Multiple Electronic and Structural Factors Control Cyclobutane Pyrimidine Dimer and 6–4 Thymine–Thymine Photodimerization in a DNA Duplex

The T–T photodimerization paths leading to the formation of cyclobutane pyrimidine dimer (CPD) and 6–4 pyrimidine pyrimidone (64‐PP), the two main DNA photolesions, have been resolved for a T–T step in a DNA duplex by two complementary state‐of‐the‐art quantum mechanical approaches: QM(CASPT2//CASSC...

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Published in:Chemistry : a European journal 2017-10, Vol.23 (60), p.15177-15188
Main Authors: Conti, Irene, Martínez‐Fernández, Lara, Esposito, Luciana, Hofinger, Siegfried, Nenov, Artur, Garavelli, Marco, Improta, Roberto
Format: Article
Language:English
Subjects:
64-PP
Charge transfer
Chemical Physics
Chemistry
Cyclobutane
Deoxyribonucleic acid
DFT calculations
DNA
photodimerization
Physics
Quantum mechanics
Thymine
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container_issue 60
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creator Conti, Irene
Martínez‐Fernández, Lara
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Garavelli, Marco
Improta, Roberto
description The T–T photodimerization paths leading to the formation of cyclobutane pyrimidine dimer (CPD) and 6–4 pyrimidine pyrimidone (64‐PP), the two main DNA photolesions, have been resolved for a T–T step in a DNA duplex by two complementary state‐of‐the‐art quantum mechanical approaches: QM(CASPT2//CASSCF)/MM and TD‐DFT/PCM. Based on the analysis of several different representative structures, we define a new‐ensemble of cooperating geometrical and electronic factors (besides the distance between the reacting bonds) ruling T–T photodimerization in DNA. CPD is formed by a barrierless path on an exciton state delocalized over the two bases. Large interbase stacking and shift values, together with a small pseudorotation phase angle for T at the 3′‐end, favor this reaction. The oxetane intermediate, leading to a 64‐PP adduct, is formed on a singlet T→T charge‐transfer state and is favored by a large interbase angle and slide values. A small energy barrier (
doi_str_mv 10.1002/chem.201703237
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Based on the analysis of several different representative structures, we define a new‐ensemble of cooperating geometrical and electronic factors (besides the distance between the reacting bonds) ruling T–T photodimerization in DNA. CPD is formed by a barrierless path on an exciton state delocalized over the two bases. Large interbase stacking and shift values, together with a small pseudorotation phase angle for T at the 3′‐end, favor this reaction. The oxetane intermediate, leading to a 64‐PP adduct, is formed on a singlet T→T charge‐transfer state and is favored by a large interbase angle and slide values. A small energy barrier (&lt;0.3 eV) is associated to this path, likely contributing to the smaller quantum yield observed for this process. 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subjects 64-PP
Charge transfer
Chemical Physics
Chemistry
Cyclobutane
Deoxyribonucleic acid
DFT calculations
DNA
photodimerization
Physics
Quantum mechanics
Thymine
title Multiple Electronic and Structural Factors Control Cyclobutane Pyrimidine Dimer and 6–4 Thymine–Thymine Photodimerization in a DNA Duplex
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