Preparation of polyetherol-appended sulfur porphyrazines and investigations of peripheral metal ion binding in polar solvents

We describe the complete synthesis and characterization of a new family of peripherally functionalized porphyrazines (pz's) with four, three, or two (in a trans conformation) bis[thioethoxy(ethoxy)ethanol] moieties appended at the pyrroles. These "polyetherol" groups serve as weak exocyclic binding sites for a number of metal ions and also provide solubility of the pz's in low molecular-weight alcohols and water. Electronic spectra of the modified porphyrazines exhibit distinct changes in the visible region (both absorbance and fluorescence) in response to treatment with Ag+, Pb2+, Cd2+, Cs+, and Ni2+ in solution. Such properties make these compounds intriguing candidates for incorporation into the transducer layers in optically based chemical sensors.     

Surface resonance transition of roughened Cu(1 1 0)

The temperature dependence of the reflection anisotropy spectroscopy (RAS) of a Cu(1 1 0) surface has been studied over the temperature range 700-1000 K. Because of the roughening transition at 900 K, the bimodal feature at 4.2 eV for a clean surface shifted to 4.3 eV on annealing. A significant decrease in intensity of the same energy level was also observed with increasing annealing temperature. In the annealing temperature range 700-1000 K, anharmonic behavior is expected to be the predominant process of atomic disordering at the surface. Changes in the RAS of Cu(1 1 0) as a result of thermal processing can be understood in terms of the associated changes in surface states. The RAS signal for a surface resonance transition at 4.2 eV is associated with monoatomic [0 0 1] steps.     

The approximation of planar curve evolutions by stable fully implicit finite element schemes that equidistribute

On the basis of our previous work, we introduce novel fully discrete, fully practical parametric finite element approximations for geometric evolution equations of curves in the plane. The fully implicit approximations are unconditionally stable and intrinsically equidistribute the vertices at each time level. We present iterative solution methods for the systems of nonlinear equations arising at each time level and present several numerical results. The ideas easily generalize to the evolution of curve networks and to anisotropic surface energies. © 2010 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 2010     

Valence band and surface core-level shift studies of the oxygen-induced p(3 × 1) reconstruction of the W(1 0 0) surface

Using synchrotron radiation, W 4f_7/2 and valence-band (VB) photoelectron spectroscopy was used to study the oxidation states of the p(3 × 1) reconstructed surface of W(1 0 0) produced by oxygen adsorption at 1500 K. The W 4f_7/2 study showed two features at 0.40 and 1.50 eV higher binding energies relative to the bulk feature which represent shifts to lower binding energies compared to the W 4f_7/2 features of the as-grown oxygen films on W(1 0 0). Co-existence of these features is a characteristic of the formation of the p(3 × 1) structure. The VB studies of this system and as-grown oxygen films at room temperature (RT) showed an oxygen-induced feature for the p(3 × 1) structure for which the peak maximum had shifted by 0.9 eV to higher binding energies compared to the as-grown films. The direction of shifts in the W 4f_7/2 and VB spectra for the p(3 × 1) structure confirmed the reduction of the charge transfer from W to oxygen compared to the as-grown films. A study of the VB changes with photon energy shows that the main component of the oxygen-induced feature in the p(3 × 1) VB at 6.6 ± 0.2 eV is related to a hybridized state between W 5d and O 2p electrons.     

Determinantal formulae for matrices with sparse inverses

The determinant of a matrix is expressed in terms of certain of its principal minors by a formula which can be “read off” from the graph of the inverse of the matrix. The only information used is the zero pattern of the inverse, and each zero pattern yields one or more corresponding formulae for the determinant.     

Generalized no-broadcasting theorem

We prove a generalized version of the no-broadcasting theorem, applicable to essentially any nonclassical finite-dimensional probabilistic model satisfying a no-signaling criterion, including ones with "superquantum" correlations. A strengthened version of the quantum no-broadcasting theorem follows, and its proof is significantly simpler than existing proofs of the no-broadcasting theorem.     

Measurement of the pseudoscalar decay constant fDs using charm-tagged events in e+e- collisions at square root s=10.58 GeV

Using 230.2 fb-1 of e+e- annihilation data collected with the BABAR detector at and near the peak of the Upsilon(4S) resonance, 489+/-55 events containing the pure leptonic decay Ds+-->micro;+numicro have been isolated in charm-tagged events. The ratio of partial widths Gamma(D+-->micro+numicro)/Gamma(Ds+-->phipi+) is measured to be 0.143+/-0.018+/-0.006 allowing a determination of the pseudoscalar decay constant fDs=(283+/-17+/-7+/-14) MeV. The errors are statistical, systematic, and from the Ds+-->phipi+ branching ratio, respectively.     

Measurement of the B0-->pi(-l)(+nu) form-factor shape and branching fraction, and determination of /Vub/ with a loose neutrino reconstruction technique

We report the results of a study of the exclusive charmless semileptonic decay, B0-->pi(-l)(+nu), undertaken with approximately 227 x 10(6) BB pairs collected at the Upsilon(4S) resonance with the BABAR detector. The analysis uses events in which the signal B decays are reconstructed with an innovative loose neutrino reconstruction technique. We obtain partial branching fractions in 12 bins of q2, the momentum transfer squared, from which we extract the f + (q2) form-factor shape and the total branching fraction B(B0-->pi(-l)(+nu))=(1.46+/-0.07stat+/-0.08syst) x 10(-4). Based on a recent unquenched lattice QCD calculation of the form factor in the range q2>16 GeV2, we find the magnitude of the Cabibbo-Kobayashi-Maskawa matrix element /Vub/ to be (4.1+/-0.2stat +/- 0.2syst(+0.6)-0.4_{FF}) x 10(-3), where the last uncertainty is due to the normalization of the form factor.     

On the interactions of alkyl 2-hydroxycarboxylic acids with alkoxysilanes: selective esterification of simple 2-hydroxycarboxylic acids

The interactions of a range of monocarboxylic acids with tetramethoxysilane Si(OMe)(4) (TMOS), in methanol (MeOH), have been investigated by using (1)H, (13)C and (29)Si solution-phase NMR spectroscopy and electrospray mass spectrometry (ESMS). Si(OMe)(4) acts as a catalyst/reagent in the selective methylation of 2-hydroxycarboxylic acids (2HOAs) in MeOH at room temperature: glycolic acid, lactic acid and 2-hydroxybutyric acid are esterified more than a hundred times faster in MeOH and Si(OMe)(4) than in MeOH alone. No acceleration of methylation is observed for carboxylic acids lacking the 2-hydroxy group. Methylation of the 2HOAs is associated with the condensation of individual siloxane units to form oligomers. A mechanism is proposed in which 2HOAs attach to silicon via the alkoxy group, then subsequently via the carboxyl group in an intramolecular rearrangement to form an unstable and reactive cyclic intermediate. This intermediate may lead to accelerated methylation of the carboxylic acid via nucleophilic attack of MeOH at the carbonyl group, while a separate reaction pathway leads to condensation of silanols and/or alkoxysilanes leading to oligosiloxanes. The mechanism has implications for the use of 2HOAs as templates in sol-gel silica preparation.