Conformational Dependence of Electron Transfer across de novo Designed Metalloproteins

Flash photolysis and pulse radiolysis measurements demonstrate a conformational dependence of electron transfer rates across a 16-mer helical bundle (three-helix metalloprotein) modified with a capping CoIII(bipyridine)3 electron acceptor at the N terminus and a 1-ethyl-1′-ethyl-4,4′-bip yridinium d...

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Veröffentlicht in:Proceedings of the National Academy of Sciences - PNAS 1996-09, Vol.93 (18), p.9521-9526
Hauptverfasser: Mutz, Mitchell W., McLendon, George L., Wishart, James F., Gaillard, Elizabeth R., Corin, Alan F.
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container_end_page 9526
container_issue 18
container_start_page 9521
container_title Proceedings of the National Academy of Sciences - PNAS
container_volume 93
creator Mutz, Mitchell W.
McLendon, George L.
Wishart, James F.
Gaillard, Elizabeth R.
Corin, Alan F.
description Flash photolysis and pulse radiolysis measurements demonstrate a conformational dependence of electron transfer rates across a 16-mer helical bundle (three-helix metalloprotein) modified with a capping CoIII(bipyridine)3 electron acceptor at the N terminus and a 1-ethyl-1′-ethyl-4,4′-bip yridinium donor at the C terminus. For the CoIII(peptide)3-1-ethyl-1$^{\prime}$ -ethyl-4,4′-bipyridinium maquettes, the observed transfer is a first order, intramolecular process, independent of peptide concentration or laser pulse energy. In the presence of 6 M urea, the random coil bundle (≈ 0% helicity) has an observed electron transfer rate constant of kobs = 900 ± 100 s-1. In the presence of 25% trifluoroethanol (TFE), the helicity of the peptide is 80% and the kobs increases to 2000 ± 200 s-1. Moreover, the increase in the rate constant in TFE is consistent with the observed decrease in donor--acceptor distance in this solvent. Such bifunctional systems provide a class of molecules for testing the effects of conformation on electron transfer in proteins and peptides.
doi_str_mv 10.1073/pnas.93.18.9521
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source Jstor Complete Legacy; MEDLINE; PubMed Central; Alma/SFX Local Collection; Free Full-Text Journals in Chemistry
subjects Amino Acid Sequence
Biochemistry
Chemistry
Circular Dichroism
Drug Design
Electrodes
Electron transfer
Electron Transport
Electrons
Metalloproteins
Metalloproteins - chemistry
Molecular Sequence Data
Phosphates
Photolysis
Protein Conformation
Proteins
Radiolysis
Sodium
Viologens
Voltammetry
title Conformational Dependence of Electron Transfer across de novo Designed Metalloproteins
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