Wiring Photosystem I for Direct Solar Hydrogen Production

被引:125
作者
Lubner, Carolyn E. [1 ]
Grimme, Rebecca [1 ]
Bryant, Donald A. [2 ]
Golbeck, John H. [1 ,2 ]
机构
[1] Penn State Univ, Dept Chem, University Pk, PA 16802 USA
[2] Penn State Univ, Dept Biochem & Mol Biol, University Pk, PA 16802 USA
基金
美国国家科学基金会;
关键词
IRON-SULFUR CLUSTERS; H-2-FORMING METHYLENETETRAHYDROMETHANOPTERIN DEHYDROGENASE; LIGAND 4FE-4S CLUSTER; REACTION-CENTER CORE; CUCUMIS-SATIVUS L; SP; PCC; 6803; F-A; CHARGE SEPARATION; ELECTRON-TRANSFER; ACTIVE-SITE;
D O I
10.1021/bi901704v
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
The generation of H-2 by the use of solar energy is a promising way to supply humankind's energy needs while simultaneously mitigating environmental concerns that arise due to climate change. The challenge is to find a way to connect a photochemical module that harnesses the sun's energy to a catalytic module that generates H-2 with high quantum yields and rates. In this review, we describe a technology that employs a.,molecular wire" to connect a terminal [4Fe-4S] cluster of Photosystem I directly to a catalyst, which call be either a Pt nanoparticle or the distal [4Fe-4S] cluster of all [FeFe]- or [NiFe]-hydrogenase enzyme. The keys to connecting these two moieties are surface-located cysteine residues, which serve as ligands to Fe-S clusters and which call be changed through site-specific mutagenesis to glycine residues, and the use of a molecular wire terminated ill sulfhydryl groups to connect the two modules. The sulfhydryl groups at the end of the molecular wire form a direct chemical linkage to a Suitable catalyst or can chemically rescue a [4Fe-4S] cluster, thereby generating a strong coordination bond. Specifically, the molecular Wire call connect the F-B iron-sulfur Cluster of Photosystem I either to a Pt nanoparticle or, by using the same type of genetic modification, to the differentiated iron atom of the distal [4Fe-4S]center dot(Cys)(3)(Gly) cluster of hydrogenase. When electrons are Supplied by a sacrificial donor, this technology forms the cathode of a photochemical half-cell that evolves H-2 when illuminated. If such a device were connected to the anode of a photochemical half-cell that oxidizes water, an in vitro solar energy converter could be realized that generates Only O-2 and H-2 in the light. A similar methodology can be used to connect Photosystem I to other redox proteins that have surface-located [4Fe-4S] clusters. The controlled light-driven production of strong reductants by such systems can be used to produce other biofuels or to provide mechanistic insights into enzymes catalyzing multielectron, proton-coupled reactions.
引用
收藏
页码:404 / 414
页数:11
相关论文
共 70 条
[1]   Functional organization of a plant photosystem I: Evolution of a highly efficient photochemical machine [J].
Amunts, Alexey ;
Nelson, Nathan .
PLANT PHYSIOLOGY AND BIOCHEMISTRY, 2008, 46 (03) :228-237
[2]   Chemical rescue of a site-modified ligand to a [4Fe-4S] cluster in PsaC, a bacterial-like dicluster ferredoxin bound to Photosystem I [J].
Antonkine, Mikhail L. ;
Maes, Estelle M. ;
Czemuszewiez, Roman S. ;
Breitenstein, Christoph ;
Bill, Eckhard ;
Falzone, Christopher J. ;
Balasubramanian, Ramakrishnan ;
Lubner, Carolyn ;
Bryant, Donald A. ;
Golbeck, John H. .
BIOCHIMICA ET BIOPHYSICA ACTA-BIOENERGETICS, 2007, 1767 (06) :712-724
[3]   Properties of the [NiFe]-hydrogenase maturation protein HypD [J].
Blokesch, Melanie ;
Boeck, August .
FEBS LETTERS, 2006, 580 (17) :4065-4068
[4]   Enhanced photocatalytic hydrogen evolution by covalent attachment of plastocyanin to photosystem I [J].
Evans, BR ;
O'Neill, HM ;
Hutchens, SA ;
Bruce, BD ;
Greenbaum, E .
NANO LETTERS, 2004, 4 (10) :1815-1819
[5]  
Fontecilla-Camps JC, 2009, AMINO ACIDS, V37, P22
[6]  
GIBBS M, 1973, P WORKSH BIOS CONV W
[7]  
Golbeck J.H., 2004, ENERGY TRANSDUCTION
[8]  
Golbeck J.H., 1987, Prog. Photosynth. Res., Proc. Int. Congr. Photosynth., 7th, V1, P253
[9]   ISOLATION OF THE INTACT PHOTOSYSTEM-I REACTION CENTER CORE CONTAINING P700 AND IRON-SULFUR CENTER FX [J].
GOLBECK, JH ;
PARRETT, KG ;
MEHARI, T ;
JONES, KL ;
BRAND, JJ .
FEBS LETTERS, 1988, 228 (02) :268-272
[10]   A comparative analysis of the spin state distribution of in vitro and in vivo mutants of PsaC -: A biochemical argument for the sequence of electron transfer in Photosystem I as FX → FA → FB → ferredoxin/flavodoxin [J].
Golbeck, JH .
PHOTOSYNTHESIS RESEARCH, 1999, 61 (02) :107-144