Design, synthesis, and evaluation of a biomimetic artificial photolyase model.
Two new artificial photolyase models that recognize pyrimidine dimers in protic and aprotic organic solvents as well as in water through a combination of charge and hydrogen-bonding interactions and use a mimic of the flavine to achieve repair through reductive photoinduced electron transfer are presented. Fluorescence and NMR titration studies show that it forms a 1:1 complex with pyrimidine dimers with binding constants of approximately 10(3) M(-1) in acetonitrile or methanol, while binding constants in water at pH 7.2 are slightly lower. Excitation of the complex with visible light leads to clean and rapid cycloreversion of the pyrimidine dimer through photoinduced electron transfer catalysis. The reaction in water is significantly faster than in organic solvents. The reaction slows down at higher conversions due to product inhibition.
Wiest
Olaf
O
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556-5670, USA. owiest@nd.edu
Harrison
Christopher B
CB
Saettel
Nicolas J
NJ
Cibulka
Radek
R
Sax
Mirjam
M
König
Burkhard
B
D040761:Biomimetic Materials / Q000138:chemical synthesis / Q000737:chemistry / Q000378:metabolism; D004255:Deoxyribodipyrimidine Photo-Lyase / Q000138:chemical synthesis / Q000737:chemistry / Q000378:metabolism; D006860:Hydrogen Bonding; D008956:Models, Chemical; D015394:Molecular Structure; D011740:Pyrimidine Dimers / Q000737:chemistry / Q000378:metabolism; D012997:Solvents / Q000737:chemistry; D013997:Time Factors; D014867:Water / Q000737:chemistry
D011740:Pyrimidine Dimers; D012997:Solvents; D014867:Water; D004255:Deoxyribodipyrimidine Photo-Lyase