A kinetic and thermodynamic understanding of O2 tolerance in [NiFe]-hydrogenases

被引:124
作者
Cracknell, James A. [1 ]
Wait, Annemarie F. [1 ]
Lenz, Oliver [2 ]
Friedrich, Baerbel [2 ]
Armstrong, Fraser A. [1 ]
机构
[1] Univ Oxford, Inorgan Chem Lab, Dept Chem, Oxford OX1 3QR, England
[2] Humboldt Univ, Inst Biol Mikrobiol, D-10115 Berlin, Germany
基金
英国工程与自然科学研究理事会; 英国生物技术与生命科学研究理事会;
关键词
electrochemistry; hydrogen; hydrogenase; oxygen tolerance; Ralstonia eutropha; RALSTONIA-EUTROPHA H16; LOW-LEVEL H-2; NIFE HYDROGENASE; CARBON-MONOXIDE; OXIDATION; MICROORGANISMS; INACTIVATION; VOLTAMMETRY; ACTIVATION; ENZYMES;
D O I
10.1073/pnas.0905959106
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
In biology, rapid oxidation and evolution of H-2 is catalyzed by metalloenzymes known as hydrogenases. These enzymes have unusual active sites, consisting of iron complexed by carbonyl, cyanide, and thiolate ligands, often together with nickel, and are typically inhibited or irreversibly damaged by O-2. The Knallgas bacterium Ralstonia eutropha H16 (Re) uses H-2 as an energy source with O-2 as a terminal electron acceptor, and its membrane-bound uptake [NiFe]-hydrogenase (MBH) is an important example of an "O-2-tolerant'' hydrogenase. The mechanism of O-2 tolerance of Re MBH has been probed by measuring H-2 oxidation activity in the presence of O-2 over a range of potential, pH and temperature, and comparing with the same dependencies for individual processes involved in the attack by O-2 and subsequent reactivation of the active site. Most significantly, O-2 tolerance increases with increasing temperature and decreasing potentials. These trends correlate with the trends observed for reactivation kinetics but not for H-2 affinity or the kinetics of O-2 attack. Clearly, the rate of recovery is a crucial factor. We present a kinetic and thermodynamic model to account for O-2 tolerance in Re MBH that may be more widely applied to other [NiFe]-hydrogenases.
引用
收藏
页码:20681 / 20686
页数:6
相关论文
共 25 条
[1]   Dynamic electrochemical investigations of hydrogen oxidation and production by enzymes and implications for future technology [J].
Armstrong, Fraser A. ;
Belsey, Natalie A. ;
Cracknell, James A. ;
Goldet, Gabrielle ;
Parkin, Alison ;
Reisner, Erwin ;
Vincent, Kylie A. ;
Wait, Annemarie F. .
CHEMICAL SOCIETY REVIEWS, 2009, 38 (01) :36-51
[2]   Hydrogen Production by a Hyperthermophilic Membrane-Bound Hydrogenase in Water-Soluble Nanolipoprotein Particles [J].
Baker, Sarah E. ;
Hopkins, Robert C. ;
Blanchette, Craig D. ;
Walsworth, Vicki L. ;
Sumbad, Rhoda ;
Fischer, Nicholas O. ;
Kuhn, Edward A. ;
Coleman, Matt ;
Chromy, Brett A. ;
Letant, Sonia E. ;
Hoeprich, Paul D. ;
Adams, Michael W. W. ;
Henderson, Paul T. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (22) :7508-+
[3]  
Bard A.J., 2001, ELECTROCHEMICAL METH
[4]   The soluble NAD+-reducing [NiFe]-Hydrogenase from Ralstonia eutropha H16 consists of six subunits and can be specifically activated by NADPH [J].
Burgdorf, T ;
van der Linden, E ;
Bernhard, M ;
Yin, QY ;
Back, JW ;
Hartog, AF ;
Muijsers, AO ;
de Koster, CG ;
Albracht, SPJ ;
Friedrich, B .
JOURNAL OF BACTERIOLOGY, 2005, 187 (09) :3122-3132
[6]   Enzymes as working or inspirational electrocatalysts for fuel cells and electrolysis [J].
Cracknell, James A. ;
Vincent, Kylie A. ;
Armstrong, Fraser A. .
CHEMICAL REVIEWS, 2008, 108 (07) :2439-2461
[7]   Enzymatic oxidation of H2 in atmospheric O2:: The electrochemistry of energy generation from trace H2 by aerobic microorganisms [J].
Cracknell, James A. ;
Vincent, Kylie A. ;
Ludwig, Marcus ;
Lenz, Oliver ;
Friedrich, Baerbel ;
Armstrong, Fraser A. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (02) :424-+
[8]   Enlarging the gas access channel to the active site renders the regulatory hydrogenase HupUV of Rhodobacter capsulatus O2 sensitive without affecting its transductory activity [J].
Duché, O ;
Elsen, S ;
Cournac, L ;
Colbeau, A .
FEBS JOURNAL, 2005, 272 (15) :3899-3908
[9]   Structure/function relationships of [NiFe]- and [FeFe]-hydrogenases [J].
Fontecilla-Camps, Juan C. ;
Volbeda, Anne ;
Cavazza, Christine ;
Nicolet, Yvain .
CHEMICAL REVIEWS, 2007, 107 (10) :4273-4303
[10]   Hydrogen production under aerobic conditions by membrane-bound hydrogenases from Ralstonia species [J].
Goldet, Gabrielle ;
Wait, Annemarie F. ;
Cracknell, James A. ;
Vincent, Kylie A. ;
Ludwig, Marcus ;
Lenz, Oliver ;
Friedrich, Baerbel ;
Armstrong, Fraser A. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (33) :11106-11113