Electron transfer in amino acid.nucleic acid base complexes: EPR, ENDOR, and DFT study of X-irradiated N-formylglycine.cytosine complex crystals.

Electron transfer in amino acid.nucleic acid base complexes: EPR, ENDOR, and DFT study of X-irradiated N-formylglycine.cytosine complex crystals. Research Abstract Details 

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Electron transfer in amino acid.nucleic acid base complexes: EPR, ENDOR, and DFT study of X-irradiated N-formylglycine.cytosine complex crystals. Abstract Text:

Einar Sagstuen,David M Close,Randi ,Eli O Hole,William H Nelson,Einar Sagstuen,David M Close,Randi ,Eli O Hole,William H Nelson,

Single crystals of the 1:1 complex of the nucleic acid base cytosine and the dipeptide N-formylglycine (C.NFG) have been irradiated at 10 and 273 K to doses of about 70 kGy and studied at temperatures between 10 and 293 K using 24 GHz (K-band) and 9.5 GHz (X-band) electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), and ENDOR-induced EPR (EIE) spectroscopy. In this complex, the cytosine base is hydrogen bonded at positions N3 and N4 to the carboxylic group of the dipeptide, and the N3 position of cytosine has become protonated by the carboxylic group. At 10 K, two major radicals were characterized and identified. One of these (R1) is ascribed to the decarboxylated N-formylglycine one-electron oxidized species. The other (R2) is the N3-protonated cytosine one-electron reduced species. A third minority species (R3) appears to be a different conformation or protonation state of the one-electron reduced cytosine radical. Upon warming, the R2 and R3 radicals decay at about 100 K, and at 295 K, the only cytosine-centered radicals present are the C5 and C6 H-addition radicals (R5, R6). The R1 radical decays at about 150 K, and a glycine backbone radical (R4) grows in slowly. Thus, in the complex, a complete separation of initial oxidation and reduction events occurs, with oxidation localized at the dipeptide moiety, whereas reduction occurs at the nucleic acid base moiety. DFT calculations indicate that this separation is driven by large differences in electron affinities and ionization potentials between the two constituents of the complex. Once the initial oxidation and reduction products are trapped, no further electron transfer between the two constituents of the complex takes place.

Electron transfer in amino acid.nucleic acid base complexes: EPR, ENDOR, and DFT study of X-irradiated N-formylglycine.cytosine complex crystals. Publishing Authors By Initials

E Sagstuen,DM Close,R ,EO Hole,WH Nelson,E Sagstuen,DM Close,R ,EO Hole,WH Nelson,

For similar investigative techniques: chemistry, analytical: spectrum analysis research abstracts see: investigative techniques: chemistry, analytical: spectrum analysis research

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Electron transfer in amino acid.nucleic acid base complexes: EPR, ENDOR, and DFT study of X-irradiated N-formylglycine.cytosine complex crystals. Journal Published:

PUBLICATION TYPE: Research Support, N.I.H., Extr

Journal: The journal of physical chemistry. A

VOLUME: 110

Page Numbers: 8653-62

Journal Abbreviation:

ISSN: 1089-5639

DAY: 20

MONTH: Jul

YEAR: 2006

Electron transfer in amino acid.nucleic acid base complexes: EPR, ENDOR, and DFT study of X-irradiated N-formylglycine.cytosine complex crystals. Information

Number of References:

LANGUAGE: eng

NlmUniqueID: 9890903

Electron transfer in amino acid.nucleic acid base complexes: EPR, ENDOR, and DFT study of X-irradiated N-formylglycine.cytosine complex crystals. Keywords Mesh Terms:

KEYWORDS: Spectrum Analysis

MESH TERMS: chemistry

Chemical & Substance for Abstract: Electron transfer in amino acid.nucleic acid base complexes: EPR, ENDOR, and DFT study of X-irradiated N-formylglycine.cytosine complex crystals. Information

Substance Name: Cytosine

Registry Number: 71-30-7

Grant and Affiliation Information for Electron transfer in amino acid.nucleic acid base complexes: EPR, ENDOR, and DFT study of X-irradiated N-formylglycine.cytosine complex crystals.

AFFILIATION: Department of Physics, University of Oslo, P.O. Box 1048 Blindern, N-0316 Oslo, Norway. einar.sagstuen@fys.uio.no

Country: United States

AGENCY: United States NCI

GRANT: CA36810

ACRONYM: CA

MEDLINETA: J Phys Chem A

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