Premium
Dynamics of Excess‐Electron Transfer through Alternating Adenine:Thymine Sequences in DNA
Author(s) -
Lin ShihHsun,
Fujitsuka Mamoru,
Majima Tetsuro
Publication year - 2015
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.201503115
Subject(s) - thymine , trimer , electron transfer , stacking , flash photolysis , dna , diphenylacetylene , chemistry , electron acceptor , pyrimidine dimer , photochemistry , nucleotide , nucleobase , photoinduced electron transfer , reaction rate constant , biophysics , kinetics , dna damage , biochemistry , dimer , biology , physics , organic chemistry , quantum mechanics , gene , catalysis
This paper presents the results of an investigation into the sequence‐dependent excess‐electron transfer (EET) dynamics in DNA, which plays an important role in DNA damage/repair. There are many published studies on EET in consecutive adenine:thymine (A:T) sequences ( Tn ), but those in alternating A:T sequences ( ATn ) remain limited. Here, two series of functionalized DNA oligomers, Tn and ATn , were synthesized with a strongly electron‐donating photosensitizer, a trimer of ethylenedioxythiophene ( 3 E ), and an electron acceptor, diphenylacetylene ( DPA ). Laser flash photolysis experiments showed that the EET rate constant of AT3 is two times lower than that of T3 due to the lack of π‐stacking of Ts in AT3 . Thus, it was indicated that excess‐electron hopping is affected by the interaction between LUMOs of nucleotides.