Premium
Investigation of the Pathways of Excess Electron Transfer in DNA with Flavin‐Donor and Oxetane‐Acceptor Modified DNA Hairpins
Author(s) -
Breeger Sascha,
von Meltzer Martin,
Hennecke Ulrich,
Carell Thomas
Publication year - 2006
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200600074
Subject(s) - flavin group , dna , electron transfer , cleave , chemistry , oxetane , electron acceptor , duplex (building) , acceptor , electron donor , cleavage (geology) , photochemistry , stereochemistry , enzyme , biochemistry , materials science , catalysis , polymer chemistry , physics , condensed matter physics , fracture (geology) , composite material
Oxetane is a potential intermediate that is enzymatically formed during the repair of (6–4) DNA lesions by special repair enzymes (6–4 DNA photolyases). These enzymes use a reduced and deprotonated flavin to cleave the oxetane by single electron donation. Herein we report synthesis of DNA hairpin model compounds containing a flavin as the hairpin head and two different oxetanes in the stem structure of the hairpin. The data show that the electron moves through the duplex even over distances of 17 Å. Attempts to trap the moving electron with N 2 O showed no reduction of the cleavage efficiency showing that the electron moves through the duplex and not through solution. The electron transfer is sequence dependent. The efficiency is reduced by a factor of 2 in GC rich DNA hairpins.