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Recognition and oxidative strand sci...
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Humphreys, Kristi Jean.
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Recognition and oxidative strand scission of nucleic acids by multinuclear copper(II) coordination complexes.
紀錄類型:
書目-語言資料,印刷品 : Monograph/item
正題名/作者:
Recognition and oxidative strand scission of nucleic acids by multinuclear copper(II) coordination complexes./
作者:
Humphreys, Kristi Jean.
面頁冊數:
184 p.
附註:
Adviser: Kenneth D. Carlin.
Contained By:
Dissertation Abstracts International62-10B.
標題:
Chemistry, Biochemistry. -
電子資源:
http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3028284
ISBN:
0493403353
Recognition and oxidative strand scission of nucleic acids by multinuclear copper(II) coordination complexes.
Humphreys, Kristi Jean.
Recognition and oxidative strand scission of nucleic acids by multinuclear copper(II) coordination complexes.
- 184 p.
Adviser: Kenneth D. Carlin.
Thesis (Ph.D.)--The Johns Hopkins University, 2002.
The compound [Cu<sub>2</sub><super>II</super>(<bold>D</bold><super>1 </super>)(H<sub>2</sub>O)<sub>2</sub>](ClO<sub>4</sub>)<sub>4</sub>·2H<sub> 2</sub>O mediates efficient oxidative cleavage of DNA under conditions conducive for reduction of the metal centers and subsequent activation of dioxygen. Relative to a mononuclear analogue, the binuclear complex more rapidly effects degradation of both plasmids and oligonucleotides. Cleavage requires both the complex and a reductant and likely proceeds through a nondiffusible O<sub> 2</sub>-derived intermediate, the formation of which may be dependent on the presence of multiple metal ions in the same complex.
ISBN: 0493403353Subjects--Topical Terms:
1017722
Chemistry, Biochemistry.
Recognition and oxidative strand scission of nucleic acids by multinuclear copper(II) coordination complexes.
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The compound [Cu<sub>2</sub><super>II</super>(<bold>D</bold><super>1 </super>)(H<sub>2</sub>O)<sub>2</sub>](ClO<sub>4</sub>)<sub>4</sub>·2H<sub> 2</sub>O mediates efficient oxidative cleavage of DNA under conditions conducive for reduction of the metal centers and subsequent activation of dioxygen. Relative to a mononuclear analogue, the binuclear complex more rapidly effects degradation of both plasmids and oligonucleotides. Cleavage requires both the complex and a reductant and likely proceeds through a nondiffusible O<sub> 2</sub>-derived intermediate, the formation of which may be dependent on the presence of multiple metal ions in the same complex.
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A trinuclear copper complex, [Cu<sub>3</sub><super>II</super>(<bold> L</bold>)(H<sub>2</sub>O)<sub>3</sub>(NO<sub>3</sub>)<sub>2</sub>](NO<sub> 3</sub>)<sub>4</sub>·5H<sub>2</sub>O, exhibits a remarkable ability to promote specific strand scission at helix/coil junctions. Strand scission occurs on the 3<super>′</super> overhang at the junction of a hairpin or frayed duplex structure and is not dependent on the identity of the base at which cleavage occurs. Target recognition minimally requires a purine at the first unpaired position and a guanine at the second unpaired position on the 5<super>′</super> extension. Selective strand scission requires both a reductant and dioxygen and does not appear to involve a diffusible radical. Comparisons between the trinuclear copper complex and mononuclear compounds indicate that the recognition and reactivity described in this report are also dependent on the multinuclearity of the complex.
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The compound [Cu<sub>2</sub><super>II</super>(<bold>D</bold><super>1 </super>)(H<sub>2</sub>O)<sub>2</sub>](ClO<sub>4</sub>)<sub>4</sub> also selectively promotes cleavage of DNA on nucleotide strands that extend from the 3<super> ′</super> side of frayed duplex structures at a site two residues displaced from the junction. The minimal requirements for reaction include a guanine in the first unpaired position of the 3<super>′</super> overhang adjacent to the cleavage site and an adenine in the parallel position on the 5<super> ′</super> overhang. Recognition and strand scission are independent of the nucleobase at the cleavage site. The necessary presence of both a reductant and dioxygen indicates that the intermediate responsible for cleavage is produced by the activation of dioxygen by a copper(I) form of the binuclear complex. The unique coordination and reactivity properties of [Cu<sub>2</sub><super> II</super>(<bold>D</bold><super>1</super>)(H<sub>2</sub>O)<sub>2</sub>](ClO<sub> 4</sub>)<sub>4</sub> are critical for its efficiency and site selectivity since mononuclear compounds and a binuclear analogue exhibit only nonselective cleavage of DNA.
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http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3028284
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