Hydrogen dissociation and diffusion on Ni- and Ti-doped Mg(0001) surfaces

It is well-known, both theoretically and experimentally, that alloying MgH(2) with transition elements can significantly improve the thermodynamic and kinetic properties for H(2) desorption, as well as the H(2) intake by Mg bulk. Here, we present a density functional theory investigation of hydrogen dissociation and surface diffusion over a Ni-doped surface and compare the findings to previously investigated Ti-doped Mg(0001) and pure Mg(0001) surfaces. Our results show that the energy barrier for hydrogen dissociation on the pure Mg(0001) surface is high, while it is small/null when NiTi are added to the surface as dopants. We find that the binding energy of the two H atoms near the dissociation site is high on Ti, effectively impeding diffusion away from the Ti site. By contrast, we find that on Ni, the energy barrier for diffusion is much reduced. Therefore, although both Ti and Ni promote H(2) dissociation, only Ni appears to be a good catalyst for Mg hydrogenation, allowing diffusion away from the catalytic sites. Experimental results corroborate these theoretical findings, i.e., faster hydrogenation of the Ni-doped Mg sample as opposed to the reference Mg- or Ti-doped Mg.     

Direct monitoring of metal ion transfer between two trafficking proteins

To avoid the toxic effects of both essential and nonessential metal ions, cells elaborate a variety of metal ion trafficking proteins that regulate metal ion mobility. While structures of several trafficking proteins have been determined, kinetic characterization of metal ion transfer between cognate protein partners and the factors controlling transfer has lagged behind, in part due to a limitation on methods to monitor the rapid transfer. In this Communication we report studies on the kinetics of Hg2+ transfer between separately expressed components of the flavoenzyme mercuric ion reductase (MerA) that take advantage of the sensitivity of the flavin fluorescence to the charge state of a cysteine thiol in the Hg2+ binding pathway. The thiolate form of C558 in the Tn501 MerA partially quenches the fluorescence of the oxidized enzyme. Protonation or binding of Hg2+ to the thiolate increases the fluorescence, providing a sensitive probe for kinetic analysis of the Hg2+ binding reaction. The kinetics of Hg2+ transfer in both directions between the cysteine pair of the separately expressed N-terminal domain and the C-terminal cysteines (C558, C559) of the catalytic core are presented, along with a model describing the overall process.     

Palladium-catalyzed oxidative cyclizations: synthesis of dihydropyranones and furanones

A boron-mediated syn- and anti-stereoselective aldol reaction giving rise to various beta-hydroxyenones was coupled to a Pd((II))-mediated oxidative cyclization to give 2,3,6-trisubstituted syn- and anti-dihydropyranones in good yields. The Pd((II))-mediated oxidative cyclization was expanded to alpha-hydroxyenones leading to furan-3(2H)-one derivatives, which include natural product bullatenone and a known precursor of geiparvarin. The sole product of the oxidative cyclization of alpha,beta-dihydroxyenone was a five-membered furan-3(2H)-one derivative, suggesting that the ring closure of these diols is both chemo- and regioselective.     

Experimental methods of X-ray stress analysis

A technique is described for measuring residual stresses in steels and composite materials by X-ray diffraction. Specimen preparation, X-ray diffractometer alignment, diffraction-peak location, and the determination of the elastic modulus, Poisson's ratio and stress factor are covered. Application examples include measurement of heat-treating and shot-peening stresses in steels and grinding and temperature stresses in WC-Co composites.     

The influence of spread of excitation on the detection of amplitude modulation imposed on sinusoidal carriers at high levels

The improvement in amplitude modulation (AM) detection thresholds with increasing level of a sinusoidal carrier has been attributed to listening on the high-frequency side of the excitation pattern, where the growth of excitation is more linear, or to an increase in the number of "channels" via spread of excitation. In the present study, AM detection thresholds were measured using a 1000-Hz sinusoidal carrier. Thresholds for modulation frequencies of 4-64 Hz improved by about 10-20 dB as the carrier level increased from 10 dB SL (14.5 dB SPL on average) to 80 dB SPL. To minimize the use of spread of excitation with an 80-dB carrier, tonal "restrictors" with frequencies of 501, 801, 1210, and 1510 Hz were used alone and in combination. High-frequency restrictors elevated AM detection thresholds, whereas low-frequency restrictors did not, indicating that excitation on the high side is more important for detecting AM. Results of modeling suggest that the improvement in AM detection thresholds at high levels is likely due to the use of a relatively linear growth of response on the high-frequency side of the excitation pattern.     

Development of Low-Cost Instrumentation for Single Point Autofluorescence Lifetime Measurements

Autofluorescence lifetime measurements, which can provide label-free readouts in biological tissues, contrasting e.g. different types and states of tissue matrix components and different cellular metabolites, may have significant clinical potential for diagnosis and to provide surgical guidance. However, the cost of the instrumentation typically used currently presents a barrier to wider implementation. We describe a low-cost single point time-resolved autofluorescence instrument, exploiting modulated laser diodes for excitation and FPGA-based circuitry for detection, together with a custom constant fraction discriminator. Its temporal accuracy is compared against a “gold-standard” instrument incorporating commercial TCSPC circuitry by resolving the fluorescence decays of reference fluorophores presenting single and double exponential decay profiles. To illustrate the potential to read out intrinsic contrast in tissue, we present preliminary measurements of autofluorescence lifetime measurements of biological tissues ex vivo. We believe that the lower cost of this instrument could enhance the potential of autofluorescence lifetime metrology for clinical deployment and commercial development.     

Statistical properties of many-particle spectra. II. Two-point correlations and fluctuations

The two-point correlation function for complex spectra described by the Gaussian Orthogonal Ensemble (GOE) is calculated, and its essential simplicity displayed, by an elementary procedure which derives from orthogonal invariance and the dominance of intrinsic binary correlations. The resultant function is used for an approximate calculation of the standard fluctuation measures. Good agreements are found with exact results where these are available, this incidentally demonstrating that the measures are, for the most part, two-point measures. It is shown that they vary slowly over the spectrum, a result which is in agreement both with experiment and with Monte Carlo calculations. The same technique can be used for higher-order correlation functions, and possibly also for more complicated ensembles in which case the results would be relevant to the question why GOE fluctuations give a good account of experimental results.     

An investigation of the laryngeal system as the resonance source of the singer''s formant

Since its introduction, the Sundberg model of the laryngeal system as the resonance source of the singer's formant has gained wide acceptance. However, no studies directly testing this hypothesis in vivo have previously been reported. Thus, the present study was undertaken to test this hypothesis on three classically trained professional male singers. The vocal behaviors of the singer-subjects were evaluated during modal and pulse register phonation via magnetic resonance imaging, strobolaryngoscopy, and acoustic analysis. Results indicated the subjects did not achieve the laryngopharyngeal/laryngeal outlet cross-sectional area ratio requisite to the model and that the formant remained robust in pulse register phonation. It was concluded that these subjects' behaviors were not consistent with Sundberg's model and that the model was inadequate to account for the generation of the singer's formant in these three subjects.     

Study of the centrally produced ωρ0 and ωω systems inpp interactions at 300 GeV/c

We have performed a search for vector-vector final states centrally produced in proton proton interactions at 300 GeV/c using the CERN Ω spectrometer. Evidence is found for ωρ⁰ production in the reactionpp→p _f (2π⁺2π^?2π⁰)p _s and for ωω production in the reactionpp→p _f (2π⁺2π^?2π⁰)p _s . However no evidence is found for ωø production in the reactionpp→p _f (K ⁺ K ^?π⁺π^?π⁰)p _s .     

Equilibrium point damage prognosis models for structural health monitoring

Most structural dynamic systems are of high order; however, they often exhibit phenomena that can be dealt with effectively using low order models. This paper presents a method for describing certain kinds of damage evolution in mechanical systems. The method relies on a simple principle that as damage evolves in a structural dynamic system, the damage indicator (i.e., diagnostic feature) behaves like a stable quasi-stationary equilibrium point in a subsidiary non-linear bifurcating system within the so-called damage center manifold. It is shown that just as linear normal modes govern the behavior of linear structures with idealized damping, so too do non-linear normal forms govern the evolution of damage within structures in many instances. The method is justified with citations from the literature on certain types of mechanical failure and then applied in an experimental case involving reversible damage in a bolted fastener. Off-line experiments on a rotorcraft fuselage show that the evolution of damage is sensitive to both temporal and spatial bifurcation parameters. A diagnostic sensing strategy whereby output-only transmissibility features are used to decrease the order of high order structural dynamic measurements is also described.