Near-UV Induced Interstrand Cross-Links in Anthraquinone−DNA Duplexes

Bergeron, François; Nair, Vandana Kuttappan; Wagner, J. Richard

doi:10.1021/ja064625u

Cited by 17 publications

(17 citation statements)

References 8 publications

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“…One solution to the dual problems of low formation efficiencies and fast charge recombination for singlet SRIPs is the use of triplet excited states as electron acceptors. Anthraquinone (Aq) derivatives undergo rapid intersystem crossing and have been widely used in studies of photoinduced electron transfer in DNA. − However, the dynamics and efficiency of charge separation and charge recombination in Aq-DNA systems have received relatively little attention. Charge recombination of either a triplet CRIP or SRIP to form the singlet ground state is spin forbidden and thus potentially slower than charge transport over multiple base pairs in D-B n -A systems with DNA base-pair bridges.…”

Section: Introductionmentioning

confidence: 99%

Structure and Dynamics of Photogenerated Triplet Radical Ion Pairs in DNA Hairpin Conjugates with Anthraquinone End Caps

et al. 2012

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A series of DNA hairpins (AqGn) possessing a tethered anthraquinone (Aq) end-capping group were synthesized in which the distance between the Aq and a guanine-cytosine (G-C) base pair was systematically varied by changing the number (n - 1) of adenine-thymine (A-T) base pairs between them. The photophysics and photochemistry of these hairpins were investigated using nanosecond transient absorption and time-resolved electron paramagnetic resonance (TREPR) spectroscopy. Upon photoexcitation, (1*)Aq undergoes rapid intersystem crossing to yield (3*)Aq, which is capable of oxidizing purine nucleobases resulting in the formation of (3)(Aq(-•)Gn(+•)). All (3)(Aq(-•)Gn(+•)) radical ion pairs exhibit asymmetric TREPR spectra with an electron spin polarization phase pattern of absorption and enhanced emission (A/E) due to their different triplet spin sublevel populations, which are derived from the corresponding non-Boltzmann spin sublevel populations of the (3*)Aq precursor. The TREPR spectra of the (3)(Aq(-•)Gn(+•)) radical ion pairs depend strongly on their spin-spin dipolar interaction and weakly on their spin-spin exchange coupling. The anisotropy of (3)(Aq(-•)Gn(+•)) makes it possible to determine that the π systems of Aq(-•) and G(+•) within the radical ion pair are parallel to one another. Charge recombination of the long-lived (3)(Aq(-•)Gn(+•)) radical ion pair displays an unusual bimodal distance dependence that results from a change in the rate-determining step for charge recombination from radical pair intersystem crossing for n < 4 to coherent superexchange for n > 4.

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Section: Introductionmentioning

confidence: 99%

Structure and Dynamics of Photogenerated Triplet Radical Ion Pairs in DNA Hairpin Conjugates with Anthraquinone End Caps

et al. 2012

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“…Hypericin is used as a photosensitizer in photodynamical therapy of cancer and displays photoinduced virucidal (anti-viral, anti-retroviral) and antitumor activities 6 7 8 9 10 . Moreover, when anthraquinone is designed as photonucleases and reacts with DNA, they can cleave the single or double-strand DNA at special sites 11 12 13 14 . J. R. Wagner and his co-worker reported the formation of novel interstrand corss-links between anthraquinone and thymine in DNA 13 .…”

mentioning

confidence: 99%

“…Moreover, when anthraquinone is designed as photonucleases and reacts with DNA, they can cleave the single or double-strand DNA at special sites 11 12 13 14 . J. R. Wagner and his co-worker reported the formation of novel interstrand corss-links between anthraquinone and thymine in DNA 13 . D. Zhong and A. H. Zewail et al .…”

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confidence: 99%

Ultrafast investigation of photoinduced charge transfer in aminoanthraquinone pharmaceutical product

Zhang

Sun

Zhou

et al. 2017

Sci Rep

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We investigated the mechanism of intramolecular charge transfer and the following radiationless dynamics of the excited states of 1-aminoanthraquinone using steady state and time-resolved absorption spectroscopy combined with quantum chemical calculations. Following photoexcitation with 460 nm, conformational relaxation via twisting of the amino group, charge transfer and the intersystem crossing (ISC) processes have been established to be the major relaxation pathways responsible for the ultrafast nonradiative of the excited S1 state. Intramolecular proton transfer, which could be induced by intramolecular hydrogen bonding is inspected and excluded. Time-dependent density functional theory (TDDFT) calculations reveal the change of the dipole moments of the S0 and S1 states along the twisted coordinate of the amino group, indicating the mechanism of twisted intra-molecular charge transfer (TICT). The timescale of TICT is measured to be 5 ps due to the conformational relaxation and a barrier on the S1 potential surface. The ISC from the S1 state to the triplet manifold is a main deactivation pathway with the decay time of 28 ps. Our results observed here have yield a physically intuitive and complete picture of the photoinduced charge transfer and radiationless dynamics in anthraquinone pharmaceutial products.

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“…To incorporate an AQ sensitizer into the DNA backbone, ODN 1A C H T U N G T R E N N U N G (AQ 1 ) was prepared by coupling AQ succinimidyl ester [27] with ODN (N), which possessed an amino linker in the middle of sequential bases. [28] In this study, we used a partial sequence of the human p53 gene corresponding to codons 280-285 of exon 8 and targeted the m C at codon 282. [29] The sequences and structures of ODNs used in this study are summarized in Scheme 3.…”

Section: Resultsmentioning

confidence: 99%

Anthraquinone‐Sensitized Photooxidation of 5‐Methylcytosine in DNA Leading to Piperidine‐Induced Efficient Strand Cleavage

Yamada

Kitauchi

Tanabe

et al. 2011

Chemistry A European J

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One-electron photooxidations of 5-methyl-2'-deoxycytidine (d(m)C) and 5-trideuteriomethyl-2'-deoxycytidine ([D(3)]d(m)C) by sensitization with anthraquinone (AQ) derivatives were investigated. Photoirradiation of an aerated aqueous solution containing d(m)C and anthraquinone 2-sulfonate (AQS) afforded 5-formyl-2'-deoxycytidine (d(f)C) and 5-hydroxymethyl-2'-deoxycytidine (d(hm)C) in good yield through an initial one-electron oxidation process. The deuterium isotope effect on the AQS-sensitized photooxidation of d(m)C suggests that the rate-determining step in the photosensitized oxidation of d(m)C involves internal transfer of the C5-hydrogen atom of a d(m)C-tetroxide intermediate to produce d(f)C and d(hm)C. In the case of a 5-methylcytosine ((m)C)-containing duplex DNA with an AQ chromophore that is incorporated into the backbone of the DNA strand so as to be immobilized at a specific position, (m)C underwent efficient direct one-electron oxidation by the photoexcited AQ, which resulted in an exclusive DNA strand cleavage at the target (m)C site upon hot piperidine treatment. In accordance with the suppression of the strand cleavage at 5-trideuterio-methylcytosine observed in a similar AQ photosensitization, it is suggested that deprotonation at the C5-methyl group of an intermediate (m)C radical cation may occur as a key elementary reaction in the photooxidative strand cleavage at the (m)C site. Incorporation of an AQ sensitizer into the interior of a strand of the duplex enhanced the one-electron photooxidation of (m)C, presumably because of an increased intersystem crossing efficiency that may lead to efficient piperidine-induced strand cleavage at an (m)C site in a DNA duplex.

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Near-UV Induced Interstrand Cross-Links in Anthraquinone−DNA Duplexes

Cited by 17 publications

References 8 publications

Structure and Dynamics of Photogenerated Triplet Radical Ion Pairs in DNA Hairpin Conjugates with Anthraquinone End Caps

Structure and Dynamics of Photogenerated Triplet Radical Ion Pairs in DNA Hairpin Conjugates with Anthraquinone End Caps

Ultrafast investigation of photoinduced charge transfer in aminoanthraquinone pharmaceutical product

Anthraquinone‐Sensitized Photooxidation of 5‐Methylcytosine in DNA Leading to Piperidine‐Induced Efficient Strand Cleavage

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