GPx-Like Activity of Selenides and Selenoxides: Experimental Evidence for the Involvement of Hydroxy Perhydroxy Selenane as the Active Species

被引：163

作者：

Nascimento, Vanessa ^{[1
]}

Alberto, Eduardo E. ^{[2
]}

Tondo, Daniel W. ^{[1
]}

Dambrowski, Daniel ^{[1
]}

Detty, Michael R. ^{[2
]}

Nome, Faruk ^{[1
]}

Braga, Antonio L. ^{[1
]}

机构：

[1] Univ Fed Santa Catarina, Dept Chem, Florianopolis, SC, Brazil

[2] SUNY Buffalo, Dept Chem, Buffalo, NY 14260 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2012年 / 134卷 / 01期

关键词：

DENDRIMERIC ORGANOCHALCOGEN CATALYSTS; CYCLIC SELENINATE ESTERS; ANTIOXIDANT ACTIVITY; SODIUM-BROMIDE; METHIONINE SELENOXIDE; REMARKABLE ACTIVITY; IN-SITU; GLUTATHIONE; OXIDATION; PEROXIDE;

D O I：

10.1021/ja209570y

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reaction mechanism of the GPx-like oxidation of PhSH with H2O2 catalyzed by selenoxides proceeds via formation of the hydroxy perhydroxy selenane, which is a stronger oxidizing agent than selenoxide. A hydroxy perhydroxy selenane intermediate was observed by electrospray ionization mass spectrometry and Se-77 NMR spectroscopy in reactions of selenoxide 8 with H2O2. The initial velocity of oxidation of PhSH by H2O2 with selenoxide 8 is 4 orders of magnitude higher than that of 8 without peroxide. Selenoxide 8 is not reduced to selenide 6 by PhSH in the presence of H2O2. While electronic substituent effects have minimal impact on the catalytic performance of selenoxides, chelating groups increase the rate of catalysis.

引用

页码：138 / 141

页数：4

共 74 条

[1] THE OXIDATION OF EBSELEN METABOLITES TO THIOL OXIDANTS CATALYZED BY LIVER-MICROSOMES AND PERFUSED-RAT-LIVER
AKERBOOM, TPM
SIES, H
ZIEGLER, DM
[J]. ARCHIVES OF BIOCHEMISTRY AND BIOPHYSICS, 1995, 316 (01) : 220 - 226
[2] Alberto E. E., 2011, SELENIUM TELLURIUM C
[3] Catalytic Application of Selenium and Tellurium Compounds as Glutathione Peroxidase Enzyme Mimetics
Alberto, Eduardo E.
do Nascimento, Vanessa
Braga, Antonio L.
[J]. JOURNAL OF THE BRAZILIAN CHEMICAL SOCIETY, 2010, 21 (11) : 2032 - 2041
[4] Efficient Synthesis of Modular Amino Acid Derivatives Containing Selenium with Pronounced GPx-Like Activity
Alberto, Eduardo E.
Soares, Letiere C.
Sudati, Jessie H.
Borges, Antonio C. A.
Rocha, Joao B. T.
Braga, Antonio. L.
[J]. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2009, 2009 (25) : 4211 - 4214
[5] Rapid and Quantitative Disulfide Bond Formation for a Polypeptide Chain Using a Cyclic Selenoxide Reagent in an Aqueous Medium
Arai, Kenta
Dedachi, Kenichi
Iwaoka, Michio
[J]. CHEMISTRY-A EUROPEAN JOURNAL, 2011, 17 (02) : 481 - 485
[6] Reduction of methionine selenoxide to selenomethionine by glutathione
Assmann, A
Briviba, K
Sies, H
[J]. ARCHIVES OF BIOCHEMISTRY AND BIOPHYSICS, 1998, 349 (01) : 201 - 203
[7] Aromatic derivatives and tellurium analogues of cyclic seleninate esters and spirodioxyselenuranes that act as glutathione peroxidase mimetics
Back, TG
Kuzma, DA
Parvez, M
[J]. JOURNAL OF ORGANIC CHEMISTRY, 2005, 70 (23) : 9230 - 9236
[8] The exceptional glutathione peroxidase-like activity of di(3-hydroxypropyl) selenide and the unexpected role of a novel spirodioxaselenanonane intermediate in the catalytic cycle
Back, TG
Moussa, Z
Parvez, M
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (10) : 1268 - 1270
[9] Diselenides and allyl selenides as glutathione peroxidase mimetics.: Remarkable activity of cyclic seleninates produced in situ by the oxidation of allyl ω-hydroxyalkyl selenides
Back, TG
Moussa, Z
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (44) : 13455 - 13460
[10] Remarkable activity of a novel cyclic seleninate ester as a glutathione peroxidase mimetic and its facile in situ generation from allyl 3-hydroxypropyl selenide
Back, TG
Moussa, Z
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (41) : 12104 - 12105

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