Potential energy surface and moleculardynamics of MbNO: existence of an unsuspected FeON minimum

Ligands such as CO, O2, or NO are involved in the biological function of myoglobin. Here we investigate the energetics and dynamics of NO interacting with the Fe(II) heme group in native myoglobin using ab initio and molecular dynamics simulations. At the global minimum of the ab initio potential energy surface (PES), the binding energy of 23.4 kcal/mol and the Fe-NO structure compare well with the experimental results. Interestingly, the PES is found to exhibit two minima: There exists a metastable, linear Fe-O-N minimum in addition to the known, bent Fe-N-O global minimum conformation. Moreover, the T-shaped configuration is found to be a saddle point, in contrast to the corresponding minimum for NO interacting with Fe(III). To use the ab initio results for finite temperature molecular dynamics simulations, an analytical function was fitted to represent the Fe-NO interaction. The simulations show that the secondary minimum is dynamically stable up to 250 K and has a lifetime of several hundred picoseconds at 300 K. The difference in the topology of the heme-NO PES from that assumed previously (one deep, single Fe-NO minimum) suggests that it is important to use the full PES for a quantitative understanding of this system. Why the metastable state has not been observed in the many spectroscopic studies of myoglobin interacting with NO is discussed, and possible approaches to finding it are outlined.

On the existence of extreme waves and the Stokes conjecture with vorticity

This is a study of singular solutions of the problem of traveling gravity water waves on flows with vorticity. We show that, for a certain class of vorticity functions, a sequence of regular waves converges to an extreme wave with stagnation points at its crests. We also show that, for any vorticity function, the profile of an extreme wave must have either a corner of 120° or a horizontal tangent at any stagnation point about which it is supposed symmetric. Moreover, the profile necessarily has a corner of 120° if the vorticity is nonnegative near the free surface.

Non-existence of competitive equilibria with dynamically inconsistent preferences

This paper shows the robust non-existence of competitive equilibria even in a simple three period representative agent economy with dynamically inconsistent preferences. We distinguish between a sophisticated and naive representative agent. Even when underlying preferences are monotone and convex, at given prices, we show by example that the induced preference of the sophisticated representative agent over choices in first-period markets is both non-convex and satiated. Even allowing for negative prices, the market-clearing allocation is not contained in the convex hull of demand. Finally, with a naive representative agent, we show that perfect foresight is incompatible with market clearing and individual optimization at given prices.

A rare case of solution and solid state inter-conversion of two copper(II) dimers and a copper(II) chain

Three Cu(II)-azido complexes of formula [Cu2L2(N-3)(2)] (1), [Cu2L2(N-3)(2)]center dot H2O (2) and [CuL(N-3)](n) (3) have been synthesized using the same tridentate Schiff base ligand HL (2-[(3-methylaminopropylimino)-methyl]-phenol), the condensation product of N-methyl-1,3-propanediamine and salicyldehyde). Compounds 1 and 2 are basal-apical mu-1,1 double azido bridged dimers. The dimeric structure of 1 is centro-symmetric but that of 2 is non-centrommetric. Compound 3 is a mu-1,1 single azido bridged 1D chain. The three complexes interconvert in solution and can be obtained in pure form by carefully controlling the synthetic conditions. Compound 2 undergoes an irreversible transformation to 1 upon dehydration in the solid state. The magnetic properties of compounds 1 and 2 show the presence of weak antiferromagnetic exchange interactions mediated by the double 1,1-N-3 azido bridges (J = -2.59(4) and -0.10(1) cm-(1), respectively). The single 1,1-N-3 bridge in compound 3 mediates a negligible exchange interaction.

Scattering of electromagnetic waves by rough interfaces and inhomogeneous layers

We consider a two-dimensional problem of scattering of a time-harmonic electromagnetic plane wave by an infinite inhomogeneous conducting or dielectric layer at the interface between semi-infinite homogeneous dielectric half-spaces. The magnetic permeability is assumed to be a fixed positive constant. The material properties of the media are characterized completely by an index of refraction, which is a bounded measurable function in the layer and takes positive constant values above and below the layer, corresponding to the homogeneous dielectric media. In this paper, we examine only the transverse magnetic (TM) polarization case. A radiation condition appropriate for scattering by infinite rough surfaces is introduced, a generalization of the Rayleigh expansion condition for diffraction gratings. With the help of the radiation condition the problem is reformulated as an equivalent mixed system of boundary and domain integral equations, consisting of second-kind integral equations over the layer and interfaces within the layer. Assumptions on the variation of the index of refraction in the layer are then imposed which prove to be sufficient, together with the radiation condition, to prove uniqueness of solution and nonexistence of guided wave modes. Recent, general results on the solvability of systems of second kind integral equations on unbounded domains establish existence of solution and continuous dependence in a weighted norm of the solution on the given data. The results obtained apply to the case of scattering by a rough interface between two dielectric media and to many other practical configurations.

On the existence of two-dimensional Euler flows satisfying energy-Casimir stability criteria

The energy-Casimir stability method, also known as the Arnold stability method, has been widely used in fluid dynamical applications to derive sufficient conditions for nonlinear stability. The most commonly studied system is two-dimensional Euler flow. It is shown that the set of two-dimensional Euler flows satisfying the energy-Casimir stability criteria is empty for two important cases: (i) domains having the topology of the sphere, and (ii) simply-connected bounded domains with zero net vorticity. The results apply to both the first and the second of Arnold’s stability theorems. In the spirit of Andrews’ theorem, this puts a further limitation on the applicability of the method. © 2000 American Institute of Physics.

Transreal proof of the existence of universal possible worlds

Transreal arithmetic is total, in the sense that the fundamental operations of addition, subtraction, multiplication and division can be applied to any transreal numbers with the result being a transreal number [1]. In particular division by zero is allowed. It is proved, in [3], that transreal arithmetic is consistent and contains real arithmetic. The entire set of transreal numbers is a total semantics that models all of the semantic values, that is truth values, commonly used in logics, such as the classical, dialetheaic, fuzzy and gap values [2]. By virtue of the totality of transreal arithmetic, these logics can be implemented using total, arithmetical functions, specifically operators, whose domain and counterdomain is the entire set of transreal numbers

Quasi-sure existence of Gaussian rough paths and large deviation principles for capacities

We construct a quasi-sure version (in the sense of Malliavin) of geometric rough paths associated with a Gaussian process with long-time memory. As an application we establish a large deviation principle (LDP) for capacities for such Gaussian rough paths. Together with Lyons' universal limit theorem, our results yield immediately the corresponding results for pathwise solutions to stochastic differential equations driven by such Gaussian process in the sense of rough paths. Moreover, our LDP result implies the result of Yoshida on the LDP for capacities over the abstract Wiener space associated with such Gaussian process.

Missed, not missing: phylogenomic evidence for the existence of Avian FoxP3

The Forkhead box transcription factor FoxP3 is pivotal to the development and function of regulatory T cells (Tregs), which make a major contribution to peripheral tolerance. FoxP3 is believed to perform a regulatory role in all the vertebrate species in which it has been detected. The prevailing view is that FoxP3 is absent in birds and that avian Tregs rely on alternative developmental and suppressive pathways. Prompted by the automated annotation of foxp3 in the ground tit (Parus humilis) genome, we have questioned this assumption. Our analysis of all available avian genomes has revealed that the foxp3 locus is missing, incomplete or of poor quality in the relevant genomic assemblies for nearly all avian species. Nevertheless, in two species, the peregrine falcon (Falco peregrinus) and the saker falcon (F. cherrug), there is compelling evidence for the existence of exons showing synteny with foxp3 in the ground tit. A broader phylogenomic analysis has shown that FoxP3 sequences from these three species are similar to crocodilian sequences, the closest living relatives of birds. In both birds and crocodilians, we have also identified a highly proline-enriched region at the N terminus of FoxP3, a region previously identified only in mammals.

Existence of pullback attractors for pullback asymptotically compact processes

This paper is concerned with the existence of pullback attractors for evolution processes. Our aim is to provide results that extend the following results for autonomous evolution processes (semigroups) (i) An autonomous evolution process which is bounded, dissipative and asymptotically compact has a global attractor. (ii) An autonomous evolution process which is bounded, point dissipative and asymptotically compact has a global attractor. The extension of such results requires the introduction of new concepts and brings up some important differences between the asymptotic properties of autonomous and non-autonomous evolution processes. An application to damped wave problem with non-autonomous damping is considered. (C) 2009 Elsevier Ltd. All rights reserved.

Existence of secondary bifurcations or isolas for PDEs

In this paper, we introduce a method to conclude about the existence of secondary bifurcations or isolas of steady state solutions for parameter dependent nonlinear partial differential equations. The technique combines the Global Bifurcation Theorem, knowledge about the non-existence of nontrivial steady state solutions at the zero parameter value and explicit information about the coexistence of multiple nontrivial steady states at a positive parameter value. We apply the method to the two-dimensional Swift-Hohenberg equation. (C) 2011 Elsevier Ltd. All rights reserved.

ABELIANIZED OBSTRUCTION FOR FIXED POINTS OF FIBER-PRESERVING MAPS OF SURFACE BUNDLES

Let f: M -> M be a fiber-preserving map where S -> M -> B is a bundle and S is a closed surface. We study the abelianized obstruction, which is a cohomology class in dimension 2, to deform f to a fixed point free map by a fiber-preserving homotopy. The vanishing of this obstruction is only a necessary condition in order to have such deformation, but in some cases it is sufficient. We describe this obstruction and we prove that the vanishing of this class is equivalent to the existence of solution of a system of equations over a certain group ring with coefficients given by Fox derivatives.

Existence of orthogonal geodesic chords on Riemannian manifolds with concave boundary and homeomorphic to the N-dimensional disk

In this paper we give a proof of the existence of an orthogonal geodesic chord on a Riemannian manifold homeomorphic to a closed disk and with concave boundary. This kind of study is motivated by the link (proved in Giambo et al. (2005) [8]) of the multiplicity problem with the famous Seifert conjecture (formulated in Seifert (1948) [1]) about multiple brake orbits for a class of Hamiltonian systems at a fixed energy level. (C) 2010 Elsevier Ltd. All rights reserved.