東華大學圖書館 |

語系: 繁體中文

說明(常見問題)

回圖書館首頁

手機版館藏查詢

登入

回首頁

切換: 標籤 | MARC模式 | ISBD

Copper-dioxygen complex mediated ali...

Li, Lei.

FindBook

Google Book

Amazon

博客來

Copper-dioxygen complex mediated aliphatic carbon-hydrogen bond and DNA nucleobase oxidation.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Copper-dioxygen complex mediated aliphatic carbon-hydrogen bond and DNA nucleobase oxidation./
作者:	Li, Lei.
面頁冊數:	255 p.
附註:	Source: Dissertation Abstracts International, Volume: 66-12, Section: B, page: 6613.
Contained By:	Dissertation Abstracts International66-12B.
標題:	Chemistry, Inorganic. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3197187
ISBN:	9780542430145

Copper-dioxygen complex mediated aliphatic carbon-hydrogen bond and DNA nucleobase oxidation.
Li, Lei.

Copper-dioxygen complex mediated aliphatic carbon-hydrogen bond and DNA nucleobase oxidation. - 255 p.

Source: Dissertation Abstracts International, Volume: 66-12, Section: B, page: 6613.

Thesis (Ph.D.)--The Johns Hopkins University, 2006.

Copper-dioxygen species are utilized by copper enzymes to effect aliphatic C-H bond oxidations. The investigation of biomimetic substrate oxidations with copper-O2 species employing polydentate ligands may be helpful in the elucidation of enzymatic reaction mechanisms, or even application to practical systems. On the other hand, highly reactive copper-O 2 intermediates could mediate DNA or protein oxidation reactions in vivo; thus, copper-O2 reactivity studies may shed light on their biological reactivity and/or control.

ISBN: 9780542430145Subjects--Topical Terms:

517253
Chemistry, Inorganic.

Copper-dioxygen complex mediated aliphatic carbon-hydrogen bond and DNA nucleobase oxidation.
LDR:03746nmm 2200313 4500 001 1827519
005 20070104081153.5
008 130610s2006 eng d
020 $a 9780542430145
035 $a (UnM)AAI3197187
035 $a AAI3197187
040 $a UnM $c UnM
100 1 $a Li, Lei. $3 1266105
245 1 0 $a Copper-dioxygen complex mediated aliphatic carbon-hydrogen bond and DNA nucleobase oxidation.
300 $a 255 p.
500 $a Source: Dissertation Abstracts International, Volume: 66-12, Section: B, page: 6613.
500 $a Adviser: Kenneth D. Karlin.
502 $a Thesis (Ph.D.)--The Johns Hopkins University, 2006.
520 $a Copper-dioxygen species are utilized by copper enzymes to effect aliphatic C-H bond oxidations. The investigation of biomimetic substrate oxidations with copper-O2 species employing polydentate ligands may be helpful in the elucidation of enzymatic reaction mechanisms, or even application to practical systems. On the other hand, highly reactive copper-O 2 intermediates could mediate DNA or protein oxidation reactions in vivo; thus, copper-O2 reactivity studies may shed light on their biological reactivity and/or control.
520 $a In Chapters 1 and 2, a dinuclear phenolate-containing copper(II) complex [CuII2(PD'O)(H2O)]3+ is discussed and its specific guanine (G) nucleobase oxidation reaction in the presence of 3-mercaptopropionic acid and molecular O2 is described. Required reaction conditions have been thoroughly studied in terms of a serious of freyed duplex DNA sequences, nature of copper complex and reductants, as well as the necessity of O2 involvement. The guanine oxidation products have been determined by electronspray ionization spectrometry (ESI-MS). Structural analysis of a copper guanosine complex [CuII 2(PD'O)(guanosine)]3+ suggests that copper-G coordination likely plays a role in reaction target recognition. A mu-hydroperoxide dicopper(II) species is suggested to be responsible for the G oxidation reaction.
520 $a In Chapters 3 and 4, the synthesis and spectroscopic characterization of the mu-hydroperoxide dicopper(II) species [CII2(PD'O -)(-O2H)]2+ are discussed. The most striking feature of this species is its aliphatic C-H bond oxidation reactivity. Upon thermal decay, it not only hydroxylates the nitrile solvent, releasing aldehyde and cyanide, but also oxidatively N-dealkylates and further dehydrogenates the ligand itself to give a Schiff base product. With added excess PPh3, decomposition of [CuII2(PD'O -)(-O2H)]2+ leads to the formation of a crosslinked ligand with a new C-O bond formed between the phenolate oxygen and a ligand methylene arm. A tetranuclear copper cluster {[Cu II2(PD'O-)(-OH)]2} 4+ with two OH- ligands bridging the dicopper(II) moieties is also obtained from the [CuII2(PD'O-)( -O2H)]2+ decay reaction.
520 $a In Chapter 5, the formation of an end-on peroxide species [{Cu II(L)}2(O22-)]2+ (2) with an anisole containing polypyridylamine ligand L is described. Though 2 is a close analogue of the well characterized while oxidative "inert" end-on peroxide [{CuII(TMPA)}2(O 22-)]2+ (3), as revealed by UV and rR spectroscopy, it exhibits a very interesting alkylbenzene C-H bond oxidation reactivity. Toluene is converted to benzaldehyde and ethylbenzene to acetophenone and 1-phenylethanol. The nature of this active Cu2O 2 species is discussed and the possible electrophilic character of the end-on peroxo species 2 is suggested.
590 $a School code: 0098.
650 4 $a Chemistry, Inorganic. $3 517253
650 4 $a Chemistry, Biochemistry. $3 1017722
690 $a 0488
690 $a 0487
710 2 0 $a The Johns Hopkins University. $3 1017431
773 0 $t Dissertation Abstracts International $g 66-12B.
790 1 0 $a Karlin, Kenneth D., $e advisor
790 $a 0098
791 $a Ph.D.
792 $a 2006
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3197187