TY - JOUR
T1 - Effect of NH2 rotation on the fluorescence of 2-aminopurine in solution
AU - Abou-Zied, Osama K.
N1 - Funding Information:
The author would like to thank Sultan Qaboos University (Grant No. IG/SCI/CHEM/12/01 ) for supporting this work.
PY - 2013/6/1
Y1 - 2013/6/1
N2 - Since the introduction of 2-aminopurine (2AP) in 1969 as a fluorescent analogue of adenine, its intense fluorescence in aqueous solution and the subsequent reduction of this intensity in DNA has been a powerful tool for studies of structural changes in DNA. Herein, we show that the unusual intense fluorescence of 2AP in water is attributed to the formation of a closed complex between one water molecule and 2AP in the excited state. This configuration restricts the rotation of the 2-NH2 group which subsequently lowers the nonradiative decay rate. We supported this finding by attaching heavy masses to the amino group, dimethyl (2-(N(Me)2)) and diethyl (2-(N(Et) 2)). By examining the fluorescence behavior in dioxane (an apolar, aprotic solvent), the lighter NH2 group can rotate in the excited state more freely which enhances the nonradiative loss of fluorescence. On the other hand, this rotation slows down sharply in the two heavy-group derivatives, leading to a restoration of the fluorescence intensity and lifetime very close to that of 2AP in water. Depletion of fluorescence was observed in the 2AP derivatives in water and is attributed to the population of a twisted intramolecular charge transfer (TICT) state due to the strong electron donating power of the NR2 groups, an effect that is absent for the parent 2AP.
AB - Since the introduction of 2-aminopurine (2AP) in 1969 as a fluorescent analogue of adenine, its intense fluorescence in aqueous solution and the subsequent reduction of this intensity in DNA has been a powerful tool for studies of structural changes in DNA. Herein, we show that the unusual intense fluorescence of 2AP in water is attributed to the formation of a closed complex between one water molecule and 2AP in the excited state. This configuration restricts the rotation of the 2-NH2 group which subsequently lowers the nonradiative decay rate. We supported this finding by attaching heavy masses to the amino group, dimethyl (2-(N(Me)2)) and diethyl (2-(N(Et) 2)). By examining the fluorescence behavior in dioxane (an apolar, aprotic solvent), the lighter NH2 group can rotate in the excited state more freely which enhances the nonradiative loss of fluorescence. On the other hand, this rotation slows down sharply in the two heavy-group derivatives, leading to a restoration of the fluorescence intensity and lifetime very close to that of 2AP in water. Depletion of fluorescence was observed in the 2AP derivatives in water and is attributed to the population of a twisted intramolecular charge transfer (TICT) state due to the strong electron donating power of the NR2 groups, an effect that is absent for the parent 2AP.
KW - 2-Aminopurine
KW - DNA base analogue
KW - Fluorescence
KW - Hydrogen bond
KW - Internal rotation
KW - Lifetime
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U2 - 10.1016/j.jphotochem.2013.03.007
DO - 10.1016/j.jphotochem.2013.03.007
M3 - Article
AN - SCOPUS:84877100488
SN - 1010-6030
VL - 261
SP - 1
EP - 6
JO - Journal of Photochemistry and Photobiology A: Chemistry
JF - Journal of Photochemistry and Photobiology A: Chemistry
ER -