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Mechanistic studies of enzymatic C-H...

Deng, Dayi.

Mechanistic studies of enzymatic C-H bond hydroxylation by radical clocks.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Mechanistic studies of enzymatic C-H bond hydroxylation by radical clocks.
Author:	Deng, Dayi.
Description:	158 p.
Notes:	Adviser: John T. Groves.
Notes:	Source: Dissertation Abstracts International, Volume: 68-01, Section: B, page: 0271.
Contained By:	Dissertation Abstracts International68-01B.
Subject:	Chemistry, Biochemistry.
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3247796

Mechanistic studies of enzymatic C-H bond hydroxylation by radical clocks.
Deng, Dayi.

Mechanistic studies of enzymatic C-H bond hydroxylation by radical clocks. - 158 p.

Adviser: John T. Groves.

Thesis (Ph.D.)--Princeton University, 2007.

A class of mechanistic substrates has been applied for the mechanistic studies of aerobic and anaerobic enzymatic oxidations of hydrocarbons. Mechanistic studies of cytochrome P450 C-H bond hydroxylation reveal a radical mechanism and the possibility of a cationic intermediate deriving from an electron-transfer process by the originally formed radical intermediate. Mechanistic studies of T4MO (toluene 4-monooxygenase) by norcarane, 1,1-diethylpropane, 1,1-dimethylpropane reveal a similar conclusion as in P450s. These mechanistic probes have been further utilized in the studies of whole-cell cultures containing P450s and AlkB, which again demonstrate the same theory. Therefore, as a general rule, aerobic oxidations of hydrocarbons by biologically important systems are best described as a 'hydrogen abstraction and oxygen rebound' process.Subjects--Topical Terms:

226900
Chemistry, Biochemistry.

Mechanistic studies of enzymatic C-H bond hydroxylation by radical clocks.
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100 0 $a Deng, Dayi. $3 264311
245 1 0 $a Mechanistic studies of enzymatic C-H bond hydroxylation by radical clocks.
300 $a 158 p.
500 $a Adviser: John T. Groves.
500 $a Source: Dissertation Abstracts International, Volume: 68-01, Section: B, page: 0271.
502 $a Thesis (Ph.D.)--Princeton University, 2007.
520 # $a A class of mechanistic substrates has been applied for the mechanistic studies of aerobic and anaerobic enzymatic oxidations of hydrocarbons. Mechanistic studies of cytochrome P450 C-H bond hydroxylation reveal a radical mechanism and the possibility of a cationic intermediate deriving from an electron-transfer process by the originally formed radical intermediate. Mechanistic studies of T4MO (toluene 4-monooxygenase) by norcarane, 1,1-diethylpropane, 1,1-dimethylpropane reveal a similar conclusion as in P450s. These mechanistic probes have been further utilized in the studies of whole-cell cultures containing P450s and AlkB, which again demonstrate the same theory. Therefore, as a general rule, aerobic oxidations of hydrocarbons by biologically important systems are best described as a 'hydrogen abstraction and oxygen rebound' process.
520 # $a These radical-clocks have been further utilized in the mechanistic studies of the classical Kharasch reaction and other biomimic important systems. Reaction mechanisms have been fully explored. The results demonstrate the accuracy and effectiveness of radical clocks.
590 $a School code: 0181.
650 # 0 $a Chemistry, Biochemistry. $3 226900
690 $a 0487
710 0 # $a Princeton University. $3 212488
773 0 # $g 68-01B. $t Dissertation Abstracts International
790 $a 0181
790 1 0 $a Groves, John T., $e advisor
791 $a Ph.D.
792 $a 2007
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