Understanding the factors controlling the photo-oxidation of natural DNA by enantiomerically pure intercalating ruthenium polypyridyl complexes through TA/TRIR studies with polydeoxynucleotides and mixed sequence oligodeoxynucleotides.
Understanding the factors controlling the photo-oxidation of natural DNA by enantiomerically pure intercalating ruthenium polypyridyl complexes through TA/TRIR studies with polydeoxynucleotides and mixed sequence oligodeoxynucleotides.
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DOI：
10.1039/d0sc02413a
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发表时间：
2020-08-06
期刊：
影响因子：
8.4
通讯作者：
Kelly JM
中科院分区：
文献类型：
--
作者：
Keane PM;O'Sullivan K;Poynton FE;Poulsen BC;Sazanovich IV;Towrie M;Cardin CJ;Sun XZ;George MW;Gunnlaugsson T;Quinn SJ;Kelly JM
钌聚吡啶复合物可以敏化核酸和其他生物分子的光氧化，显示出光治疗应用的潜力。在本文中，结合使用瞬时可见光吸收 (TrA) 和时间分辨红外 (TRIR) 光谱来比较聚合 {poly(dG-dC)、poly(dA-dT) 和天然 DNA} 和小型混合序列双链体形成寡脱氧核苷酸中 [Ru(TAP)2(dppz)]2+ 对映体对鸟嘌呤的光氧化作用。电子转移产物很容易通过中心位于 ca 的 TRIR 特征带的出现来监测。鸟嘌呤自由基阳离子的波长为 1700 cm−1，谱带中心位于 ca。还原钌络合物的 TrA 波长为 515 nm。研究发现，有效的电子转移需要将复合物插入含有 G-C 碱基对的位点。值得注意的是，电子转移发生前由束缚激发态引起的 TRIR 光谱核碱基振动的变化可用于识别混合序列寡脱氧核苷酸和天然 DNA 中的首选嵌入位点。有趣的是，对于天然DNA，虽然发现猝灭在皮秒范围内效率低下，但电子转移过程发生较慢，而所研究的混合序列双链体形成寡脱氧核苷酸则没有发现这种情况。有效的电子转移需要将复合物插入 G-C 碱基对处。通过在电子转移前对核碱基振动进行 TRIR 监测来识别首选嵌入位点。
Ruthenium polypyridyl complexes which can sensitise the photo-oxidation of nucleic acids and other biological molecules show potential for photo-therapeutic applications. In this article a combination of transient visible absorption (TrA) and time-resolved infra-red (TRIR) spectroscopy are used to compare the photo-oxidation of guanine by the enantiomers of [Ru(TAP)2(dppz)]2+ in both polymeric {poly(dG-dC), poly(dA-dT) and natural DNA} and small mixed-sequence duplex-forming oligodeoxynucleotides. The products of electron transfer are readily monitored by the appearance of a characteristic TRIR band centred at ca. 1700 cm−1 for the guanine radical cation and a band centered at ca. 515 nm in the TrA for the reduced ruthenium complex. It is found that efficient electron transfer requires that the complex be intercalated at a G-C base-pair containing site. Significantly, changes in the nucleobase vibrations of the TRIR spectra induced by the bound excited state before electron transfer takes place are used to identify preferred intercalation sites in mixed-sequence oligodeoxynucleotides and natural DNA. Interestingly, with natural DNA, while it is found that quenching is inefficient in the picosecond range, a slower electron transfer process occurs, which is not found with the mixed-sequence duplex-forming oligodeoxynucleotides studied. Efficient electron transfer requires the complex to be intercalated at a G-C base-pair. Identification of preferred intercalation sites is achieved by TRIR monitoring of the nucleobase vibrations before electron transfer.
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影响因子：
3.8
作者：
Banyay, M;Sarkar, M;Gräslund, A
通讯作者：
Gräslund, A
影响因子：
4.3
作者：
Keane, Paraic M.;Hall, James P.;Kelly, John M.
通讯作者：
Kelly, John M.
DOI：
10.1002/anie.201502608
发表时间：
2015-07-13
期刊：
Angewandte Chemie (International ed. in English)
影响因子：
--
作者：
Keane PM;Poynton FE;Hall JP;Sazanovich IV;Towrie M;Gunnlaugsson T;Quinn SJ;Cardin CJ;Kelly JM
通讯作者：
Kelly JM
影响因子：
4.3
作者：
Elias, Benjamin;Creely, Caitriona;Kelly, John M.
通讯作者：
Kelly, John M.
影响因子：
4.6
作者：
Boynton AN;Marcélis L;McConnell AJ;Barton JK
通讯作者：
Barton JK