Photoenzymatic Hydroxylation of Ethylbenzene Catalyzed by Unspecific Peroxygenase: Origin of Enzyme Inactivation and the Impact of Light Intensity and Temperature

被引：34

作者：

Burek, Bastien O. ^{[1
,2
,3
]}

de Boer, Sabrina R. ^{[1
,2
]}

Tieves, Florian ^{[4
]}

Zhang, Wuyuan ^{[4
]}

van Schie, Morten ^{[4
]}

Bormann, Sebastian ^{[1
,2
]}

Alcalde, Miguel ^{[5
]}

Holtmann, Dirk ^{[1
,2
]}

Hollmann, Frank ^{[4
]}

Bahnemann, Detlef W. ^{[3
,6
]}

Bloh, Jonathan Z. ^{[1
,2
]}

机构：

[1] DECHEMA Forsch Inst, Chem Technol Grp, Theodor Heuss Allee 25, D-60486 Frankfurt, Germany

[2] DECHEMA Forsch Inst, Ind Biotechnol Grp, Theodor Heuss Allee 25, D-60486 Frankfurt, Germany

[3] Leibniz Univ Hannover, Inst Tech Chem, Callinstr 3, D-30167 Hannover, Germany

[4] Delft Univ Technol, Dept Biotechnol, Van der Maasweg 9, NL-2629 HZ Delft, Netherlands

[5] CSIC, Dept Biocatalysis, Inst Catalysis, Madrid 28049, Spain

[6] St Petersburg State Univ, Lab Photoact Nanocomposite Mat, Ulyanovskaya Str 1, St Petersburg 198504, Russia

来源：

CHEMCATCHEM | 2019年 / 11卷 / 13期

基金：

欧洲研究理事会;

关键词：

peroxygenases; photocatalysis; hydrogen peroxide; light intensity; enzyme inactivation; HYDROGEN-PEROXIDE; OXYFUNCTIONALIZATION REACTIONS; ELECTROENZYMATIC SYNTHESIS; MOLECULAR-OXYGEN; WATER OXIDATION; EPOXIDATION; MECHANISM; ALCOHOLS; SYSTEM; H2O2;

D O I：

10.1002/cctc.201900610

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Photoenzymatic cascades can be used for selective oxygenation of C-H-Bonds under mild conditions circumventing the hydrogen peroxide mediated peroxygenase inactivation via in situ H2O2 generation. Here, we report the "on demand" production of hydrogen peroxide via methanol assisted reduction of molecular oxygen using UV-illuminated titanium dioxide (Aeroxide P25) combined with the enantioselective hydroxylation of ethylbenzene to (R)-1-phenylethanole catalyzed by the Unspecific Peroxygenase from Agrocybe Aegerita. For the application of the system it is important to understand the influence of the reaction parameters to be able to optimize the system. Therefore, we systematically investigated product formation and enzyme inactivation as well as ROS formation (H2O2, (OH)-O-. and O-.(2)-) applying different light intensities and temperatures. As a result, Turnover Numbers up to 220 000, photonic efficiencies up to 13.6 % and production rates up to 0.9 mM h(-1) were achieved.

引用

页码：3093 / 3100

页数：8

共 57 条

[1] Exploring the catalase activity of unspecific peroxygenases and the mechanism of peroxide-dependent heme destruction [J].