Investigation by EPR and ENDOR spectroscopy of the novel 4Fe ferredoxin fromPyrococcus furiosus

The hyperthermophilic archaeonPyrococcus furiosus contains a four-Fe ferredoxin (Pf- Fd) that differs from most other 4Fe-Fd’s in that its [Fe₄S₄] cluster is anchored to protein by only three cysteinyl residues.Pf- Fd also is of interest because in its reduced form, [Fe₄S₄]⁺, the cluster exhibits bothS = 1/2 andS = 3/2 spin states. Addition of excess cyanide ion converts the cluster exclusively to anS = 1/2 state (g₁ = 2.09, g₂ = 1.95, g₃ = 1.92), however dialysis restores the EPR signal of native reduced protein indicating that the cluster is not irreversibly altered by cyanide. Both the native protein and protein in the presence of excess cyanide ion (Pf- Fd 4Fe-CN) were investigated here using the techniques of electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy. In particular,Pf- Fd 4Fe-CN was investigated using¹³CN^? and C¹⁵N^? ligands.¹³C and¹⁵N ENDOR indicated that a single cyanide ion bound directly, with the cluster showing an unusually small contact interaction (a_iso(¹³C)～ ?3 MHz, a_iso(¹⁵N) ～ 0). This is in contrast to cyanide bound to monomeric low-spin Fe(III)-containing proteins such as transferrin and myoglobin, for which the¹³C hyperfine coupling has a large isotropic component (a_iso(¹³C) ≈ ?30 MHz). This small contact interaction is not due to low spin density of Fe, as⁵⁷Fe ENDOR of the singly and triply labeledPf- Fd 4FeCN isotopologs, [⁵⁷FeFe₃S₄]⁺ and [Fe⁵⁷Fe₃S₄]⁺, show hyperfine coupling characteristic for [Fe₄S₄]⁺ clusters, particularly for the Fe to which cyanide binds. Thus, the low spin density on¹³C is not due to low spin density on the Fe ion to which it binds. Further theoretical work is needed to explain the contrast between the strong electronic effect of cyanide ion binding with the low spin density on the ligand.     

Gamma radiation effects on an amine antioxidant added in an ethylene-propylene copolymer

The aim of this work was to compare the gamma radiation induced effects on samples of an ethylene-propylene copolymer antioxidant free with samples loaded with an antioxidant characterised by the presence of an -NH functional group. The employed techniques were Electron Spin Resonance spectroscopy (ESR) and High Performance Liquid Chromatography (HPLC). Stable radicals R---NO° due to the interaction of free radicals produced in the irradiated polymer with the antioxidant have been observed by ESR at room temperature. The time evolution of the ESR signals following the irradiation was examined at different doses. The amount of antioxidant not involved in the oxidation reactions has been determined using HPLC.     

Radiative characteristics of pulsed power driven Z-pinch aluminumplasmas

In this paper, we study the dynamics of a massive aluminum Z-pinch plasma load and evaluate its performance as a soft X-ray radiator. A radiation hydrodynamic model self-consistently driven by a circuit describes the dynamics. Comparisons are made for the K- and L-shell soft X-ray emission as a function of the ionization dynamic model. The ionization dynamic models are represented by: 1) a time-dependent nonequilibrium (NEQ) model, 2) a collisional radiative equilibrium (CRE) model, and 3) a local thermodynamic equilibrium (LTE) model. For all three scenarios the radiation is treated 1) in the free streaming optically thin approximation where the plasma is treated as a volume emitter and 2) in the optically thick regime where the opacity for the lines and continuum is self-consistently calculated online and the radiation is transported through the plasma. Each simulation is carried out independently to determine the sensitivity of the implosion dynamics to the ionization and radiation model, i.e., how the ionization dynamic model affects the radiative yield and emission spectra. Results are presented for the L- and K-shell radiation yields and emission spectra as a function of photon energy from 10 eV to 10 keV. Also, departure coefficients from LTE are presented for selected levels and ionization stages     

Decisive Role of Symmetry in Structures of Three-Body Systems

A three-body system of identical particles is considered in order to demonstrate that the quantum-mechanical symmetry plays a decisive role in determining microscopic structures. Received March 14, 1994; revised July 29, 1994; accepted for publication October 19, 1994     

Cylindrical spike model for the formation of diamondlike thin films by ion deposition

T /n_S of n_T rearrangements and n_S atoms in the spike volume as the crucial parameter characterizing the ability of a given ion–target combination to achieve complete rearrangement of the spike volume. n_T/n_S>1 is the optimum condition for diamondlike film growth. For aC films the ion energy dependence of n_T/n_S agrees well with the measured sp³ bond fraction. For Ar⁺-ion-assisted deposition of aC we find n_T/n_S>1 above 50 eV with no pronounced ion energy dependence. Furthermore, our model predicts optimum conditions for the formation of cubic boron nitride between 50 eV and 3 keV. Accepted: 14 October 1997     

Quasiparticle bandstructures of covalent semiconductors and their surfaces

The exchange-correlation self-energies and quasiparticle shifts are calculated for band states of covalent materials (diamond, silicon) and their (001) 2×1 surface in order to solve the bulk and surface band-gap problem of the LDA. The screening properties are described by a model dielectric function taking into account the spatial nonlocality in the surface case assuming specular electron reflection. The wave functions are expanded in terms of localized orbitals. The quasiparticle bandstructures obtained are in reasonable agreement with experimental results.