Structure of cytochrome a3-Cua3 couple in cytochrome c oxidase as revealed by nitric oxide binding studies

The addition of NO to oxidized cytochrome c oxidase (ferrocytochrome c:oxygen oxidoreductase, EC 1.9.3.1) causes the appearance of a high-spin heme electron paramagnetic resonance (EPR) signal due to cytochrome a3. This suggests that NO coordinates to Cu{a3}+2 and breaks the antiferromagnetic couple by forming a cytochrome a3+3-Cu{a3}+2-NO complex. The intensity of the high-spin cytochrome a3 signal depends on the method of preparation of the enzyme and maximally accounts for 58% of one heme. The effect of N3- on the cytochrome a3+3-Cu{a3}+2-NO complex is to reduce cytochrome a3 to the ferrous state, and this is followed by formation of a new complex that exhibits EPR signals characteristic of a triplet species. On the basis of optical and EPR results, a NO bridge between cytochrome a3+2 and Cu{a3}+2 is proposed-i.e., cytochrome a3+2-NO-Cu{a3}+2. The half-field transition observed at g = 4.34 in the EPR spectrum of this triplet species exhibits resolved copper hyperfine splittings with |A{}| = 0.020 cm-1, indicating that the Cu{a3}+2 in the cytochrome a3+2-NO-Cu{a3}+2 complex is similar to a type 2 copper site

Understanding the Impact of Open-Framework Conglomerates on Water-Oil Displacements: Victor Interval of the Ivishak Reservoir, Prudhoe Bay Field, Alaska

The Victor Unit of the Ivishak Formation in the Prudhoe Bay Oilfield is characterized by high net-to-gross fluvial sandstones and conglomerates. The highest permeability is found within sets of cross-strata of open-framework conglomerate (OFC). They are preserved within unit bar deposits and assemblages of unit bar deposits within compound (braid) bar deposits. They are thief zones limiting enhanced oil recovery. We incorporate recent research that has quantified important attributes of their sedimentary architecture within preserved deposits. We use high-resolution models to demonstrate the fundamental aspects of their control on oil production rate, water breakthrough time, and spatial and temporal distribution of residual oil saturation. We found that when the pressure gradient is oriented perpendicular to the paleoflow direction, the total oil production and the water breakthrough time are larger, and remaining oil saturation is smaller, than when it is oriented parallel to paleoflow. The pressure difference between production and injection wells does not affect sweep efficiency, although the spatial distribution of oil remaining in the reservoir critically depends on this value. Oil sweep efficiency decreases slightly with increase in the proportion of OFC cross-strata. Whether or not clusters of connected OFC span the domain does not visibly affect sweep efficiency.Comment: 27 pages including 14 figure

Possible effects of tilt order on phase transitions of a fixed connectivity surface model

We study the phase structure of a phantom tethered surface model shedding light on the internal degrees of freedom (IDOF), which correspond to the three-dimensional rod like structure of the lipid molecules. The so-called tilt order is assumed as IDOF on the surface model. The model is defined by combining the conventional spherical surface model and the XY model, which describes not only the interaction between lipids but also the interaction between the lipids and the surface. The interaction strength between IDOF and the surface varies depending on the interaction strength between the variables of IDOF. We know that the model without IDOF undergoes a first-order transition of surface fluctuations and a first-order collapsing transition. We observe in this paper that the order of the surface fluctuation transition changes from first-order to second-order and to higher-order with increasing strength of the interaction between IDOF variables. On the contrary, the order of collapsing transition remains first-order and is not influenced by the presence of IDOF.Comment: 20 pages, 14 figure

My Private Cloud Overview: A Trust, Privacy and Security Infrastructure for the Cloud

Based on the assumption that cloud providers can be trusted (to a certain extent) we define a trust, security and privacy preserving infrastructure that relies on trusted cloud providers to operate properly. Working in tandem with legal agreements, our open source software supports: trust and reputation management, sticky policies with fine grained access controls, privacy preserving delegation of authority, federated identity management, different levels of assurance and configurable audit trails. Armed with these tools, cloud service providers are then able to offer a reliable privacy preserving infrastructure-as-a-service to their clients

Magnetic Instability in Strongly Correlated Superconductors

Recently a new phenomenological Hamiltonian has been proposed to describe the superconducting cuprates. This so-called Gossamer Hamiltonian is an apt model for a superconductor with strong on-site Coulomb repulsion betweenthe electrons. It is shown that as one approaches half-filling the Gossamer superconductor, and hence the superconducting state, with strong repulsion is unstable toward an antiferromagnetic insulator an can undergo a quantum phase transition to such an insulator if one increases the on-site Coulomb repulsion

Ab initio investigation of intermolecular interactions in solid benzene

A computational strategy for the evaluation of the crystal lattice constants and cohesive energy of the weakly bound molecular solids is proposed. The strategy is based on the high level ab initio coupled-cluster determination of the pairwise additive contribution to the interaction energy. The zero-point-energy correction and non-additive contributions to the interaction energy are treated using density functional methods. The experimental crystal lattice constants of the solid benzene are reproduced, and the value of 480 meV/molecule is calculated for its cohesive energy

Two-Stage Rotational Disordering of a Molecular Crystal Surface: C60

We propose a two-stage mechanism for the rotational surface disordering phase transition of a molecular crystal, as realized in C$_{60}$ fullerite. Our study, based on Monte Carlo simulations, uncovers the existence of a new intermediate regime, between a low temperature ordered $(2 \times 2)$ state, and a high temperature $(1 \times 1)$ disordered phase. In the intermediate regime there is partial disorder, strongest for a subset of particularly frustrated surface molecules. These concepts and calculations provide a coherent understanding of experimental observations, with possible extension to other molecular crystal surfaces.Comment: 4 pages, 2 figure

Electron Spin Relaxation of Cu_A and Cytochrome a in Cytochrome c Oxidase. Comparison to heme, copper, and sulfur radical complexes

The method of continuous saturation has been used to measure the electron spin relaxation parameter T_(1)T_(2) at temperatures between 10 and 50 K for a variety of S = 1/2 species including: Cu_A and cytochrome a of cytochrome c oxidase, the type 1 copper in several blue copper proteins, the type 2 copper in laccase, inorganic Cu(II) complexes, sulfur radicals, and low spin heme proteins. The temperature dependence and the magnitude of T_(1)T_(2) for all of the species examined are accounted for by assuming that the Van Vleck Raman process dominates the electron spin-lattice relaxation. Over the entire temperature range examined, the relaxation of the type 1 coppers in six to seven times faster than that of type 2 copper, inorganic copper, and sulfur radicals, in spite of the similar g-anisotropies of these species. This result may indicate that the coupling of the phonon bath to the spin center is more effective in type 1 coppers than in the other complexes studied. The relaxation of Cu_A of cytochrome oxidase exhibits an unusual temperature dependence relative to the other copper complexes studied, suggesting that the protein environment of this center is different from that of the other copper centers studied and/or that Cu_A is influenced by a magnetic dipolar interaction with another, faster-relaxing paramagnetic site in the enzyme. A comparison of the saturation characteristics of the Cu_A EPR signal in native and partially reduced CO complexes of the enzyme also suggests the existence of such an interaction. The implications of these results with respect to the disposition of the metal centers in cytochrome oxidase are discusse

Highly accurate calculations of the rotationally excited bound states in three-body systems

An effective optimization strategy has been developed to construct highly accurate bound state wave functions in various three-body systems. Our procedure appears to be very effective for computations of weakly bound states and various excited states, including rotationally excited states, i.e. states with $L \ge 1$. The efficiency of our procedure is illustrated by computations of the excited $P^{*}(L = 1)-$states in the $dd\mu, dt\mu$ and $tt\mu$ muonic molecular ions, $P(L = 1)-$states in the non-symmetric $pd\mu, pt\mu$ and $dt\mu$ ions and $2^{1}P(L = 1)-$ and $2^{3}P(L = 1)-$states in He atom(s)

Phase transitions of an intrinsic curvature model on dynamically triangulated spherical surfaces with point boundaries

An intrinsic curvature model is investigated using the canonical Monte Carlo simulations on dynamically triangulated spherical surfaces of size upto N=4842 with two fixed-vertices separated by the distance 2L. We found a first-order transition at finite curvature coefficient \alpha, and moreover that the order of the transition remains unchanged even when L is enlarged such that the surfaces become sufficiently oblong. This is in sharp contrast to the known results of the same model on tethered surfaces, where the transition weakens to a second-order one as L is increased. The phase transition of the model in this paper separates the smooth phase from the crumpled phase. The surfaces become string-like between two point-boundaries in the crumpled phase. On the contrary, we can see a spherical lump on the oblong surfaces in the smooth phase. The string tension was calculated and was found to have a jump at the transition point. The value of \sigma is independent of L in the smooth phase, while it increases with increasing L in the crumpled phase. This behavior of \sigma is consistent with the observed scaling relation \sigma \sim (2L/N)^\nu, where \nu\simeq 0 in the smooth phase, and \nu=0.93\pm 0.14 in the crumpled phase. We should note that a possibility of a continuous transition is not completely eliminated.Comment: 15 pages with 10 figure