager; Andersen, Jens Enevold Thaulov; Ulstrup, Jens.

In: Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical, Vol. 106, No. 6, 2002, p. 1131-1152.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Electronic Properties of Functional Biomolecules at Metal/Aqueous Solution Interfaces

AU - Zhang, Jingdong

AU - Chi, Qijin

AU - Kuznetsov, A.M.

AU - Hansen, Allan Glargaard

AU - Wackerbarth, Hainer

AU - Christensen, Hans Erik Mølager

AU - Andersen, Jens Enevold Thaulov

AU - Ulstrup, Jens

PY - 2002

Y1 - 2002

N2 - Monolayers of molecules, which retain their function in the adsorbed state on solid surfaces, are important in materials science, analytical detection, and other technology approaching the nanoscale. Molecular monolayers, including layers of functional biological macromolecules, offer new insight in electronic properties and stochastic single-molecule features and can be probed by new methods which approach the single-molecule level. Olle of these is in situ scanning tunneling microscopy (STM) in which single-molecule electronic properties directly in aqueous solution are probed. In situ STM combined with physical electrochemistry, single-crystal electrodes, and spectroscopic methods is now a new dimension in interfacial bioelectrochemistry. We overview first same approaches to spectroscopic single-molecule imaging, including fluorescence spectroscopy, chemical reaction dynamics, atomic force microscopy, and electrochemical single-electron transfer. We then focus on in situ STM. In addition to high structural resolution, in situ STM offers a singlemolecule spectroscopic perspective. This emerges most clearly when adsorbate molecules contain accessible redox leveis, and the tunneling current decomposes into successive single-molecule interfacial electron transfer (ET) steps. Theories of electrochemical ET and in situ STM of redox molecules as well as specific cases are addressed. Two-step in situ STM represents different molecular mechanisms and even new ET phenomena, related to coherent many-electron transfer. A number of systems are noted to accord with these views. The discussion is concluded by attention to Olle of the still very few redox protein s addressed by in situ STM, the bine copper protein Pseudomonas aeruginosa azurin. Use of comprehensive electrochemical techniques has ascertained that well-defined protein monolayers in two opposite orientations can be formed and interfacial tunneling patterns disclosed. P. aeruginosa azurin emerges as by far the most convincing case where in situ STM of functional metalloproteins to single-molecule resolution has been achieved. This comprehensive approach holds promise for broader lise of in situ STM as a single-molecule spectroscopy of metalloproteins and illuminates prerequisites and limitations of in situ STM of biological macromolecules.

AB - Monolayers of molecules, which retain their function in the adsorbed state on solid surfaces, are important in materials science, analytical detection, and other technology approaching the nanoscale. Molecular monolayers, including layers of functional biological macromolecules, offer new insight in electronic properties and stochastic single-molecule features and can be probed by new methods which approach the single-molecule level. Olle of these is in situ scanning tunneling microscopy (STM) in which single-molecule electronic properties directly in aqueous solution are probed. In situ STM combined with physical electrochemistry, single-crystal electrodes, and spectroscopic methods is now a new dimension in interfacial bioelectrochemistry. We overview first same approaches to spectroscopic single-molecule imaging, including fluorescence spectroscopy, chemical reaction dynamics, atomic force microscopy, and electrochemical single-electron transfer. We then focus on in situ STM. In addition to high structural resolution, in situ STM offers a singlemolecule spectroscopic perspective. This emerges most clearly when adsorbate molecules contain accessible redox leveis, and the tunneling current decomposes into successive single-molecule interfacial electron transfer (ET) steps. Theories of electrochemical ET and in situ STM of redox molecules as well as specific cases are addressed. Two-step in situ STM represents different molecular mechanisms and even new ET phenomena, related to coherent many-electron transfer. A number of systems are noted to accord with these views. The discussion is concluded by attention to Olle of the still very few redox protein s addressed by in situ STM, the bine copper protein Pseudomonas aeruginosa azurin. Use of comprehensive electrochemical techniques has ascertained that well-defined protein monolayers in two opposite orientations can be formed and interfacial tunneling patterns disclosed. P. aeruginosa azurin emerges as by far the most convincing case where in situ STM of functional metalloproteins to single-molecule resolution has been achieved. This comprehensive approach holds promise for broader lise of in situ STM as a single-molecule spectroscopy of metalloproteins and illuminates prerequisites and limitations of in situ STM of biological macromolecules.

U2 - 10.1021/jp0129941

DO - 10.1021/jp0129941

M3 - Journal article

VL - 106

SP - 1131

EP - 1152

JO - Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical

JF - Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical

SN - 1520-6106

IS - 6

ER -