Structure of an Odorant-Binding Protein from the Mosquito Aedes aegypti Suggests a Binding Pocket Covered by a pH-Sensitive ""Lid""

Background: The yellow fever mosquito, Aedes aegypti, is the primary vector for the viruses that cause yellow fever, mostly in tropical regions of Africa and in parts of South America, and human dengue, which infects 100 million people yearly in the tropics and subtropics. A better understanding of the structural biology of olfactory proteins may pave the way for the development of environmentally-friendly mosquito attractants and repellents, which may ultimately contribute to reduction of mosquito biting and disease transmission. Methodology: Previously, we isolated and cloned a major, female-enriched odorant-binding protein (OBP) from the yellow fever mosquito, AaegOBP1, which was later inadvertently renamed AaegOBP39. We prepared recombinant samples of AaegOBP1 by using an expression system that allows proper formation of disulfide bridges and generates functional OBPs, which are indistinguishable from native OBPs. We crystallized AaegOBP1 and determined its three-dimensional structure at 1.85 angstrom resolution by molecular replacement based on the structure of the malaria mosquito OBP, AgamOBP1, the only mosquito OBP structure known to date. Conclusion: The structure of AaegOBP1 (= AaegOBP39) shares the common fold of insect OBPs with six alpha-helices knitted by three disulfide bonds. A long molecule of polyethylene glycol (PEG) was built into the electron-density maps identified in a long tunnel formed by a crystallographic dimer of AaegOBP1. Circular dichroism analysis indicated that delipidated AaegOBP1 undergoes a pH-dependent conformational change, which may lead to release of odorant at low pH (as in the environment in the vicinity of odorant receptors). A C-terminal loop covers the binding cavity and this ""lid"" may be opened by disruption of an array of acid-labile hydrogen bonds thus explaining reduced or no binding affinity at low pH.

Imidazolium fumarate

In the title compound, C(3)H(5)N(2)(+)center dot C(4)H(3)O(4)(-), the dihedral angle between the imidazolium ring and the plane formed by the fumarate anion is 80.98 (6)degrees. In the crystal structure, intermolecular O-H center dot center dot center dot O and N-H center dot center dot center dot O hydrogen bonds form extended chains along [100] and [01 (1) over bar], creating a two-dimensional network.

3-Nitrobenzoic acid-3-methyl-4-nitropyridine 1-oxide (1/1)

The title adduct, C(7)H(5)NO(4)center dot C(6)H(6)N(2)O(3), forms part of an ongoing study of the design of non-centrosymmetric systems based on 3-methy-4-nitropyridine 1-oxide. The components of the adduct are linked by intermolecular O-H center dot center dot center dot O hydrogen bonds. The rings of the two components are nearly planar, with a dihedral angle of 11.9 (2)degrees between the planes. The supramolecular structure shows that molecules of the title complex are linked into sheets by a combination of strong O-H center dot center dot center dot O and weak C-H center dot center dot center dot O hydrogen bonds.

4-{2-[4-(Dimethylamino)phenyl]ethylidene}benzonitrile

In the crystal of the title compound, C(17)H(16)N(2), molecules are linked by C-H center dot center dot center dot N hydrogen bonds, forming rings of graph-set motifs R(2)(1) (6) and R(2)(2) (10). The title molecule is close to planar, with a dihedral angle between the aromatic rings of 0.6 (1)degrees. Torsion angles confirm a conformational trans structure.

Constraints on the infrared behavior of the ghost propagator in Yang-Mills theories

We present rigorous upper and lower bounds for the momentum-space ghost propagator G(p) of Yang-Mills theories in terms of the smallest nonzero eigenvalue (and of the corresponding eigenvector) of the Faddeev-Popov matrix. We apply our analysis to data from simulations of SU(2) lattice gauge theory in Landau gauge, using the largest lattice sizes to date. Our results suggest that, in three and in four space-time dimensions, the Landau gauge ghost propagator is not enhanced as compared to its tree-level behavior. This is also seen in plots and fits of the ghost dressing function. In the two-dimensional case, on the other hand, we find that G(p) diverges as p(-2-2 kappa) with kappa approximate to 0.15, in agreement with A. Maas, Phys. Rev. D 75, 116004 (2007). We note that our discussion is general, although we make an application only to pure gauge theory in Landau gauge. Our simulations have been performed on the IBM supercomputer at the University of Sao Paulo.

N-(4-chlorophenyl)maleimide

In the title compound, C10H6ClNO2, the dihedral angle between the benzene and maleimide rings is 47.54 (9)degrees. Molecules form centrosymmetric dimers through C-H center dot center dot center dot O hydrogen bonds, resulting in rings of graph- set motif R2 2(8) and chains in the [100] direction. Molecules are also linked by C-H center dot center dot center dot Cl hydrogen bonds along [001]. In this same direction, molecules are connected to other neighbouring molecules by C-H center dot center dot center dot O hydrogen bonds, forming edge- fused R-4(4)(24) rings.

Contribution of the second Landau level to the exchange energy of the three-dimensional electron gas in a high magnetic field

We derive a closed analytical expression for the exchange energy of the three-dimensional interacting electron gas in strong magnetic fields, which goes beyond the quantum limit (L=0) by explicitly including the effect of the second, L=1, Landau level and arbitrary spin polarization. The inclusion of the L=1 level brings the fields to which the formula applies closer to the laboratory range, as compared to previous expressions, valid only for L=0 and complete spin polarization. We identify and explain two distinct regimes separated by a critical density n(c). Below n(c), the per particle exchange energy is lowered by the contribution of L=1, whereas above n(c) it is increased. As special cases of our general equation we recover various known more limited results for higher fields, and we identify and correct a few inconsistencies in some of these earlier expressions.

Hydrogen bonding in 2-(2-oxothiazolidin-3-yl)-4,5-dihydrothiazolium hydrogen sulfate monohydrate

The asymmetric unit of the title compound, C(6)H(9)N(2)OS(2)(+)center dot-HSO(4)(-)center dot H(2)O, contains a heterocyclic cation, a hydrogen sulfate anion and a water molecule. There are strong hydrogen bonds between the hydrogen sulfate anions and water molecules, forming an infinite chain along the [010] direction, from which the cations are pendent. The steric, electronic and geometric features are compared with those of similar compounds. In this way, structural relationships are stated in terms of the influence of the sulfate group on the protonation of the heterocycle and on the tautomeric equilibrium in the solid state.

Collision probabilities in the rarefaction fan of asymmetric exclusion processes

We consider the one-dimensional asymmetric simple exclusion process (ASEP) in which particles jump to the right at rate p is an element of (1/2, 1.] and to the left at rate 1 - p, interacting by exclusion. In the initial state there is a finite region such that to the left of this region all sites are occupied and to the right of it all sites are empty. Under this initial state, the hydrodynamical limit of the process converges to the rarefaction fan of the associated Burgers equation. In particular suppose that the initial state has first-class particles to the left of the origin, second-class particles at sites 0 and I, and holes to the right of site I. We show that the probability that the two second-class particles eventually collide is (1 + p)/(3p), where a collision occurs when one of the particles attempts to jump over the other. This also corresponds to the probability that two ASEP processes. started from appropriate initial states and coupled using the so-called ""basic coupling,"" eventually reach the same state. We give various other results about the behaviour of second-class particles in the ASEP. In the totally asymmetric case (p = 1) we explain a further representation in terms of a multi-type particle system, and also use the collision result to derive the probability of coexistence of both clusters in a two-type version of the corner growth model.

Exceptional times for the dynamical discrete web

The dynamical discrete web (DyDW), introduced in the recent work of Howitt and Warren, is a system of coalescing simple symmetric one-dimensional random walks which evolve in an extra continuous dynamical time parameter tau. The evolution is by independent updating of the underlying Bernoulli variables indexed by discrete space-time that define the discrete web at any fixed tau. In this paper, we study the existence of exceptional (random) values of tau where the paths of the web do not behave like usual random walks and the Hausdorff dimension of the set of such exceptional tau. Our results are motivated by those about exceptional times for dynamical percolation in high dimension by Haggstrom, Peres and Steif, and in dimension two by Schramm and Steif. The exceptional behavior of the walks in the DyDW is rather different from the situation for the dynamical random walks of Benjamini, Haggstrom, Peres and Steif. For example, we prove that the walk from the origin S(0)(tau) violates the law of the iterated logarithm (LIL) on a set of tau of Hausdorff dimension one. We also discuss how these and other results should extend to the dynamical Brownian web, the natural scaling limit of the DyDW. (C) 2009 Elsevier B.V. All rights reserved.

ON THE THREE-DIMENSIONAL BLASCHKE-LEBESGUE PROBLEM

The width of a closed convex subset of n-dimensional Euclidean space is the distance between two parallel supporting hyperplanes. The Blaschke-Lebesgue problem consists of minimizing the volume in the class of convex sets of fixed constant width and is still open in dimension n >= 3. In this paper we describe a necessary condition that the minimizer of the Blaschke-Lebesgue must satisfy in dimension n = 3: we prove that the smooth components of the boundary of the minimizer have their smaller principal curvature constant and therefore are either spherical caps or pieces of tubes (canal surfaces).

Potent Cardioprotective Effect of the 4-Anilinoquinazoline Derivative PD153035: Involvement of Mitochondrial K(ATP) Channel Activation

Background: The aim of the present study was to evaluate the protective effects of the 4-anilinoquinazoline derivative PD153035 on cardiac ischemia/reperfusion and mitochondrial function. Methodology/Principal Findings: Perfused rat hearts and cardiac HL-1 cells were used to determine cardioprotective effects of PD153035. Isolated rat heart mitochondria were studied to uncover mechanisms of cardioprotection. Nanomolar doses of PD153035 strongly protect against heart and cardiomyocyte damage induced by ischemia/reperfusion and cyanide/aglycemia. PD153035 did not alter oxidative phosphorylation, nor directly prevent Ca(2+) induced mitochondrial membrane permeability transition. The protective effect of PD153035 on HL-1 cells was also independent of AKT phosphorylation state. Interestingly, PD153035 activated K(+) transport in isolated mitochondria, in a manner prevented by ATP and 5-hydroxydecanoate, inhibitors of mitochondrial ATP-sensitive K(+) channels (mitoK(ATP)). 5-Hydroxydecanoate also inhibited the cardioprotective effect of PD153035 in cardiac HL-1 cells, demonstrating that this protection is dependent on mitoK(ATP) activation. Conclusions/Significance: We conclude that PD153035 is a potent cardioprotective compound and acts in a mechanism involving mitoK(ATP) activation.

Strong reduction of V(4+) amount in vanadium oxide/hexadecylamine nanotubes by doping with Co(2+) and Ni(2+) ions: Electron paramagnetic resonance and magnetic studies

In this work we present a complete characterization and magnetic study of vanadium oxide/hexadecylamine nanotubes (VO(x)/Hexa NT's) doped with Co(2)+ and Ni(2+) ions. The morphology of the NT's has been characterized by transmission electron microscopy, while the metallic elements have been quantified by the instrumental neutron activation analysis technique. The static and dynamic magnetic properties were studied by collecting data of magnetization as a function of magnetic field and temperature and by electron paramagnetic resonance. At difference of the majority reports in the literature, we do not observe magnetic dimers in vanadium oxide nanotubes. Also, we observed that the incorporation of metallic ions (Co(2+), S = 3/2 and Ni(2+), S = 1) decreases notably the amount of V(4+) ions in the system, from 14-16% (nondoped case) to 2%-4%, with respect to the total vanadium atoms (fact corroborated by XPS experiments) anyway preserving the tubular nanostructure. The method to decrease the amount of V(4+) in the nanotubes improves considerably their potential technological applications as Li-ion batteries cathodes. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3580252]

Metastable BrO(2+) and NBr(2+) molecules in the gas phase

The doubly positively charged gas-phase molecules BrO(2+) and NBr(2+) have been produced by prolonged high-current energetic oxygen (17 keV (16)O(-)) ion surface bombardment (ion beam sputtering) of rubidium bromide (RbBr) and of ammonium bromide (NH(4)Br) powdered ionic salt samples, respectively, pressed into indium foil. These novel species were observed at half-integer m/z values in positive ion mass spectra for ion flight times of roughly similar to 12 mu s through a magnetic-sector secondary ion mass spectrometer. Here we present these experimental results and combine them with a detailed theoretical investigation using high level ab initio calculations of the ground states of BrO(2+) and NBr(2+), and a manifold of excited electronic states. NBr(2+) and BrO(2+), in their ground states, are long-lived metastable gas-phase molecules with well depths of 2.73 x 10(4) cm(-1) (3.38 eV) and 1.62 x 10(4) cm(-1) (2.01 eV); their fragmentation channels into two monocations lie 2.31 x 10(3) cm(-1) (0.29 eV) and 2.14 x 10(4) cm(-1) (2.65 eV) below the ground state minimum. The calculated lifetimes for NBr(2+) (v '' < 35) and BrO(2+) (v '' < 18) are large enough to be considered stable against tunneling. For NBr(2+), we predicted R(e) = 3.051 a(0) and omega(e) = 984 cm(-1); for BrO(2+), we obtained 3.033 a(0) and 916 cm(-1), respectively. The adiabatic double ionization energies of BrO and NBr to form metastable BrO(2+) and NBr(2+) are calculated to be 30.73 and 29.08 eV, respectively. The effect of spin-orbit interactions on the low-lying (Lambda + S) states is also discussed. (C) 2011 American Institute of Physics. [doi:10.1063/1.3562121]

3,3-Bis[(4-chlorophenyl)sulfanyl]-1-methylpiperidin-2-one

The piperidone ring in the title compound, C(18)H(17)Cl(2)NOS(2), has a distorted half-chair conformation. The S-bound benzene rings are approximately perpendicular to and splayed out of the mean plane through the piperidone ring [dihedral angles = 71.86 (13) and 46.94 (11)degrees]. In the crystal, C-H center dot center dot center dot O interactions link the molecules into [010] supramolecular chains with a helical topology. C-H center dot center dot center dot Cl and C-H center dot center dot center dot pi interactions are also present.