On the stability of the "wired" bilirubin oxidase oxygen cathode in serum

Oxygen is electroreduced to water on the "wired" bilirubin oxidase (w-BOD) catalyst at a considerably lesser potential than on pure platinum. The w-BOD catalyst could be of value in an implantable glucose-O2 biofuel cell, operating living tissue, if it were stable in serum. We found, however, that w-BOD loses its activity in a few hours in the combined presence of the urate and O2, both of which are normal serum constituents (Bioelectrochemistry, 2004, 65, 83-88). Here we report a second major instability: When the disconnected w-BOD cathode is allowed, in the absence of urate, to poise itself at the potential of the O2/H2O half cell at pH 7.2, it loses its activity rapidly. Unlike the urate/O2 caused loss, this loss can be avoided either by applying a potential that is reducing relative to the O2/H2O half-cell potential, or by excluding O2 and adding a mildly reducing reagent, such as urate. The w-BOD cathode can be stored, therefore, in deoxygenated serum, which contains urate.     

Observation of phase separation in a strongly interacting imbalanced fermi gas

We have observed phase separation between the superfluid and the normal component in a strongly interacting Fermi gas with imbalanced spin populations. The in situ distribution of the density difference between two trapped spin components is obtained using phase-contrast imaging and 3D image reconstruction. A shell structure is clearly identified where the superfluid region of equal densities is surrounded by a normal gas of unequal densities. The phase transition induces a dramatic change in the density profiles as excess fermions are expelled from the superfluid.     

Heavy-fermion-like state in a transition metal oxide LiV2O4 single crystal: indication of Kondo resonance in the photoemission spectrum

We have performed a vacuum ultraviolet laser excited photoemission spectroscopy on a d-electron heavy-fermion-like material LiV2O4 single crystal. We observed a sharp peak structure in the density of states at approximately 4 meV above the Fermi level (E(F)). The evolution of the peak height corresponds well with the crossover behavior to the heavy-fermion-like state as observed in the thermal and transport properties. The position, shape, and temperature (T) dependence of the peak structure is quite similar to the Kondo resonance observed in conventional f-electron heavy Fermion compounds.     

A note on the rank of semigroups

The rank of a semigroup $\mathcal{A}The rank of a semigroup A\mathcal{A} of functions from a finite set X to X is the minimum of |f(X)| over f ? Af\in \mathcal{A}. Given a finite set X and a subset Y of X, we show that if A\mathcal{A} is a semigroup of functions from X to X and ℬ a transitive semigroup of functions from Y to Y, then the rank of A\mathcal{A} divides that of ℬ provided that f(X)⊆Y for some f ? Af\in \mathcal{A} and that each function in ℬ is the restriction of a function in A\mathcal{A} to Y. To prove this, we generalize a result of Friedman which says that one can partition Y into q subsets of equal weight where q is the rank of ℬ. When one extends a transitive automaton by adding new states and letters, a similar condition guarantees that the rank of the extension divides the original rank.     

Nonexistence of certain pseudogeometric graphs

Izo($r$) is the pseudogeometric graph for pG${}_r(s,t)$ which satisfies the Krein equality and of which the local graph also satisfies the Krein equality. We prove that Izo($r$) exists if and only if a spherical tight 4-design on $S^{{(2r+1)}^2?4}$ exists. Nonexistence of infinitely many spherical tight 4-designs is well known. It gives the nonexistence of Izo($r$) for infinitely many $r$. Especially, Izo(4) does not exist, which was the first open case.     

Green's theorem and Gorenstein sequences

We study consequences, for a standard graded algebra, of extremal behavior in Green's Hyperplane Restriction Theorem. First, we extend his Theorem 4 from the case of a plane curve to the case of a hypersurface in a linear space. Second, assuming a certain Lefschetz condition, we give a connection to extremal behavior in Macaulay's theorem. We apply these results to show that $(1,19,17,19,1)$ is not a Gorenstein sequence, and as a result we classify the sequences of the form $(1,a,a?2,a,1)$ that are Gorenstein sequences.     

Approximating zeros of monotone operators by proximal point algorithms

In this paper, we introduce two kinds of iterative algorithms for the problem of finding zeros of maximal monotone operators. Weak and strong convergence theorems are established in a real Hilbert space. As applications, we consider a problem of finding a minimizer of a convex function.     

The Neumann problem on ellipsoids

The Neumann problem on an ellipsoid in \(\mathbf {R}^n\) asks for a function harmonic inside the ellipsoid whose normal derivative is some specified function on the ellipsoid. We solve this problem when the specified function on the ellipsoid is a normalized polynomial (a polynomial divided by the norm of the normal vector arising from the definition of the ellipsoid). Specifically, we give a necessary and sufficient condition for a solution to exist, and we show that if a solution exists then it is a polynomial whose degree is at most the degree of the polynomial giving the specified function. Furthermore, we give an algorithm for computing this solution. We also solve the corresponding generalized Neumann problem and give an algorithm for computing its solution.     

First‐principle calculations on CO oxidation catalyzed by a gold nanoparticle

We have elucidated the mechanism of CO oxidation catalyzed by gold nanoparticles through first‐principle density‐functional theory (DFT) calculations. Calculations on selected model show that the low‐coordinated Au atoms of the Au₂₉ nanoparticle carry slightly negative charges, which enhance the O₂ binding energy compared with the corresponding bulk surfaces. Two reaction pathways of the CO oxidation were considered: the Eley–Rideal (ER) and Langmuir–Hinshelwood (LH). The overall LH reaction O_2(ads) + CO_(gas) → O_2(ads) + CO_(ads) → OOCO_(ads) → O_(ads) + CO_2(gas) is calculated to be exothermic by 3.72 eV; the potential energies of the two transition states ( TS_LH1 and TS_LH2 ) are smaller than the reactants, indicating that no net activation energy is required for this process. The CO oxidation via ER reaction Au₂₉ + O_2(gas) + CO_(gas) → Au₂₉–O_2(ads) + CO_(gas) → Au₂₉–CO_3(ads) → Au₂₉–O_(ads) + CO_2(gas) requires an overall activation barrier of 0.19 eV, and the formation of Au₂₉–CO_3(ads) intermediate possesses high exothermicity of 4.33 eV, indicating that this process may compete with the LH mechanism. Thereafter, a second CO molecule can react with the remaining O atom via the ER mechanism with a very small barrier (0.03 eV). Our calculations suggest that the CO oxidation catalyzed by the Au₂₉ nanoparticle is likely to occur at or even below room temperature. To gain insights into high‐catalytic activity of the gold nanoparticles, the interaction nature between adsorbate and substrate is also analyzed by the detailed electronic analysis. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Densities and Viscosities of Tris(acetylacetonato)cobalt(III) Complex Solutions in Various Solvents

The densities and the viscosities of tris(acetylacetonato)cobalt(III) solutions in acetonitrile, dichloromethane, chloroform, tetrachloromethane, benzene, toluene, ethylbenzene, and p-xylene were measured in the dilute concentration regions at several temperatures ranging from 278 to 313 K under ambient pressure. The partial molar volumes of the solvents and solute were calculated. They are independent of concentration and increase slightly as the temperature increases. The viscosity A- and B-coefficients of the Jones-Dole equation were obtained. The A-coefficients were found to be zero within experimental error. The B-coefficients are positive and decrease as the temperature increases. Thermodynamic quantities of activation for viscous flow were calculated on the basis of Eyring’s viscosity equation. From the quantities obtained in this study, along with some information from the literature, it is suggested that structure-making interactions occur between the segments of the complex and the solvent molecules. These interactions include electrostatic interactions between the local charge on the complex and the dipole moment of the solvent in solutions of acetonitrile and dichloromethane, interlocking packing interactions along C ₃-axis of the complex with solvent in solutions of chloroform and tetrachloromethane, and π-electron interactions between the chelate ring of the complex and the solvent in solutions of benzene, toluene, ethylbenzene, and p-xylene.