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Ruthenium(II) Polypyridine Complexes and the Electron-Transfer Reactions of Metalloproteins

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Bill Durham and Frank Millett

Department of Chemistry and Biochemistry, University of Arkansas, Fayetteville, AR 72701

J. Chem. Educ., 1997, 74 (6), p 636

DOI: 10.1021/ed074p636

Publication Date (Web): June 1, 1997

Section:

History, Education, and Documentation

Abstract

Over the past decade, a variety of ruthenium complexes have been used to study electron-transfer reactions in metalloproteins. In the majority of these studies, the ruthenium complexes provide a means of photochemically initiating a rapid electron-transfer reaction. These reactions can be used in several different schemes to: 1) probe structural features which determine the magnitude of the electronic coupling between redox centers in metalloproteins, 2) measure the rate constants for electron transfer between two metalloproteins, 3) investigate the binding interactions between two proteins and 4) measure the rate constants for formation and dissociation of protein-protein complexes. The basic reactions involved in the photochemical schemes and the covalent binding of ruthenium complexes to metalloproteins are described. Several examples involving cytochrome c and cytochrome b₅ are used to illustrate the methodology.

Keywords (Audience):

Upper-Division Undergraduate

Keywords (Domain):

Biochemistry

Keywords (Feature):

Symposium Report

Keywords (Subject):

Oxidation / Reduction

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This article has been cited by 4 ACS Journal articles (4 most recent appear below).

Effect of DNA Scaffolding on Intramolecular Electron Transfer Quenching of a Photoexcited Ruthenium(II) Polypyridine Naphthalene Diimide
Dabney W. Dixon, Nancy B. Thornton, Vera Steullet, and Thomas Netzel
Inorganic Chemistry1999 38 (24), 5526-5534
- Effect of DNA Scaffolding on Intramolecular Electron Transfer Quenching of a Photoexcited Ruthenium(II) Polypyridine Naphthalene Diimide
  Dabney W. Dixon, Nancy B. Thornton, Vera Steullet, and Thomas Netzel
  Inorganic Chemistry1999 38 (24), 5526-5534
  A RuII(bpy)2(bpy-CONH)2+ donor covalently attached by way of a CH2CH2CH2 linker to a naphthalene diimide (NDI) acceptor has been synthesized. The complex intercalates in calf thymus DNA, as indicated by the hypochromism of the naphthalene diimide moiety ...
  Abstract | Full Text HTML | Hi-Res PDF
Polymerization of 2-Ethyl-2-oxazoline Using Di-, Tetra-, and Hexafunctional Ruthenium Tris(bipyridine) Metalloinitiators
John E. McAlvin and Cassandra L. Fraser
Macromolecules1999 32 (21), 6925-6932
- Polymerization of 2-Ethyl-2-oxazoline Using Di-, Tetra-, and Hexafunctional Ruthenium Tris(bipyridine) Metalloinitiators
  John E. McAlvin and Cassandra L. Fraser
  Macromolecules1999 32 (21), 6925-6932
  Ruthenium reagents with two, four, and six chloromethyl functionalities, [(bpy)nRu{bpy(CH2Cl)2}3-n](PF6)2 (n = 02), were employed as multifunctional metalloinitiators for the cationic polymerization of 2-ethyl-2-oxazoline to generate orange, glassy ...
  Abstract | Full Text HTML | Hi-Res PDF
Direct Observation of the Ferric-Porphyrin Cation Radical as an Intermediate in the Phototriggered Oxidation of Ferric- to Ferryl-Heme Tethered to Ru(bpy)₃ in Reconstituted Myoglobin
Itaru Hamachi, Shinya Tsukiji, Seiji Shinkai, and Shigero Oishi
Journal of the American Chemical Society1999 121 (23), 5500-5506
- Direct Observation of the Ferric-Porphyrin Cation Radical as an Intermediate in the Phototriggered Oxidation of Ferric- to Ferryl-Heme Tethered to Ru(bpy)₃ in Reconstituted Myoglobin
  Itaru Hamachi, Shinya Tsukiji, Seiji Shinkai, and Shigero Oishi
  Journal of the American Chemical Society1999 121 (23), 5500-5506
  Using semisynthetic myoglobins (Ru(bpy)3-Mbs) with covalently appended Ru(bpy)3 (bpy = 2,2-bipyridine), an oxidized Mb is photoproduced through an intramolecular electron abstraction reaction as a key step. UVvis spectra, electron paramagnetic resonance ...
  Abstract | Full Text HTML | Hi-Res PDF
Intramolecular Quenching of Porphyrin Fluorescence by a Covalently Linked Ferrocene in DNA Scaffolding
Nancy B. Thornton, Hania Wojtowicz, Thomas Netzel, and Dabney W. Dixon
The Journal of Physical Chemistry B1998 102 (11), 2101-2110
- Intramolecular Quenching of Porphyrin Fluorescence by a Covalently Linked Ferrocene in DNA Scaffolding
  Nancy B. Thornton, Hania Wojtowicz, Thomas Netzel, and Dabney W. Dixon
  The Journal of Physical Chemistry B1998 102 (11), 2101-2110
  Intramolecular quenching of fluorescence from a cationic porphyrin by a covalently attached ferrocene in both solution and DNA is reported. Two ferrocenyl porphyrins have been prepared, tris(4-N-methylpyridiniumyl), mono(phenyl-OCH2CH2ferrocene)porphyrin, ...
  Abstract | Full Text HTML | Hi-Res PDF

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Ruthenium(II) Polypyridine Complexes and the Electron-Transfer Reactions of Metalloproteins