Modification of Thiols onto Single Crystal Surfaces of Gold Electrodes for Metalloportein Electrochemistry

Taniguchi, Ikuo; Yoshida, Masahito; Mie, Yasuhiro; Kudo, Kazuhiko; Nishiyama, Katsuhiko

doi:10.1007/978-4-431-65924-2_53

Cited by 9 publications

(7 citation statements)

References 6 publications

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“…The adlayer was composed of two different parts aligning to the ffiffi ffi 7 p direction, i.e., the brighter line part and a darker part consisting of two spots were alternately arranged. 70 Because corrugation heights between the two parts are different from each other (0.06 and 0.04 nm), we conclude that one orients perpendicular to the surface through thiolate S and pyrimidine N atoms in the brighter molecular row and the other takes an almost flat-lying orientation in the darker molecular row. From the cross-sectional profiles, the intermolecular spacings were found to be 0:75 AE 0:03 nm for ffiffi ffi 7 p direction and 1:42 AE 0:05 nm for the [1 1 10] atomic row direction.…”

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confidence: 69%

“…67b, 70 It is considered that the 4-PyS-Au surface interacts electrostatically with positively charged lysine residues on the cytochrome c and plays a role in an inhibition of denaturized adsorption of cytochrome c onto electrode surface to promote properly electron-transfer reaction. Since many promoter molecules have been studied to realize the promoter activity on polycrystalline Au electrodes, several results have been also reported for 2-PyS-modified Au electrode.…”

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confidence: 99%

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Molecular Assemblies of Functional Molecules on Gold Electrode Surfaces Studied by Electrochemical Scanning Tunneling Microscopy: Relationship between Function and Adlayer Structures

Yoshimoto

2006

Bulletin of the Chemical Society of Japan

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In this research, molecular assembly and function of aromatic thiols, porphyrins, phthalocyanines, and fullerenes on gold single crystal surfaces was studied by electrochemical methods and scanning tunneling microscopy (STM). Surface functions of promoter molecules such as pyridinethiols, pyrimidinethiols, and benzenethiol for cytochrome c electrochemistry were characterized by electrochemical techniques. Adlayer structures of those molecules were investigated by in situ STM, and molecular orientations for each molecule on the Au surfaces were clarified at molecular level. Adlayers of porphyrins and phthalocyanines for electrocatalytic reduction of dioxygen were examined to elucidate the relationship between activity and adlayer structure. Stable two-dimensional arrays of cobalt porphyrins indicated two-electron reduction of O 2 to H 2 O 2 , whereas two-step four-electron reduction of O 2 to H 2 O occurred because of highly mobile porphyrinatoiron molecules on the surface. Furthermore, well-defined adlayers of crown-substituted phthalocyanine for host-guest interface and binary array consisting of porphyrin and phthalocyanine for the design of supramolecular nanoarchitectures were clearly visualized by STM. Finally, a unique approach for controlling molecular orientation was found by the formation of supramolecular assemblies consisting of porphyrin and fullerene. The electrochemical redox reaction of carbonyl and ferrocene moieties was promoted by using the simple method for the construction of a 1:1 supramolecular assembled film consisting of C 60 derivative and octaethylporphyrinatometal on Au single crystal surfaces.In the field of electrochemistry, surface modification is often used for controlling electron-transfer reactions and catalytic activity. Especially, the electron-transfer reaction of a metalloprotein is currently one of the most active areas in bioelectrochemistry and related fields.

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confidence: 69%

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confidence: 99%

Molecular Assemblies of Functional Molecules on Gold Electrode Surfaces Studied by Electrochemical Scanning Tunneling Microscopy: Relationship between Function and Adlayer Structures

Yoshimoto

2006

Bulletin of the Chemical Society of Japan

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“…25 A study of 2-mercaptopyridine suggested that it interacts with Au via both the nitrogen and the sulfur. 26 However, prior to the work described herein, there have been no studies detailing the electrochemical behavior of the individual functional groups of a multifunctional adsorbate in order to determine how each moiety might influence another's response to changes in potential. Preliminary results of this work have appeared in a communication.…”

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confidence: 99%

Electrochemical Dimerization of 2-(2‘-Thienyl)pyridine Adsorbed on Au(111) Observed by in Situ Fluorescence

et al. 2004

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The study of heterodentate molecules adsorbed on metal electrodes provides an opportunity to expand the functionality of modified surfaces while offering insights into the surface and intramolecular electronic interactions of organic adsorbates. The adsorption of 2-(2'-thienyl)pyridine, a molecule containing both pyridine and thiophene moieties, on a Au(111) electrode is reported. Adsorption was characterized by electrochemistry in neutral and basic aqueous electrolyte and was compared to that of pyridine. The aqueous electrochemistry of thiophene on Au(111) was also characterized for comparison purposes. At negative potentials, in the presence of 2-(2'-thienyl)pyridine, a diffuse, pi-bonded monolayer was formed, and a phase transition to a close-packed N- and/or S-bonded configuration was observed near -0.4 V in a 1 mM solution of adsorbate, similar to that seen in pyridine on Au(111). The thiophene-like oxidative dimerization of the molecule was confirmed at positive potentials using in situ fluorescence microscopy by comparison with the spectrum of the chemically synthesized dimer.

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“…Since early reports on SAMs, many functionally modified electrodes have been used to investigate electrochemical reactions of metalloproteins (16)(17)(18)(19)(20)(21)(22)(23). For example, 4-mercaptopyridine (4-PySH) has been studied not only as a electron transfer promoter for cytochrome c (16,17), but from the standpoint of fundamental or structural chemistry using surface sensitive techniques such as surface enhanced Raman spectroscopy (SERS) (24)(25)(26) and surface enhanced infrared absorption spectroscopy (SEIRAS) (27,28).…”

Section: Introductionmentioning

confidence: 99%

Structural Change in 4-Pyridineethanethiolate Self-Assembled Monolayers on Au(111) Induced by Protonation of Pyridine Ring in Electrolyte Solutions

Nishiyama¹,

Tsuchiyama²,

Seriu³

et al. 2009

ECS Trans.

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Self-assembled monolayers (SAMs) of 4-pyridineethanethiol (4-PyEtS) formed on a Au surface was investigated by cyclic voltammetry (CV), surface enhanced infrared spectroscopy (SEIRAS), and in situ scanning tunneling microscopy (STM). On the basis of reductive desorption for 4-PyEtS on Au(111), the peak potential was observed at -0.86 V vs. Ag/AgCl (sat. KCl). The surface excess was calculated to be 5.4 × 10-10 mol cm-2 from the CV. High-resolution STM images revealed that p(5 × √3 R−30å) lattice including two molecules was found in 0.1 M NaClO4, whereas the 4-PyEtS-SAMs formed p(10 × √3 R−30å) lattice constituted from four molecules in 0.05 M HClO4. By the analysis of SEIRA spectra, the b axis of pyridine ring of 4-PyEtS-SAMs formed on an evaporated Au film electrode in 0.1 M NaClO4 was tilted to the electrode. In contrast, that in 0.1 M HCl was parallel to the surface.

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Modification of Thiols onto Single Crystal Surfaces of Gold Electrodes for Metalloportein Electrochemistry

Cited by 9 publications

References 6 publications

Molecular Assemblies of Functional Molecules on Gold Electrode Surfaces Studied by Electrochemical Scanning Tunneling Microscopy: Relationship between Function and Adlayer Structures

Molecular Assemblies of Functional Molecules on Gold Electrode Surfaces Studied by Electrochemical Scanning Tunneling Microscopy: Relationship between Function and Adlayer Structures

Electrochemical Dimerization of 2-(2‘-Thienyl)pyridine Adsorbed on Au(111) Observed by in Situ Fluorescence

Structural Change in 4-Pyridineethanethiolate Self-Assembled Monolayers on Au(111) Induced by Protonation of Pyridine Ring in Electrolyte Solutions

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