High-capacity hydrogen and nitric oxide adsorption and storage in a metal-organic framework

Gas adsorption experiments have been carried out on a copper benzene tricarboxylate metal-organic framework material, HKUST-1. Hydrogen adsorption at 1 and 10 bar (both 77 K) gives an adsorption capacity of 11.16 mmol H2 per g of HKUST-1 (22.7 mg g(-)1, 2.27 wt %) at 1 bar and 18 mmol per g (36.28 mg g(-)1, 3.6 wt %) at 10 bar. Adsorption of D2 at 1 bar (77 K) is between 1.09 (at 1 bar) and 1.20(at <100 mbar) times the H2 values depending on the pressure, agreeing with the theoretical expectations. Gravimetric adsorption measurements of NO on HKUST-1 at 196 K (1 bar) gives a large adsorption capacity of approximately 9 mmol g(-1), which is significantly greater than any other adsorption capacity reported on a porous solid. At 298 K the adsorption capacity at 1 bar is just over 3 mmol g(-1). Infra red experiments show that the NO binds to the empty copper metal sites in HKUST-1. Chemiluminescence and platelet aggregometry experiments indicate that the amount of NO recovered on exposure of the resulting complex to water is enough to be biologically active, completely inhibiting platelet aggregation in platelet rich plasma.     

Molecular flexibility effects upon liquid dynamics

Simulation results for the diffusive behavior of polymer chain/penetrant systems are analyzed. The attractive range and flexibility of simple chain molecules were varied in order to gauge the effect on dynamics. In all cases, the dimensionless diffusion coefficient, D*, is found to be a smooth, single-valued function of the packing fraction, eta. The functions D*(eta) are found to be power laws with exponents that are sensitive to both chain stiffness and particle type. For a specific system type, the D*'s for both penetrant and chain-center-of-mass extrapolate to zero at the same packing fraction, eta0. This limiting packing fraction is interpreted to be the location of the glass transition, and (eta0-eta), the distance to the glass transition.     

Observation of B(0)-->D(*-)tau(+)nu(tau) decay at Belle

We report an observation of the decay B{0}-->D{*-}tau{+}nu{tau} in a data sample containing 535x10{6} BB pairs collected with the Belle detector at the KEKB asymmetric-energy e{+}e{-} collider. We find a signal with a significance of 5.2sigma and measure the branching fraction B(B{0}-->D{*-}tau{+}nu{tau})=(2.02{-0.37}{+0.40}(stat)+/-0.37(syst))%. This is the first observation of an exclusive B decay with a b-->ctaunu{tau} transition.     

Experimental constraints on the spin and parity of the Lambdac(2880)+

We report the results of several studies of the Lambda(c)(+)pi(+)pi(-)X final state in continuum e(+)e(-) annihilation data collected by the Belle detector. An analysis of angular distributions in Lambda(c)(2880)(+)-->Sigma(c)(2455)(0,++)pi(+,-) decays strongly favors a Lambda(c)(2880)(+) spin assignment of 5/2 over 3/2 or 1/2. We find evidence for Lambda(c)(2880)(+)-->Sigma(c)(2520)(0,++)pi(+,-) decay and measure the ratio of Lambda(c)(2880)(+) partial widths Gamma(Sigma(c)(2520)pi)/Gamma(Sigma(c)(2455)pi)=0.225+/-0.062+/-0.025. This value favors the Lambda(c)(2880)(+) spin-parity assignment of 5/2(+) over 5/2(-). We also report the first observation of Lambda(c)(2940)(+)-->Sigma(c)(2455)(0,++)pi(+,-) decay and measure Lambda(c)(2880)(+) and Lambda(c)(2940)(+) mass and width parameters. These studies are based on a 553 fb(-1) data sample collected at or near the Upsilon(4S) resonance at the KEKB collider.     

Hydrogen-bonded assembly of methanol on Cu(111)

Investigation of methanol's surface chemistry on metals is a crucial step towards understanding the reactivity of this important chemical feedstock. Cu is a relevant metal for methanol synthesis and reforming, but due to the weak interaction of methanol with Cu, an atomic scale view of methanol's coverage-dependent ordering and self-assembly on Cu(111), the most abundant facet of most nanoparticles, has not yet been possible. Low and variable temperature scanning tunneling microscopy coupled with density functional theory reveal a coverage-dependent range of highly ordered structures stabilized by two hydrogen bonds per molecule. While extended chains that resemble the hydrogen-bonded zigzag structures reported for solid methanol are an efficient way to pack methanol at higher coverages, lower surface coverages yield isolated hexamer units. These hexamers form the same number of hydrogen bonds as the chains but appear to repel one another on the surface. Annealing treatments lead to the desorption of methanol with almost no decomposition. This data serves as a useful guide to both the preferred adsorption geometries and energies of a variety of methanol structures on Cu(111) surfaces as a function of surface coverage.     

Nonprecious metal catalysts for fuel cell applications: electrochemical dioxygen activation by a series of first row transition metal tris(2-pyridylmethyl)amine complexes

A series of divalent first row triflate complexes supported by the ligand tris(2-pyridylmethyl)amine (TPA) have been investigated as oxygen reduction catalysts for fuel cell applications. [(TPA)M(2+)](n+) (M = Mn, Fe, Co, Ni, and Cu) derivatives were synthesized and characterized by X-ray crystallography, cyclic voltammetry, NMR spectroscopy, magnetic susceptibility, IR spectroscopy, and conductance measurements. The stoichiometric and electrochemical O(2) reactivities of the series were examined. Rotating-ring disk electrode (RRDE) voltammetry was used to examine the catalytic activity of the complexes on a carbon support in acidic media, emulating fuel cell performance. The iron complex displayed a selectivity of 89% for four-electron conversion and demonstrated the fastest reaction kinetics, as determined by a kinetic current of 7.6 mA. Additionally, the Mn, Co, and Cu complexes all showed selective four-electron oxygen reduction (<28% H(2)O(2)) at onset potentials (~0.44 V vs RHE) comparable to state of the art molecular catalysts, while being straightforward to access synthetically and derived from nonprecious metals.     

Observation of the psi(4415)-->DD2*(2460) decay using initial-state radiation

We report measurements of the exclusive cross section for e(+)e(-)-->D(0)D(-)pi(+) over the center-of-mass energy range 4.0 GeV to 5.0 GeV with initial-state radiation and the first observation of the decay psi(4415)-->D(0)D(-)pi(+). From a study of the resonant substructure in psi(4415) decay we conclude that the psi(4415)-->D(0)D(-)pi(+) decay is dominated by psi(4415)-->DD(2)(*)(2460). We obtain B(psi(4415)-->D(0)D(-)pi(nonresonant)(+))/B(psi(4415)-->DD(2)(*)(2460)-->D(0)D(-)pi(+))<0.22 at 90% C.L. The analysis is based on a data sample collected with the Belle detector with an integrated luminosity of 673 fb(-1).     

Observation of B_(s)(0)-->phigamma and search for B_(s)(0)-->gammagamma decays at Belle

We search for the radiative penguin decays B_{s}{0}-->varphigamma and B_{s}{0}-->gammagamma in a 23.6 fb{-1} data sample collected at the Upsilon(5S) resonance with the Belle detector at the KEKB e{+}e{-} asymmetric-energy collider. We observe for the first time a radiative penguin decay of the B_{s}{0} meson in the B_{s}{0}-->varphigamma mode and we measure B(B_{s}{0}-->varphigamma)=(57_{-15}{+18}(stat)-11+12(syst))x10{-6}. No significant B_{s}{0}-->gammagamma signal is observed and we set a 90% confidence level upper limit of B(B_{s}{0}-->gammagamma)<8.7x10{-6}.     

Observation of anomalous upsilon(1S)pi+pi(-) and upsilon(2S)pi+pi(-) production near the upsilon(5S) resonance

We report the first observation of e;{+}e;{-}-->Upsilon(1S)pi;{+}pi;{-}, Upsilon(2S)pi;{+}pi;{-}, and first evidence for e;{+}e;{-}-->Upsilon(3S)pi;{+}pi;{-}, Upsilon(1S)K+K-, near the peak of the Upsilon(5S) resonance at sqrt[s] approximately 10.87 GeV. The results are based on a data sample of 21.7 fb;{-1} collected with the Belle detector at the KEKB e;{+}e;{-} collider. Attributing the signals to the Upsilon(5S) resonance, the partial widths Gamma(Upsilon(5S)-->Upsilon(1S)pi;{+}pi;{-})=0.59+/-0.04(stat)+/-0.09(syst) MeV and Gamma(Upsilon(5S)-->Upsilon(2S)pi;{+}pi;{-})=0.85+/-0.07(stat)+/-0.16(syst) MeV are obtained from the observed cross sections. These values exceed by more than 2 orders of magnitude the previously measured partial widths for dipion transitions between lower Upsilon resonances.     

Observation of B{0}-->ppK*0 with a large K*0 polarization

Using a 492 fb{-1} data sample collected near the Upsilon(4S) resonance with the Belle detector at the KEKB asymmetric-energy e{+}e{-} collider, we observe the decay B{0}-->ppK*0 with a branching fraction of (1.18{-0.25}{+0.29}(stat)+/-0.11(syst))x10{-6}. We study the decay dynamics of B{0}-->ppK*0 and compare with B{+}-->ppK*+. The K*0 meson is found to be almost 100% polarized (with a fraction of (101+/-13+/-3)% in the helicity zero state), while the K*+ meson has a (32+/-17+/-9)% fraction in the helicity zero state. The direct CP asymmetries for B{0}-->ppK*0 and B{+}-->ppK*+ are measured to be -0.08+/-0.20+/-0.02 and -0.01+/-0.19+/-0.02, respectively. In addition, we report improved measurements of the branching fractions B(B{+}-->ppK*+)=(3.38{-0.60}{+0.73}+/-0.39)x10{-6} and B(B{0}-->ppK{0})=(2.51{-0.29}{+0.35}+/-0.21)x10{-6}, which supersede our previous measurements.