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DNA ionic liquids: Transport charac...

Leone, Anthony Michael.

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DNA ionic liquids: Transport characteristics and photo-induced electron transfer.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	DNA ionic liquids: Transport characteristics and photo-induced electron transfer./
作者:	Leone, Anthony Michael.
面頁冊數:	171 p.
附註:	Source: Dissertation Abstracts International, Volume: 64-04, Section: B, page: 1716.
Contained By:	Dissertation Abstracts International64-04B.
標題:	Chemistry, Analytical. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3086559

DNA ionic liquids: Transport characteristics and photo-induced electron transfer.
Leone, Anthony Michael.

DNA ionic liquids: Transport characteristics and photo-induced electron transfer. - 171 p.

Source: Dissertation Abstracts International, Volume: 64-04, Section: B, page: 1716.

Thesis (Ph.D.)--The University of North Carolina at Chapel Hill, 2003.

Ionic liquids are described that contain duplex DNA as the anion and polyether-decorated transition metal complexes based on M(bpy350) 3<super>2+</super> as the cation (M = Co, Ni, Ru; bpy350 = 4,4<super>′</super>-(CH3(OCH2CH2) 7OCO)2-2,2<super>′</super>-bipyridine). The pure Co(bpy 350)3DNA melt does not exhibit recognizable voltammetric waves. Analysis of voltammetry and chronoamperometry of mixtures of these phases with complexes having ClO4<super>−</super> counterions (Co(bpy350)3(ClO4)2) and no other diluent provides charge transport rates from the oxidation and reduction currents for the complexes. As the mole fraction of the Co(bpy350) 3(ClO4)2 complex in the mixture is varied from ca. 0.25 to 1, the physical diffusion constants derived from the Co<super> 3+/2+</super> wave increase from 1 × 10<super>−11</super> cm<super> 2</super>/s to 5 × 10<super>−10</super> cm<super>2</super>/s, and apparent diffusion constants dominated by the Co<super>2+/1+</super> electron self-exchange increase from 1 × 10<super>−11</super> cm<super> 2</super>/s to 2 × 10<super>−8</super> cm<super>2</super>/s. DNA suppresses the Co<super>2+/1+</super> electron transfer reactions of Co complexes for which it is counterion.Subjects--Topical Terms:

586156
Chemistry, Analytical.

DNA ionic liquids: Transport characteristics and photo-induced electron transfer.
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100 1 $a Leone, Anthony Michael. $3 1945914
245 1 0 $a DNA ionic liquids: Transport characteristics and photo-induced electron transfer.
300 $a 171 p.
500 $a Source: Dissertation Abstracts International, Volume: 64-04, Section: B, page: 1716.
500 $a Advisers: H. Holden Thorp; Royce W. Murray.
502 $a Thesis (Ph.D.)--The University of North Carolina at Chapel Hill, 2003.
520 $a Ionic liquids are described that contain duplex DNA as the anion and polyether-decorated transition metal complexes based on M(bpy350) 3<super>2+</super> as the cation (M = Co, Ni, Ru; bpy350 = 4,4<super>′</super>-(CH3(OCH2CH2) 7OCO)2-2,2<super>′</super>-bipyridine). The pure Co(bpy 350)3DNA melt does not exhibit recognizable voltammetric waves. Analysis of voltammetry and chronoamperometry of mixtures of these phases with complexes having ClO4<super>−</super> counterions (Co(bpy350)3(ClO4)2) and no other diluent provides charge transport rates from the oxidation and reduction currents for the complexes. As the mole fraction of the Co(bpy350) 3(ClO4)2 complex in the mixture is varied from ca. 0.25 to 1, the physical diffusion constants derived from the Co<super> 3+/2+</super> wave increase from 1 × 10<super>−11</super> cm<super> 2</super>/s to 5 × 10<super>−10</super> cm<super>2</super>/s, and apparent diffusion constants dominated by the Co<super>2+/1+</super> electron self-exchange increase from 1 × 10<super>−11</super> cm<super> 2</super>/s to 2 × 10<super>−8</super> cm<super>2</super>/s. DNA suppresses the Co<super>2+/1+</super> electron transfer reactions of Co complexes for which it is counterion.
520 $a Undiluted voltammetry of DNA molten salts containing the powerful oxidizers Fe(bpy350)3(ClO4)2 and Ru(bpy 350)3(ClO4)2 exhibit electrocatalytic waves. Independent experiments show that Fe(bpy350)3<super> 3+</super> and Ru(bpy350)3<super>3+</super> selectively oxidize guanine and adenine in duplex DNA. Digital simulations are used to study the DNA oxidation.
520 $a Several independent models show that electron hopping among the bases of DNA is necessary to explain the measured current responses and that the relative timescale of the processes occurring are: DPHYS > DNA DAPP > M350<super>3+</super>-DNA electron transfer.
520 $a Molten salts of Ni(bpy350)3<super>2+</super> and single stranded oligonucleotides were prepared. Photo-induced electron transfer was observed between small amounts of Ru(bpz)3<super>2+</super> * (E<super>2+*/1+</super> = 1.35 V vs. SCE, bpz = 2,2<super> ′</super>-bipyrazine) added to the melt and guanine in the nucleic acid, by measuring the emission lifetime of the ruthenium complex in melts containing varying amounts of guanine-containing nucleic acid. A linear relationship was observed between the fraction of Ru(bpz)3<super>2+</super> * that was quenched and the mole fraction of guanine-containing oligonucleotides. The average electron transfer rate constant at full guanine loading was 7 × 10<super>6</super> s<super>−1</super>, which implies an average electron transfer distance of 12.5 Å (center-to-center).
590 $a School code: 0153.
650 4 $a Chemistry, Analytical. $3 586156
650 4 $a Chemistry, Inorganic. $3 517253
690 $a 0486
690 $a 0488
710 2 0 $a The University of North Carolina at Chapel Hill. $3 1017449
773 0 $t Dissertation Abstracts International $g 64-04B.
790 1 0 $a Thorp, H. Holden, $e advisor
790 1 0 $a Murray, Royce W., $e advisor
790 $a 0153
791 $a Ph.D.
792 $a 2003
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3086559