Electron density spatial profiles of the DCP source

Electron densities are measured in the high current, analytical and intervening zones of a DCP whose operating parameters are systematically varied. Detailed N_e distribution profiles are obtained for various sleeve flow, nebulizer flow, arc current and matrix concentration regimes. Flowing argon is found to establish a thermal pinch in the high current zone and to steepen gradients in plasmas employed for spectrochemical analysis. The distinctive electron density distributions in the DCP are more sensitive to modulation of gas flow variables than to changes in arc current. Magnetic pressure has no discernible role in pinch formation. Electron densities in spectroscopic regions are minimally affected by easily ionized or other matrix constituents at usual analytical concentrations.     

Aromaticity and tautomerism—VII: Empirical resonance energy and conjugation energy of pyrazole and isoxazole from heats of dehydration data

The dehydration of various 4,5-dihydro-4- and -5-hydroxy derivatives of pyrazole and isoxazole has been investigated. Heats of dehydration of 4,5-duiydro-4-hydroxy-1,3,5-tripbenylpyrazole and 4,5-dihydro-5-hydroxy-isoxazole are evaluated and used to assess the empirical resonance energy and conjugation energy of pyrazole and isoxazole. The former possesses resonance stabilisation comparable to pyrrole but that of the latter is low.     

Reduced data acquisition time in multi-dimensional NMR spectroscopy using multiple-coil probes

A new hardware-based approach is presented to reduce data acquisition times in multi-dimensional NMR spectroscopy using a multiple-coil probe. Using a four-coil setup, two-dimensional COSY and TOCSY spectra were acquired in one-quarter the time of conventional spectra by simultaneous acquisition of different effective t1 evolution times for each coil. Data processing consists of simple phase-shifting and intensity normalization of the individual data sets, and results in spectra almost identical to those acquired in a conventional manner. This method can potentially be integrated with other new data acquisition and processing schemes for further increases in data acquisition speed.     

Inhibition studies on salicylate synthase

Analogues of chorismate and isochorismate were designed and tested as potential inhibitors in the first inhibition study against a salicylate synthase.     

Electrocatalysis of peroxide reduction by Au-stabilized, Fe-containing poly(vinylpyridine) films

We show that poly(vinylpyridine) (PVP) coated glassy carbon surfaces containing Fe(CN)6(3-) exhibit catalytic activity toward electroreduction of H2O2. While Fe(CN)6(3-) is catalytically inactive in solution phase, it exhibits catalytic activity upon incorporation into the PVP film, because film incorporation leads to an open coordination site in the otherwise inert Fe(CN)6(3-) molecule. However, this catalytic activity is quickly lost during H2O2 electroreduction due to leaching of the Fe species from the PVP film. The Fe catalyst in the PVP film could be stabilized by 1 order of magnitude in time by electrodeposition of small Au particles. Characterization of the film using scanning electron microscopy, secondary ion mass spectroscopy, and Raman spectroscopy shows that covalent attachment between the Au particle and the Fe-based catalyst is a likely mechanism for catalyst stabilization.     

A novel oxidative rearrangement of 6-methoxypyran-2-ones

As part of our continuing studies of pyrone-containing natural products, a series 6-methoxypyran-2-ones were synthesized. These were found to react with molecular oxygen at 20 degrees C, and this novel reaction yielded a series of highly functionalized alpha,beta-butenolides. [reaction: see text]     

Primarily nonlinear effects observed in a driven asymmetrical vibrating wire

The purpose of the work reported here is to further experimentally explore the wide variety of behaviors exhibited by driven vibrating wires, primarily in the nonlinear regime. When the wire is driven near a resonant frequency, it is found that most such behaviors are significantly affected by the splitting of the resonant frequency and by the existence of a "characteristic" axis associated with each split frequency. It is shown that frequency splitting decreases with increasing wire tension and can be altered by twisting. Two methods are described for determining the orientation of characteristic axes. Evidence is provided, with a possible explanation, that each axis has the same orientation everywhere along the wire. Frequency response data exhibiting nonlinear generation of transverse motion perpendicular to the driving direction, hysteresis, linear generation of perpendicular motion (sometimes tubular), and generation of motion at harmonics of the driving frequency are exhibited and discussed. Also reported under seemingly unchanging conditions are abrupt large changes in the harmonic content of the motion that sometimes involve large subharmonics and harmonics thereof. Slow transitions from one stable state of vibration to another and quasiperiodic motions are also exhibited. Possible musical significance is discussed.     

A theoretical model describing the transfer characteristics of a membrane hydrophone and validation

This paper presents a theoretical model describing the transfer characteristics of a bilaminar polyvinylidene fluoride membrane hydrophone. The model applied uses a matrix formulation for one-dimensional propagation in multi-layered media. Arbitrary interconnections of piezoelectric layers are possible. The electrical transfer characteristics of the hydrophone leg and cable are modelled as transmission lines using a two-port network approach. The model is validated against measured open-circuit sensitivities for a 25 microm film thickness 0.5 mm active element diameter bilaminar hydrophone (50 microm total film thickness). Good agreement between theory and experiment is demonstrated. A 9 microm film thickness 0.5 mm active element diameter bilaminar hydrophone (18 microm total film thickness) together with amplifier is also modelled. The voltage at the output stage of the amplifier is measured and, by knowledge of the transfer characteristics of the complete system, the pressure waveform at the hydrophone position is estimated and compared with the acoustic pressure waveform derived using a laser interferometer. Good agreement is obtained.     

Phonons from powder diffraction: a quantitative model-independent evaluation

We describe a model-independent approach for the extraction of detailed lattice dynamics information from neutron powder diffraction data, based on a statistical analysis of atomistic configurations generated using reverse Monte Carlo structural refinement. Phonon dispersion curves for MgO extracted in this way are shown to reproduce many of the important features found in those determined independently using neutron triple-axis spectroscopy. By means of molecular dynamics simulations, we quantify the extent to which the diffraction data are sensitive to lattice dynamics in this system.