Adsorbate-oxide interactions during the NO + CO reaction on MgO(100) supported Pd monolayer films

The potential energy diagram for the NO+CO reaction on 1, 2, and 3 monolayer (ML) Pd films supported by MgO(100) is calculated using density functional theory. Thin Pd films are generally found to be more reactive than thick films, with a notable exception for nitrogen adsorption on 2 ML Pd/MgO(100). For this system an attractive through-the-metal adsorbate-oxide interaction of 0.5 eV is identified. Nitrogen adsorption is consequently estimated to provide a thermodynamic driving force for the reconstruction of MgO(100) supported 3 ML (or thicker) Pd clusters into thinner Pd clusters.     

Collective states in highly symmetric atomic configurations and single-photon traps

We study correlated states in circular and linear-chain configurations of identical two-level atoms containing the energy of a single quasi-resonant photon in the form of a collective excitation, where the collective behavior is mediated by exchange of transverse photons between the atoms. For a circular atomic configuration containing N atoms, the collective energy eigenstates can be determined by group-theoretical means making use of the fact that the configuration possesses a cyclic symmetry group Z _N . For these circular configurations, the carrier spaces of the various irreducible representations of the symmetry group are at most two-dimensional, so that the effective Hamiltonian on the radiationless subspace of the system can be diagonalized analytically. As a consequence, the radiationless energy eigenstates carry a Z _N quantum number p = 0, 1, …, N, which is analogous to the angular momentum quantum number l = 0, 1, … carried by particles propagating in a central potential, such as a hydrogen-like system. Just as the hydrogen s states are the only electronic wave functions that can occupy the central region of the Coulomb potential, the quasi-particle corresponding to a collective excitation of the circular atomic sample can occupy the central atom only for vanishing Z _N quantum number p. When a central atom is present, the p = 0 state splits into two, showing level crossing at certain radii; in the regions between these radii, damped oscillations between two “ extreme” p = 0 states occur, where the excitation occupies either the outer atoms or the central atom only. For large numbers of atoms in a maximally subradiant state, a critical interatomic distance of λ/2 emerges both in the linear-chain and in the circular configuration of atoms. The spontaneous decay rate of the linear configuration exhibits a jumplike “critical” behavior for next-neighbor distances close to a half-wavelength. Furthermore, both the linear-chain and the circular configurations exhibit exponential photon trapping once the next-neighbor distance becomes less than a half-wavelength, with the suppression of spontaneous decay being particularly pronounced in the circular system. In this way, circular configurations containing sufficiently many atoms may be natural candidates for single-photon traps.     

Site planning for clinical NMR systems

The installation of a nuclear magnetic resonance imaging system (NMR or MRI) in a clinical environment requires detailed planning to insure adequate safety and optimal system performance. The important considerations of site planning are discussed in this paper and solutions suggested by various system manufacturers are detailed. In addition, experimental results illustrating the effects of improper site planning are also presented.     

Search for supersymmetry at the LHC in events with jets and missing transverse energy

A search for events with jets and missing transverse energy is performed in a data sample of pp collisions collected at √s=7 TeV by the CMS experiment at the LHC. The analyzed data sample corresponds to an integrated luminosity of 1.14 fb(-1). In this search, a kinematic variable α(T) is used as the main discriminator between events with genuine and misreconstructed missing transverse energy. No excess of events over the standard model expectation is found. Exclusion limits in the parameter space of the constrained minimal supersymmetric extension of the standard model are set. In this model, squark masses below 1.1 TeV are excluded at 95% C.L. Gluino masses below 1.1 TeV are also ruled out at 95% C.L. for values of the universal scalar mass parameter below 500 GeV.     

Highly corrosion resistant siloxane-polymethyl methacrylate hybrid coatings

Siloxane-polymethyl methacrylate hybrid films were deposited on carbon steel substrates by dip-coating from a sol prepared by acid-catalyzed hydrolytic co-polycondensation of tetraethoxysilane (TEOS) and 3-methacryloxy propyl-trimethoxysilane (MPTS), followed by radical polymerization of methyl methacrylate (MMA). Structural properties of the hybrids were studied using ²⁹Si and ¹³C nuclear magnetic resonance (NMR), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA), as a function of the MMA/MPTS ratio, which ranged between 2 and 10. The efficiency of corrosion protection of hybrid-coated carbon steel was investigated by XPS, potentiodynamic polarization curves and electrochemical impedance spectroscopy after immersion of the material in acidic and neutral saline aqueous solution. The NMR and TGA results indicate a high degree of polycondensation (84%) and elevated thermal stability of 410?°C for the hybrid film with a MMA/MPTS ratio of 8, exhibiting also and excellent adhesion to the substrate. The XPS analysis confirmed the variation of the MMA phase in the hybrid, and showed that no corrosion-induced changes had occurred after 18?days immersion of the coated steel in 3.5% NaCl solution. Potentiodynamic polarization curves have shown that the hybrid coating prepared using a TEOS/MPTS ratio of 8 yielded the best anti-corrosion performance. It acts as a very efficient corrosion barrier, increasing the total impedance by almost 6 orders of magnitude and reducing the current densities by 4 orders of magnitude, compared to the bare electrode. The obtained results are discussed based on the correlation of structural information with impedance data presented for both electrolytes in the form of electrical equivalent circuits.     

Stoichiometric inhibition of amyloid beta-protein aggregation with peptides containing alternating alpha,alpha-disubstituted amino acids

We have prepared two peptides based on the hydrophobic core (Lys-Leu-Val-Phe-Phe) of amyloid beta-protein (Abeta) that contain alpha,alpha-disubstituted amino acids at alternating positions, but differ in the positioning of the oligolysine chain (AMY-1, C-terminus; AMY-2, N-terminus). We have studied the effects of AMY-1 and AMY-2 on the aggregation of Abeta and find that, at stoichiometric concentrations, both peptides completely stop Abeta fibril growth. Equimolar mixtures of AMY-1 and Abeta form only globular aggregates as imaged by scanning force microscopy and transmission electron microscopy. These samples show no signs of protofibrillar or fibrillar material even after prolonged periods of time (4.5 months). Also, 10 mol % of AMY-1 prevents Abeta self-assembly for long periods of time; aged samples (4.5 months) show only a few protofibrillar or fibrillar aggregates. Circular dichroism spectroscopy of equimolar mixtures of AMY-1 and Abeta show that the secondary structure of the mixture changes over time and progresses to a predominantly beta-sheet structure, which is consistent with the design of these inhibitors preferring a sheet-like conformation. Changing the position of the charged tail on the peptide, AMY-2 interacts with Abeta differently in that equimolar mixtures form large ( approximately 1 mum) globular aggregates which do not progress to fibrils, but precipitate out of solution. The differences in the aggregation mediated by the two peptides is discussed in terms of a model where the inhibitors act as cosurfactants that interfere with the native ability of Abeta to self-assemble by disrupting hydrophobic interactions either at the C-terminus or N-terminus of Abeta.     

Novel beta-lactam antibiotics synthesized by amination of catechols using fungal laccase

Novel cephalosporins, penicillins, and carbacephems were synthesized by amination of catechols with amino-beta-lactams like cefadroxil, amoxicillin, ampicillin and the structurally related carbacephem loracarbef using laccase from Trametes sp. All isolated monoaminated products inhibited the growth of several Gram positive bacterial strains in the agar diffusion assay, among them methicillin-resistant Staphylococcus aureus strains and vancomycin-resistant Enterococci. Observed differences in the cytotoxicity and in vivo activity in a "Staphylococcus-infected, immune suppressed mouse" model are discussed.     

Oscillating oxygen evolution at Ta anodes

Anodic Ta oxide films are said to inhibit oxygen evolution. In industry, however, large amounts of gas are evolved during the anodization of tantalum anodes for electrolytic capacitor fabrication. We quantified the oxygen by fluorescence quenching in a flow-through cuvette and found that 4% of the anodic charge are consumed for oxygen evolution. In wires or sheets, this oxygen is removed by diffusion without bubble formation and, thus, not recognized. Due to the large inner area of the sintered Ta anodes, the oxygen evolution causes strong oscillations of the current density and bubble formation. The amount of oxygen is proportional to the oxide amount formed in parallel. This is explained by a model where mobile ions during oxide growth form interband states which allow electron tunneling. Accordingly, stationary no oxygen evolution is observed.     

Synthesis and Photophysical Properties of Multichromophoric Carbonyl‐Bridged Triarylamines

The synthesis and photophysical properties of two novel multichromophoric compounds is presented. Their molecular design comprises a carbonyl‐bridged triarylamine core and either naphthalimides or 4‐(5‐hexyl‐2,2′‐bithiophene)naphthalimides as second chromophore in the periphery. The lateral chromophores are attached to the core via an amide linkage and a short alkyl spacer. The synthetic approach demonstrates a straightforward functionalization strategy for carbonyl‐bridged triarylamines. Steady‐state and time‐resolved spectroscopic investigations of these compounds, in combination with three reference compounds, provide clear evidence for energy transfer in both multichromophoric compounds. The direction of the energy transfer depends on the lateral chromophore used. Furthermore, the compound bearing the lateral 4‐(bithiophene)naphthaimides is capable of forming fluorescent gels at very low concentrations in the sub‐millimolar regime whilst retaining its energy transfer properties.