Equilibrating metal-oxide cluster ensembles for oxidation reactions using oxygen in water.

Although many enzymes can readily and selectively use oxygen in water-the most familiar and attractive of all oxidants and solvents, respectively-the design of synthetic catalysts for selective water-based oxidation processes utilizing molecular oxygen remains a daunting task. Particularly problematic is the fact that oxidation of substrates by O2 involves radical chemistry, which is intrinsically non-selective and difficult to control. In addition, metallo-organic catalysts are inherently susceptible to degradation by oxygen-based radicals, while their transition-metal-ion active sites often react with water to give insoluble, and thus inactive, oxides or hydroxides. Furthermore, pH control is often required to avoid acid or base degradation of organic substrates or products. Unlike metallo-organic catalysts, polyoxometalate anions are oxidatively stable and are reversible oxidants for use with O2 (refs 8,9,10). Here we show how thermodynamically controlled self-assembly of an equilibrated ensemble of polyoxometalates, with the heteropolytungstate anion [AIVVW11O40]6- as its main component, imparts both stability in water and internal pH-management. Designed to operate at near-neutral pH, this system facilitates a two-step O2-based process for the selective delignification of wood (lignocellulose) fibres. By directly monitoring the central Al atom, we show that equilibration reactions typical of polyoxometalate anions keep the pH of the system near 7 during both process steps.     

Individual recognition in mice mediated by major urinary proteins.

The ability to recognize individuals is essential to many aspects of social behaviour, such as the maintenance of stable social groups, parent-offspring or mate recognition, inbreeding avoidance and the modulation of competitive relationships. Odours are a primary mediator of individuality signals among many mammals. One source of odour complexity in rodents, and possibly in humans, resides in the highly polymorphic major histocompatibility complex (MHC). The olfactory acuity of mice and rats allows them to distinguish between the urinary odours of congenic strains differing only in single genes within the MHC, although the chemical mediators or odorants are unknown. However, rodent urine also contains a class of proteins, termed major urinary proteins (MUPs), that bind and release small volatile pheromones. We have shown that the combinatorial diversity of expression of MUPs among wild mice might be as great as for MHC, and at protein concentrations a million times higher. Here we show in wild house mice (Mus domesticus) that urinary MUPs play an important role in the individual recognition mechanism.     

Phot1 and phot2 mediate blue light regulation of stomatal opening.

The stomatal pores of higher plants allow for gaseous exchange into and out of leaves. Situated in the epidermis, they are surrounded by a pair of guard cells which control their opening in response to many environmental stimuli, including blue light. Opening of the pores is mediated by K(+) accumulation in guard cells through a K(+) channel and driven by an inside-negative electrical potential. Blue light causes phosphorylation and activation of the plasma membrane H(+)-ATPase that creates this potential. Thus far, no blue light receptor mediating stomatal opening has been identified, although the carotenoid, zeaxanthin, has been proposed. Arabidopsis mutants deficient in specific blue-light-mediated responses have identified four blue light receptors, cryptochrome 1 (cry1), cryptochrome 2 (cry2), phot1 and phot2. Here we show that in a double mutant of phot1 and phot2 stomata do not respond to blue light although single mutants are phenotypically normal. These results demonstrate that phot1 and phot2 act redundantly as blue light receptors mediating stomatal opening.     

Gridlock signalling pathway fashions the first embryonic artery.

Arteries and veins are morphologically, functionally and molecularly very different, but how this distinction is established during vasculogenesis is unknown. Here we show, by lineage tracking in zebrafish embryos, that angioblast precursors for the trunk artery and vein are spatially mixed in the lateral posterior mesoderm. Progeny of each angioblast, however, are restricted to one of the vessels. This arterial-venous decision is guided by gridlock (grl), an artery-restricted gene that is expressed in the lateral posterior mesoderm. Graded reduction of grl expression, by mutation or morpholino antisense, progressively ablates regions of the artery, and expands contiguous regions of the vein, preceded by an increase in expression of the venous marker EphB4 receptor (ephb4) and diminution of expression of the arterial marker ephrin-B2 (efnb2). grl is downstream of notch, and interference with notch signalling, by blocking Su(H), similarly reduces the artery and increases the vein. Thus, a notch-grl pathway controls assembly of the first embryonic artery, apparently by adjudicating an arterial versus venous cell fate decision.     

Interior penalty bilinear IFE discontinuous Galerkin methods for elliptic equations with discontinuous coefficient

<正> This paper applies bilinear immersed finite elements (IFEs) in the interior penalty discontinuousGalerkin (DG) methods for solving a second order elliptic equation with discontinuous coefficient.A discontinuous bilinear IFE space is constructed and applied to both the symmetric and nonsymmetricinterior penalty DG formulations.The new methods can solve an interface problem on a Cartesianmesh independent of the interface with local refinement at any locations needed even if the interfacehas a nontrivial geometry.Numerical examples are provided to show features of these methods.     

Positive observer design for positive Markovian jump systems with partly known transition rates

The paper is concerned with positive observer design for positive Markovian jump systems with partly known transition rates. By applying a linear co-positive type Lyapunov-Krasovskii function, a sufficient condition is proposed to ensure the stochastic stability of the error positive system and the existence of the positive observer, which is computed in linear programming. Finally, an example is given to demonstrate the validity of the main results.     

Tunable water-based lubrication behavior of alkyl- and fluoroalkyl-silanes

In this paper,we report the tribological properties of self-assembled molecular(SAM) films of fluoroalkylsilanes and non-fluoroalkylsilanes,with different chain-lengths,adsorbed on Si substrate surfaces by covalent bonds.The SAM films were characterized using a universal ball-disk experimental tester in aqueous solutions.The substrate surface was examined by X-ray photoelectron spectroscopy(XPS),and the SAM films adsorbed on the Si surfaces were inspected by contact angle measurements and XPS.Lubrication studies revealed that several kinds of fluoroalkylsilanes had similar friction coefficients;the small differences were attributed to the chain flexibility.In contrast,differences in the aqueous lubrication properties of SAM films of non-fluoroalkylsilanes were clearly identified.It is suggested that substitution with fluorine atoms and the surface affinities of fluoroalkylsilanes contributed to redistribution of surface changes,causing variations in lubrication behaviors.     

多酸衍生物非线性光学性质的理论研究新进展

近年来,分子基非线性光学材料因其优异的非线性光学特性受到了人们集中的关注,多金属氧酸盐具有多样的结构和良好的电子性质,作为优良的无机构筑模块参与到分子设计中,可以获得有较好应用前景的非线性光学材料.本文在微结构非线性光学材料方面综合概述了Keggin型和Lindqvist型多酸衍生物类非线性光学材料的理论研究及分子设计进展.     

Continuity of solution mappings for parametric generalized set-valued weak vector equilibrium problems

This paper obtains some stability results for parametric generalized set-valued weak vector equilibrium problem. Under new assumptions, which do not contain any information about solution mappings, the authors establish the continuity of the solution mapping to a parametric generalized set-valued weak vector equilibrium problem without monotonicity. These results extend and improve some results in the literature. Some examples are given to illustrate the results.