Electron Transfer through DNA in the Course of Radical-Induced Strand Cleavage

Angewandte Chemie - International Edition

Volumn 37, Issue 4, 1998, Pages 460-462

  Meggers, Eric ^a   Kusch, Dirk ^a   Spichty, Martin ^a   Wille, Uta ^a   Giese, Bernd ^a  

^a UNIVERSITY OF BASEL   (Switzerland)

Author keywords

DNA cleavage; Electron transfer; Radical ions; Radical reactions

Indexed keywords

EID: 0032473446     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19980302)37:4<460::AID-ANIE460>3.0.CO;2-U     Document Type: Article

References (44)

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38. G triple units were chosen for the experiments on the distance dependence because they are the most potent electron donating sites in DNA (see ref. [6]). We suppose that the closest G is the initially oxidized base. This assumption is permitted since the change from a single G to a triple G unit in 3′- as well as in 5′-direction has nearly the same ET-acceleration effect of 2.5 and 1.8, respectively (Table 1, entries 8, 11, and 9, 12).
39. For the determination of the distance Δr, the corresponding DNA duplex sequences were constructed in the B-form with the nucleic acid building tool in the program MacroModel V4.5. In order to mimic the planar enol ether radical cation 3, the deoxyribose enol ether 5 was modeled into the DNA structure using the AMBER* force field implemented in MacroModel V4.5. Distances Δr were taken between the radical center C3′ of the radical cation and the G carbon atom 5 which has the highest electron density of the HOMO.
40. Independent experiments with glutathione diethyl ester as a trap for radical 6 demonstrated that, in G-free DNA strands, the addition of water to radical cation 3 (3→6) occurs in about 70% yield.
41. trap. Because these ratios turned out to be independent of the conversion, the reactions follow first- or pseudo first-order kinetics.
42. -1 by pseudo first-order kinetic experiments with different concentrations of KI.
43. Note added in proof (February 2, 1998): Similar ET rates at 7 Å were reported recently: K. Fukui, K. Tanaka, Angew. Chem. 1998, 110, 167; Angew. Chem. Int. Ed. 1998, 37, 158.
44. Note added in proof (February 2, 1998): Similar ET rates at 7 Å were reported recently: K. Fukui, K. Tanaka, Angew. Chem. 1998, 110, 167; Angew. Chem. Int. Ed. 1998, 37, 158.