Synthesis of nickeliron hydrogenase in cupriavidus. Protonation of nickel iron hydrogenase models proceeds after isomerization at nickel. Mixedvalence nickeliron dithiolate models of the nifehydrogenase active site. Recently, a structural and functional nifeh2ase mimic nat. Nife hydrogenase, the enzyme of which catalyzes the reversible oxidation of molecular hydrogen to protons and electrons, contains a unique heterodinuclear thiolatebridged ni. Hydrogenases from methanogenic archaea, nickel, a novel. Nickel and iron incorporation into soluble hydrogenase of. Jul 18, 2016 nife hydrogenases are enzymes containing nickel and iron centres that catalyse hydrogen evolution with performances that rival those of platinum catalysts. Synthesis of the hydrogenase is nickeldependen t, and is stimulated by carbon dioxide as electron sink during co 2fixation. Dithiolato and diselenolatobridged nickeliron biomimetics. They are generally composed of a small subunit of about 30 kda and a large subunit of 60 kda. Synthesis of nickeliron hydrogenase in cupriavidus metallidurans is controlled by metaldependent silencing and unsilencing of genomic islands martin herzberg, a marcel schuttau, a matthias reimers, a cornelia gro. Nife hydrogenase is the most common type among the currently known hydrogenases, and its active site consists of an organometallic feni complex supported by cysteinyl thiolate ligands.
Glucose is degraded through a classical embdenmeyerhof pathway, and both nadh and reduced ferredoxin are generated. Synthetic analogues of the nickeliron hydrogenase family of. Nickeliron dithiolato hydrides relevant to the nife. Nife hydrogenase is a type of hydrogenase, which is an oxidative enzyme that reversibly convert molecular hydrogen in prokaryotes including bacteria and archaea. As the names imply, all of them use metal ions in their reactions.
Insights into fefehydrogenase structure, mechanism, and. The xray structure of the heterodimeric nife hydrogenase from desulfovibrio gigas, the enzyme responsible for the metabolism of molecular hydrogen, has been solved at 2. The hydrogenase nife center exhibits a range of epractive and eprsilent states, and the electronic structures of these forms have also been controversial. Structure and function of nife hydrogenases the journal. Hydrogen uptake 1 is coupled to the reduction of electron acceptors such as oxygen, nitrate, sulfate, carbon dioxide co. One of these enzymes acts as a chaperone, bonding to a key cysteine in the active site and wrenching the protein open to make it accessible to the other enzymes. Nifesehydrogenase chemistry american chemical society. The nickel iron hydrogenase enzymes efficiently and reversibly interconvert protons, electrons, and dihydrogen. Nifehydrogenase activity journal of biological chemistry. The first structure of a nifese hydrogenase showed the protein in the reduced state, which revealed an open coordination site between nickel and iron presumably containing a hydride ligand, which is invisible in crystallography as in the standard hydrogenases.
Mechanism of hydrogen activation by nife hydrogenases. A subclass of nickeliron hydrogenases, nifese contains selenium in the form of a. Pdf mixedvalence nickeliron dithiolate models of the. Representation of the activesite structures of anife and nifese hydrogenase in areduced, active nisi state and the corresponding syn. Jun 03, 2008 2005 dithiolatobridged dinuclear ironnickel complexes feco 2 cn 2. Synthetic models for nickeliron hydrogenase featuring redox. Bunsho kure, mikie sano, takayuki nakajima, and tomoaki tanase. Reduction of technetiumvii by desulfovibrio fructosovorans. The shelf life of the nanoparticles was tested over a 3week. On the active sites of the nife hydrogenase from desulfovibrio gigus. Other types of heterodimeric o 2tolerant nife hydrogenases have recently been characterized from several bacteria, such as the actinobacterialtype, the regulatory h 2sensing type from ralstonia, the hyd2 type from citrobacter sp. Morphology core shell and alloy and metal molar ratio ni 2 fe 10, ni 5 fe 10, and ni 10 fe 10 were tested as key nanoparticle properties. In this paper, i will focus on the metal center of nickel iron hydrogenase. Protonation of nickeliron hydrogenase models proceeds after isomerization at nickel.
At the top is a nickeliron hydrogenase pdb entry 2frv, in the center is an ironiron hydrogenase pdb entry 1feh, and at the bottom is an iron hydrogenase pdb entry 3dag and 3f47. Crystal structure of the nickeliron hydrogenase from. Synthesis of the hydrogenase is nickel dependen t, and is stimulated by carbon dioxide as electron sink during co 2fixation. Cornelia welte, uwe deppenmeier, in methods in enzymology, 2011. Nickeliron hydrogenase 5 43 5 nickeliron hydrogenase by richard cammack, victor i. Request pdf potential hydrogen bottleneck in nickeliron hydrogenase the role of twostate reactivity at the enzyme active site with respect to binding of molecular h2 for the high and low. Protonation of nickeliron hydrogenase models proceeds after. Production and application of a soluble hydrogenase from. The active site of nife hydrogenases, which is located in the large subunit of the enzyme, consists of a binuclear metal cluster formed by ni and fe see fig. Hydrogenases are metalloenzymes with an active site that contains, under a reducing atmosphere, iron, nickel and sulfur as well as diatomic. Fefehydrogenases or one iron and one nickel center in. Reduction of technetiumvii bydesulfovibrio fructosovorans.
Journal of the american chemical society 2014, 6 35, 1238512395. Plasmaemission metal analysis detected in all three fractions the presence of iron plus nickel and selenium in. Nife hydrogenases are organometallic enzymes containing nickel and iron centers that catalyze hydrogen evolution with performances that. The oxidation of these electron carriers must be coupled to h2 production, but the mechanism by which this occurs is unknown. Under conditions of nickel limitation, some methanogens synthesize a nickel independent fe hydrogenase instead of f 420reducing nife hydrogenase and by that reduce their nickel requirement. These series of genetic and biochemical approaches demonstrated that the periplasmic nickeliron hydrogenase of sulfatereducing bacteria functions as a tcvii reductase. Jones, graham joseph 2018 synthetic analogues of the nickeliron hydrogenase family of metalloenzymes. Nickel ledge soft xray spectroscopy of nickel iron.
S77 23, 24, and also nifese hydrogenase from desulfovibrio vulgaris miyazaki f dvmf 25, 26. Structurefunction relationships among the nickelcontaining. The purified nickel iron hydrogenase performed tcvii reduction and precipitation at high rates. Nickelcentred proton reduction catalysis in a model of nife. Reported here are synthetic models for nickel iron hydrogenase featuring redoxactive auxiliaries that mimic the iron sulfur cofactors. May 04, 2009 protonation of nickeliron hydrogenase models proceeds after isomerization at nickel. Removal of synthetic azo dye using bimetallic nickeliron. Discovery of diatomic ligands, co and cnin nife active site. At the top is a nickel iron hydrogenase pdb entry 2frv, in the center is an iron iron hydrogenase pdb entry 1feh, and at the bottom is an iron hydrogenase pdb entry 3dag and 3f47.
The active site, which appears to contain, besides nickel, a second metal ion, is buried in the 60k subunit. A combined epr and mossbauer study indicates that the majority of the iron atoms are bound in the form of iron sulfur clusters. Nickelironsulfurseleniumcontaining hydrogenases from. For instance, the nickeliron hydrogenases require at least seven enzymes, powered by gtp and atp, to build their active sites. Request pdf nickeliron dithiolato hydrides relevant to the nifehydrogenase active site the ferrous dithiolato carbonyl fes2c3h6co2dppe 1 condenses with nicl2dppe to. Nickeliron hydrogenase enzymes nifeh 2 ases catalyze the transfer of electrons from hydrogen gas h 2 to a redox partner 15. Fefe and nifehydrogenase diversity, mechanism, and. This activation of h 2 for the release of electrons andor hydride ions has tremendous potential applications from energy generation to industrial synthesis, and so h 2 ases are currently the focus of much research across many disciplines. Hydrogenases catalyze the reversible oxidation of hydrogen and allow bacteria to use hydrogen as an energy source for their growth. Mixedvalence nickeliron dithiolate models of the nife hydrogenase active site. These redox proteins feature iron sulfur clusters that relay electrons to and from their active sites. The nife hydrogenase h2ase has been characterized in the nir state with a hydride bridging between fe and ni but displaced toward the ni. Divided into three classes based on their metal content, the fe, fefe, and nifehydrogenases are evolutionarily unrelated but share similar. A hydrogenase is an enzyme that catalyses the reversible oxidation of molecular hydrogen h 2, as shown below.
Oxygentolerant, oxygensensitive, and other nonstandard nife hydrogenases employ very similar active sites for catalysis. Request pdf mechanism of hydrogen activation by nife hydrogenases the active site of nife hydrogenases contains a strictly conserved arginine that. Several types of nickeliron hydrogenases were described in methanogenic archaea vignais et al. Hydrogenases and alternative energy strategies wiley online. The crystal structure of the nickel iron hydrogenases isolated from desulfovibrio gigas was determined by volbeda and his colleagues in 1995. The hydrogenase from desulfovibrio baculatus dsm 1743 was purified from each of three different fractions. The nife hydrogenase isolated from desulfouibrio gigas was poised. Pdf thesis as examined repository staff only until 19 july 2020.
Hydrogen production from model complexes of the fefe and. Claude hatchikian introduction the nife hydrogenases are the most commonly found hydrogenases in sulfatereducing bacteria. Hydrogenases can be divided into two major superfamilies. Bimetallic nanoparticles comprised of iron fe and nickel ni were investigated for the removal of an azo dye contaminant in water. Reduction of technetiumvii bydesulfovibrio fructosovorans is mediated by the nickeliron hydrogenase article pdf available in applied and environmental microbiology 6710. Among them is the f 420 nonreducing hydrogenase, which is composed of a small electron transfer subunit and a large catalytic subunit harboring a nickeliron center. A functional nifehydrogenase mimic that catalyzes electron. The fe hydrogenase harbors a unique iron guanylylpyridinol cofactor fegp cofactor, in which a lowspin iron is ligated by two co, one coch 2.
The hydrogenase gene cluster of rhizobium leguminosarum bv. Journal of the american chemical society, 635, 1238512395. Incorporation of both metals into the enzyme required protein synthesis as evident from studies inhibiting translation by chloramphenicol. The ironhydrogenase of thermotoga maritima utilizes. Nickel iron hydrogenase an overview sciencedirect topics.
Fe complex in which the iron center is coordinated by co and cn. These series of genetic and biochemical approaches demonstrated that the periplasmic nickel iron hydrogenase of sulfatereducing bacteria functions as a tcvii reductase. Synthetic active site model of the nifese hydrogenase. Since nickel incorporation was identical to that of iron, linkage of nickel to the soluble hydrogenase may be similar to that of iron. Understanding the copious iron is in form of fes clusters, 1950s. In nearly all of the synthetic nir models reported so far, the hydride ligand is either displaced toward fe, or terminally bound to fe. Dithiolato and diselenolatobridged nickeliron biomimetics for the active site of nifehydrogenases licheng song, yu lu, liang zhu, and qianli li department of chemistry, state key laboratory of elementoorganic chemistry and collaborative innovation center of chemical science and engineering tianjin.
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