Proton-detected scalar coupling based assignment strategies in MAS solid-state NMR spectroscopy applied to perdeuterated proteins

Assignment of proteins in MAS (magic angle spinning) solid-state NMR relies so far on correlations among heteronuclei. This strategy is based on well dispersed resonances in the ¹⁵N dimension. In many complex cases like membrane proteins or amyloid fibrils, an additional frequency dimension is desirable in order to spread the amide resonances. We show here that proton detected HNCO, HNCA, and HNCACB type experiments can successfully be implemented in the solid-state. Coherences are sufficiently long lived to allow pulse schemes of a duration greater than 70 ms before incrementation of the first indirect dimension. The achieved resolution is comparable to the resolution obtained in solution-state NMR experiments. We demonstrate the experiments using a triply labeled sample of the SH3 domain of chicken α-spectrin, which was re-crystallized in H₂O/D₂O using a ratio of 1/9. We employ paramagnetic relaxation enhancement (PRE) using EDTA chelated Cu^II to enable rapid data acquisition.     

Coherent and incoherent π0 photoproduction from the deuteron

Differential cross-sections for the reactions d (γ,π⁰)d and d (γ,π⁰)pn have been measured at MAMI with the TAPS detector setup in the energy range 140 MeV < E _γ < 306 MeV. By use of the Glasgow tagging spectrometer an 0.8 MeV energy resolution for photons incident on the target was achieved. The π⁰ missing energy resolution was sufficient for a reliable separation of coherent and incoherent channels. The data for the break-up channel exhibit very strong final state interaction effects, whereas the observed angular dependence of the inclusive process d (γ,π⁰)X is in quantitative agreement with predictions for a quasi-free process. The observed absolute d (γ,π⁰)X cross-sections, on the other hand, are significantly smaller than predicted by the quasi-free process for E _γ >∼ 250 MeV. Associating this failure with the π⁰ photoproduction on the neutron would suggest that its cross-section is up to 25% below the presently believed value. Received: 13 February 2001 / Accepted: 13 April 2001     

The effect of oxidation on the surface-near lattice relaxation in FeNi nanoparticles

The near-surface oxidation-induced lattice relaxation and compositional changes of FeNi alloy nano-particles are investigated. Using a newly developed transfer system, the particle structure was characterised by means of aberration-corrected HR-TEM prior to exposing the particles to ambient air. This allows for a comparison of oxidised and un-oxidised particles, respectively. Independent of the oxidation, the surface-near and/or interface-near metal lattice was found to be expanded by up to 3%. EELS profiles clearly reveal an enrichment of Fe at the particle surfaces. MD simulations in combination with HR-TEM contrast simulations were conducted to investigate the effect of the Fe enrichment on the structural relaxation. The results show that a surface-near over-stoichiometric enrichment of Fe indeed causes a dilation that counteracts a compression of the lattice at the particle surface as obtained for homogeneously alloyed particles. Besides, the large lattice mismatch between the metallic cores and the NiFe₂O₄ shells causes the formation of step dislocations in the close vicinities of the interface. In essence, the surface-near lattice relaxation in oxide free particles is found to be due to a segregation of Fe to the surface, whereas in the case of shell–core particles, no systematic influence of the oxide on the lattice relaxation was found.     

Signature of a type-a glass transition and intrinsic confinement effects in a binary glass-forming system

We study dynamically highly asymmetric binary mixtures comprised of small methyl tetrahydrofuran (MTHF) molecules and polystyrene. Combined use of dielectric spectroscopy, ^{2}H nuclear magnetic resonance, incoherent quasielastic neutron scattering, and depolarized dynamic light scattering allows us to selectively probe the dynamics of the components in a broad dynamic range. It turns out that the mixtures exhibit two glass transitions in a wide concentration range although being fully miscible on a macroscopic scale. In between both glass transition temperatures, the dynamics of the small molecules show strong confinement effects, e.g., a crossover from Vogel-Fulcher to Arrhenius behavior of the time constants. Moreover, the dynamical behavior of small molecules close to the slow matrix is consistent with mode coupling theory predictions for a type-A glass transition, which was expected from recent theoretical and simulation studies in comparable systems.     

Signatures of non-Abelian statistics in nonlinear Coulomb blockade transport

Signatures of the non-Abelian statistics of quasiparticles in the ν=5/2 quantum Hall state are predicted to be present in the current-voltage characteristics of tunneling through one or two quantum Hall puddles of Landau filling ν(a) embedded in a bulk of filling ν(b) with (ν(a),ν(b))=(2,5/2) and (ν(a),ν(b))=(5/2,2).     

Enhancement of chloroform degradation by the combination of hydrodynamic and acoustic cavitation

The decomposition of chloroform by the combination of hydrodynamic and acoustic cavitation (Hydrodynamic-Acoustic-Cavitation/HAC) has been investigated. The flow rate and the hole diameter of the orifice plate remarkably affect the conversion of chloroform in the combined system. The conversion increases with increasing fluid velocity without any restriction. With a 2.8mm orifice plate the conversion reaches an optimal value. A synergistic effect has been obtained by the hybrid method of acoustic and hydrodynamic cavitation. The total synergistic effect achieves 17% and 73% per pass, respectively. The analysis of the energy efficiencies shows different results. Due to high optimization potential, this hybrid method can be visualized as a new step for wastewater treatment.