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Subject = Phenazines;
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Displaying Results 1 - 2 of 2 on page 1 of 1
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Reversal of a Single Base-Pair Step Controls Guanine Photo-Oxidation by an Intercalating Ruthenium(II) Dipyridophenazine Complex
(2020)
Keane, Páraic M.; Poynton, Fergus E.; Hall, James P.; Quinn, Susan J.
Reversal of a Single Base-Pair Step Controls Guanine Photo-Oxidation by an Intercalating Ruthenium(II) Dipyridophenazine Complex
(2020)
Keane, Páraic M.; Poynton, Fergus E.; Hall, James P.; Quinn, Susan J.
Abstract:
Small changes in DNA sequence can often have major biological effects. Here the rates and yields of guanine photo-oxidation by Λ-[Ru(TAP)2(dppz)]2+ have been compared in 5′-{CCGGATCCGG}2 and 5′-{CCGGTACCGG}2 using pico/nanosecond transient visible and time-resolved IR (TRIR) spectroscopy. The inefficiency of electron transfer in the TA sequence is consistent with the 5′-TA-3′ versus 5′-AT-3′ binding preference predicted by X-ray crystallography. The TRIR spectra also reveal the differences in binding sites in the two oligonucleotides.
Irish Research Council
Science Foundation Ireland
Royal Irish Academy/Royal Society International Exchange Scheme
UK Biotechnology and Biological Sciences Research Council
College of Science, UCD
UK Science and Technology Facilities Council
http://hdl.handle.net/10197/11605
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Spectro-electrochemical Studies on [Ru(TAP)2 (dppz)]2+ - Insights into the Mechanism of its Photosensitized Oxidation of Oligonucleotides
(2020)
Keane, Páraic M.; Tory, Joanne; Towrie, Michael; Quinn, Susan J.
Spectro-electrochemical Studies on [Ru(TAP)2 (dppz)]2+ - Insights into the Mechanism of its Photosensitized Oxidation of Oligonucleotides
(2020)
Keane, Páraic M.; Tory, Joanne; Towrie, Michael; Quinn, Susan J.
Abstract:
[Ru(TAP) 2 (dppz)] 2+ (TAP = 1,4,5,8-tetraazaphenanthrene; dppz = dipyrido[3,2-a:2′,3′-c]phenazine) is known to photo-oxidize guanine in DNA. Whether this oxidation proceeds by direct photoelectron transfer or by proton-coupled electron transfer is still unknown. To help distinguish between these mechanisms, spectro-electrochemical experiments have been carried out with [Ru(TAP) 2 (dppz)] 2+ in acetonitrile. The UV-vis and mid-IR spectra obtained for the one-electron reduced product were compared to those obtained by picosecond transient absorption and time-resolved infrared experiments of [Ru(TAP) 2 (dppz)] 2+ bound to guanine-containing DNA. An interesting feature of the singly reduced species is an electronic transition in the near-IR region (with λ max at 1970 and 2820 nm). Density functional and time-dependent density functional theory simulations of the vibrational and electronic spectra of [Ru(TAP) 2 (dppz)] 2+ , the reduced complex [Ru(TAP) 2 (dppz)] + , and four isomers of ...
http://hdl.handle.net/10197/11604
Displaying Results 1 - 2 of 2 on page 1 of 1
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