NiFe

Eig. 5. The Widmanstatten pattern ia this poHshed and etched section of the Gibbeon iron meteorite is composed of iatergrown crystals of kamacite and taenite, NiFe phases that differ ia crystal stmcture and Ni content. Ni concentration gradients at crystal boundaries ia this 3-cm-wide sample can be used to estimate the initial cooling rates and corresponding size of the asteroid from which the meteorite was derived. 

The first paper about NiFe layers evaporated under an angle was pubHshed in the early 1960s (40). The films prepared this way are often called obHque-incidence or angle-of-incidence films. It was found that these kinds of films show an anisotropy whose strength depends on the angle of incidence of the atoms (a/ during deposition (Fig. 15). If is between 0 and 65 the anisotropy Hes parallel to the film plane and perpendicular to the incidence plane. 

Hgure 2 XRF spectrum of MnFe/NiFe thin film. 

In multiple-layer thin films, it is possible that some of the elements may be present simultaneously in two or more layers. XRF analysis of this type of film can be complicated and cannot be made solely from their observed intensities. Additional information, such as the compositions or thickness of some of the layers is needed. The amount of addidonal non-XRF information required depends on the complexity of the film. For example, in the analysis of a FeMn/NiFe double-layer film, the additional information needed can be the composition or thickness of either the FeMn or NiFe layer. Using the composition or thickness of one of the film predetermined from a single-layer film deposited under identical condidons, XRF analysis of the FeMn/NiFe film was successfiil. ... 

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NiFe-hydrogenase Bacteria H2 2H + 2e- [FesS4] 2[Fe4S4p- NiFe center -70 59... 

Fig. 1. Proposed electron transport pathway in D. gigas NiFe-hydrogenase. Selected distances are given in angstroms. Modified with permission from Ref. (157).

The spatial arrangement of the Fe-S clusters in D. gigas NiFe-hydrogenase (see Fig. 1) suggests an active role for the [Fe3S4] ° cluster in mediating electron transfer from the NiFe active site to the... 

The multifrequency EPR and Mdssbauer properties of the [FesSJ in C. vinosum NiFe-hydrogenase are particularly interesting since they provide evidence of magnetic interactions with nearby paramagnetic species (151, 154, 155). The magnetically isolated form exhibits a well-resolved, almost axial EPR signal, g = 2.018, 2.016, 2.002, indicative of minimal conformational heterogeneity. However, a com-... 

This review concerns proteins that contain both nickel and iron. Below are listed the three known proteins of this class and the reactions that they catalyze. The active sites of all of these consist of het-erometallic nickel-iron-sulfur (NiFeS) clusters. The terms used will he explained later in the text. 

EPR spectra and g values for the various states of the hydrogenase from Thiocapsa roseopersicina 64) are depicted in Fig. 4. These spectra are representative of those of the other NiFe hydrogenases. 

The biologically uncommon Ni center associated with FeS clusters is a powerful and unique catalytic unity. In this chapter we have reviewed the structural and mechanistic aspects of three NiFeS centers the active site of hydrogenase and Clusters A and C of CODH/ACS. In the former, the association of a Ni center with the most unusual FeCOCN2 unit is a fascinating one. Model chemists, spectroscopists, and crystallographers have joined efforts to try and elucidate the reaction mechanism. Although a consensus is being slowly reached, the exact roles of the different active site components have not yet been fully established. Ni appears to be the catalytic center proper, whereas the unusual Fe center may be specially suited to bind a by-... 

The [NiFe] hydrogenase from D. gigas has been used as a prototype of the [NiFe] hydrogenases. The enzyme is a heterodimer (62 and 26 kDa subunits) and contains four redox active centers one nickel site, one [3Fe-4S], and two [4Fe-4S] clusters, as proven by electron paramagnetic resonance (EPR) and Mosshauer spectroscopic studies (174). The enzyme has been isolated with different isotopic enrichments [6 Ni (I = I), = Ni (I = 0), Fe (I = 0), and Fe (I = )] and studied after reaction with H and D. Isotopic substitutions are valuable tools for spectroscopic assignments and catalytic studies (165, 166, 175). 

Most of the as-isolated [NiFe] hydrogenases are inactive, and the nickel center exhibits an intense rhombic EPR signal termed Ni-A (g = 2.31, 2.26, and 2.02) with variable amounts of a second nickel species, named Ni-B (g = 2.33, 2.16, and 2.02), with slightly different... 

Fig. 8. The structure of D. gigas hydrogenase showing the novel heterodinuclear [NiFe] site, the three iron-sulfur clusters, and the tracing of the polypeptide chain...

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