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.     

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     

Gas transport through homogeneous and asymmetric polyethersulfone membranes

Both homogeneous and asymmetric polyethersulfone (PES) membranes were prepared by solvent casting. The sorption and permeation behavior of CO₂, O₂, and N₂ using these two kinds of cast PES membranes and commercially available homogeneous PES film was investigated to extract the pressure dependence of gas permeability and the permselectivity for CO₂ relative to N₂, and to confirm the validity of the working assumption that a skin layer in an asymmetric membrane can be essentially replaced by a thick homogeneous dense membrane. The pressure dependence of the mean permeability coefficient to CO₂ in homogeneous membranes obeys the dual-mode mobility model. The ideal separation factor for CO₂ relative to N₂ at an upstream pressure of 0.5 MPa attains ca. 40, while the permeability to CO₂ is about 2.7 Barrer at the same upstream pressure. The same separation factor in asymmetric membranes amounts to 35. The diffusion behavior for the skin layer in an asymmetric membrane with a thin skin layer can be simulated approximately by that in a homogeneous dense membrane. © 1993 John Wiley & Sons, Inc.     

A testbench for the nested dipole hypothesis of Kosterlitz and Thouless

We consider the two-dimensional one-component plasma without a background and confined to a half-plane near a metal wall. The particles are also subjected to an external potential acting perpendicular to the wall with an inverse-power-law Boltzmann factor. The model has a known solvable isotherm which exhibits a Kosterlitz-Thouless-type transition from a conductive to an insulator phase as the power law is varied. This allows predictions of theoretical methods of analyzing the Kosterlitz-Thouless transition to be compared with the exact solution. In particular, we calculate the asymptotic density profile by resumming its low-fugacity expansion near the zero-density critical coupling in the insulator phase, and solving a mean-field equation deduced from the first BGY equation. Agreement with the exact solution is obtained. As the former calculation makes essential use of the nested dipole hypothesis of Kosterlitz and Thouless, the validity of this hypothesis is explicitly verified.     

Enumeration of Full Graphs: Onset of the Asymptotic Region

A full graph on n vertices, as defined by Fulkerson, is a representation of the intersection and containment relations among a system of n sets. It has an undirected edge between vertices representing intersecting sets and a directed edge from a to b if the corresponding set A contains B;. Kleitman, Lasaga, and Cowen gave a unified argument to show that asymptotically, almost all full graphs can be obtained by taking an arbitrary undirected graph on the n vertices, distinguishing a clique in this graph, which need not be maximal, and then adding directed edges going out from each vertex in the clique to all vertices to which there is not already an existing undirected edge. Call graphs of this type members of the dominant class. This article obtains the first upper and lower bounds on how large n has to be, so that the asymptotic behavior is indeed observed. It is shown that when n > 170, the dominant class predominates, while when n < 17, the full graphs in the dominant class compose less than half of the total number of realizable full graphs on n vertices.     

Critical thickness and stress relaxation in YBaCuO (123) strained epitaxial layers and YBaCuO based strained superlattices

An energy model has been used to calculate the critical thickness h _c of YBaCuO thin films and YBaCuO based superlattices within an isotropic or anisotropic approximation. The critical thickness of single layers calculated from the anisotropic model (16 nm) is in good agreement with the previously published experimental values which are spread out from 4 to 20 nm. In the case of superlattices, relaxation appears to be governed by the critical thickness of the elementary sub-layers and is then better evaluated through the calculation performed for YBaCuO single layers. XRD measurements on YBa₂Cu₃O₇/PrBa₂Cu_3?xGa_xO₇ superlattices grown on {100{ SrTiO₃ have evidenced a tetragonal stress in the YBaCuO ab plane which remains expanded when the YBaCuO elementary layer thickness is lower than 4.8 nm (4 YBaCuO cells). However the critical temperature of the shortest period superlattices is only slightly affected by this expanded stress in contrast to the effect of an elastic stress externally applied along the ab plane of YBaCuO thin films.     

Surface characterization of fluorinated polymers (PTFE, PVDF, PFA) for use in ultratrace analysis

Surface characterization of new unused PTFE, PFA and PVDF labware has been carried out by light microscopy, scanning electron microscopy, profilometry and atomic force microscopy. It has been found that in spite of higher micro-roughness, PFA exhibits the lowest nano-roughness and hence seems best suited as vessel material for relatively mild pressureless chemical operations for sample preparation of ultrapure substances, as container material for storage of ultrapure liquids, and for transport of such liquids, e.g., from the producer in the chemical to the end user in the microelectronics industry. This suitability refers only to the surface quality of the investigated materials. PTFE-surfaces, due to the sintering process of production, exhibit the most unfavourable surface quality of the investigated fluorinated polymers.