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Photoinduced charge transfer between neighboring bases plays an important role in DNA. One of its important effects is shown in its ability to affect the photochemical yields of the formation of cyclobutane pyrimidine dimer (CPD) products between adjacent pyrimidine bases. In this work we examine how the energies of charge transfer states depend on the sequences of oligonucleotides using a hybrid quantum and molecular mechanics (QM/MM) methodology combined with the algebraic diagrammatic construction through a second order electronic structure method for excited states. Specifically, we examine 10 sequences with guanine being on the 5′ or 3′ position of two pyrimidine bases. The results show that the energies of charge transfer states are affected by the nature of the donor acceptor pair, by the distance between them, and by other electrostatic effects created by the surrounding environment.
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Stabilization of the Triplet Biradical Intermediate of 5‐Methylcytosine Enhances Cyclobutane Pyrimidine Dimer (CPD) Formation in DNA
Abstract Cyclobutane pyrimidine dimer (CPD) is a photoproduct formed by two stacked pyrimidine bases through a cycloaddition reaction upon irradiation. Owing to its close association with skin cancer, the mechanism of CPD formation has been studied thoroughly. Among many aspects of CPD, its formation involving 5‐methylcytosine (5mC) has been of special interest because the CPD yield is known to increase with C5‐methylation of cytosine. In this work, high‐level quantum mechanics/molecular mechanics (QM/MM) calculations are used to examine a previously experimentally detected pathway for CPD formation in hetero (thymine‐cytosine and thymine‐5mC) dipyrimidines, which is facilitated through intersystem crossing in thymine and formation of a triplet biradical intermediate. A DNA duplex model system containing a core sequence TmCG or TCG is used. The stabilization of a radical center in the biradical intermediate by the methyl group of 5mC can lead to increased CPD yield in TmCG compared with its non‐methylated counterpart, TCG, thereby suggesting the existence of a new pathway of CPD formation enhanced by 5mC.
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- Award ID(s):
- 1800171
- PAR ID:
- 10236604
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Chemistry – A European Journal
- Volume:
- 26
- Issue:
- 62
- ISSN:
- 0947-6539
- Format(s):
- Medium: X Size: p. 14181-14186
- Size(s):
- p. 14181-14186
- Sponsoring Org:
- National Science Foundation
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