Synthesis of nickel nanoparticles supported on hollow samaria-doped ceria particles via the solution-spray plasma technique: Anode catalysts for SOFCs

Aiming at SOFC anode applications, we have synthesized nanometer-sized nickel catalysts supported on hollow spherical particles of samaria-doped ceria (Ni/SDC) by spraying a mixed solution of nickel, samarium, and cerium nitrates into an atmospheric pressure plasma. The as-prepared particles consisted of SDC (average diameter d_SDC = ca. 0.8 µm) and uniformly dispersed nanometer-sized NiO particles. When reduced in H₂ at 800 °C or 1000 °C, Ni nanoparticles (average diameter d_Ni = 34 nm) were found to be embedded uniformly into the SDC surface.     

Microfaceting explains complicated structures on rutile TiO2 surfaces

Surface structures on rutile TiO2 (001) have been studied by using scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional calculations. Prior investigations have observed many kinds of complicated surface structures; however, detailed atomic structures and the mechanism of the reconstructions are still unknown. We evaluate the energetical stability of the surface structures. The calculational results suggest that a [111] microfaceting model is energetically stable compared with the unreconstructed (1 x 1) model. We propose microfaceting structural models that are in good agreement with atomically resolved STM images. This structural concept can be extended to other rutile TiO2 surfaces in general.     

Copper-mediated and copper-catalyzed cross-coupling of indoles and 1,3-azoles: double C-H activation

A new bronze age: the described copper-mediated cross-coupling with double C-H activation can provide a convergent access to indole-containing biheteroaryls that are of high interest in pharmaceutical and medicinal chemistry. In this strategy an easily attachable and detachable 2-pyrimidyl directing group is used. Moreover, a variant that is catalytic in copper is achieved by using atmospheric oxygen as an ideal co-oxidant.     

Protein conformational gating of enzymatic activity in xanthine oxidoreductase

In mammals, xanthine oxidoreductase can exist as xanthine dehydrogenase (XDH) and xanthine oxidase (XO). The two enzymes possess common redox active cofactors, which form an electron transfer (ET) pathway terminated by a flavin cofactor. In spite of identical protein primary structures, the redox potential difference between XDH and XO for the flavin semiquinone/hydroquinone pair (E(sq/hq)) is ~170 mV, a striking difference. The former greatly prefers NAD(+) as ultimate substrate for ET from the iron-sulfur cluster FeS-II via flavin while the latter only accepts dioxygen. In XDH (without NAD(+)), however, the redox potential of the electron donor FeS-II is 180 mV higher than that for the acceptor flavin, yielding an energetically uphill ET. On the basis of new 1.65, 2.3, 1.9, and 2.2 ? resolution crystal structures for XDH, XO, the NAD(+)- and NADH-complexed XDH, E(sq/hq) were calculated to better understand how the enzyme activates an ET from FeS-II to flavin. The majority of the E(sq/hq) difference between XDH and XO originates from a conformational change in the loop at positions 423-433 near the flavin binding site, causing the differences in stability of the semiquinone state. There was no large conformational change observed in response to NAD(+) binding at XDH. Instead, the positive charge of the NAD(+) ring, deprotonation of Asp429, and capping of the bulk surface of the flavin by the NAD(+) molecule all contribute to altering E(sq/hq) upon NAD(+) binding to XDH.     

Absolute and convective instabilities of two-dimensional bluff body wakes in ground effect

Local and global instabilities are investigated of wakes of general two-dimensional bluff bodies placed near and parallel to a plane boundary or ground. A spatio-temporal linear stability analysis is first applied to a four-parameter family of local wake profiles to investigate the fundamental local stability characteristics of the wake in ground effect. The analysis shows significant dependencies of the stability characteristics of the wake on the distance from the wake centreline to the ground (normalised by the wake width), and also on the velocity ratio of the near- and far-ground sides of the wake. The analysis is then compared with earlier experiments on a circular cylinder to examine, according to the transition scenario of the steep global modes, the streamwise variation of the local stability characteristics of the wake in ground effect. The comparison indicates that the near wake region of the cylinder changes from being absolutely unstable to being convectively unstable when the cylinder comes down into the near-ground range in which the von Kármán-type vortex shedding from the cylinder is suppressed, being qualitatively consistent with the transition scenario for general wake-type flows. A possible explanation is also given for the counter-intuitive relation between the thickness of the boundary layer on the ground and the critical gap distance for the cessation of the von Kármán-type vortex shedding in ground effect.     

Efficient deanilidation of phosphoranilidates by the use of nitrites and acetic anhydride

Reagent systems of sodium– and tetrabutylammonium nitrite–acetic anhydride were proved to be extremely efficient for the deanilidation of nucleoside 3′-phosphoranilidates, whose reactions were rapid with the former and instant with the latter. It was further found that the reagent system is applicable to oligonucleotide synthesis provided that the exocyclic amino groups of 2′-deoxyadenosine, 2′-deoxyguanosine, and 2′-deoxycytidine were protected by succinylation.     

Role of cyclic dithiocarbonate as a promoter in the reaction of epoxide and imine in the presence of water

It was demonstrated that the reaction of epoxide and imine as a latent initiator under highly humid conditions was accelerated by addition of 5‐phenoxymethyl‐1,3‐oxathiolane‐2‐thione ( 1 ). When 1 was added to a mixture of glycidyl phenyl ether and an imine, the reaction of the epoxide with an amine released from the imine became faster than was the case without 1 , that is, 1 worked as a promoter of the reaction. The curing rate and initial adhesive strength of epoxy resin increased compared with that without 1 . © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4276–4283, 2004     

The thermodynamic Bethe ansatz and the 1/N correction to the density phase transition in the Gross-Neveu model

We compute the 1/N correction to the location of the previously found first-order phase transition in the Gross-Neveu model at a chemical potential where m is the fermion mass. We employ an expression for the free energy f(μ) given by the thermodynamic Bethe ansatz under the approximation that the fundamental fermions dominate the ground state, and combine it with the effective potential evaluated at zero chemical potential.

Our result is .     

An attractor universe in six-dimensional N = 2 supergravity Kaluza-Klein theory

Cosmological solutions are investigated in six-dimensional, N = 2 supergravity Kaluza-Klein theory. It is shown that the solution of (the four-dimensional Friedmann universe)×(a constant S²) is the attractor, i.e. all the cosmological solutions starting from arbitrary initial conditions (apart from the time reversal ones) approach the above space-time asymptotically without any fine-tuning. The Friedmann solution is asymptotically “unique” in the later stage of the universe in six-dimensional N = 2 supergravity.