Measurement and phase-shift analysis of the p parameter in π+p scattering at 236 MeV

The P parameter for π⁺p scattering at 236.3 MeV has been measured between 50° and 146° c.m. with very low background using a butanol polarized proton target. The resulting D phases are in fair agreement with dispersion relation values.     

Turbulence measurements in a transonic two-passage turbine cascade

This paper presents detailed turbulence measurements in a two-dimensional, transonic, double passage turbine cascade. Particle image velocimetry was used to obtain mean velocity and turbulence measurements all around a single turbine blade within about 2 mm of the blade and wall surfaces. The passage walls were designed using an optimization procedure so that the blade surface pressure distribution matches that of the blade in an infinite cascade. The resulting experimental model captures much of the complexity of a real turbine stage (including high streamline curvature, strong accelerations, and shocks) in a passage with a continuous wall shape, allowing for high measurement resolution and well controlled boundary conditions for comparison to CFD. The measurements show that in the inviscid regions of the passage the absolute level of the turbulent fluctuations does not change significantly as the flow accelerates, while the local turbulence intensity drops rapidly as the flow accelerates. These results provide a benchmark data set that can be used to improve turbulence models.     

Comparison of Continuous Wave, Spin Echo, and Rapid Scan EPR of Irradiated Fused Quartz

The E' defect in irradiated fused quartz has spin lattice relaxation times (T(1)) about 100 to 300 μs and spin-spin relaxation times (T(2)) up to about 200 μs, depending on the concentration of defects and other species in the sample. These long relaxation times make it difficult to record an unsaturated continuous wave (CW) electron paramagnetic resonance (EPR) signal that is free of passage effects. Signals measured at X-band (~9.5 GHz) by three EPR methods: conventional slow-scan field modulated EPR, rapid scan EPR, and pulsed EPR, were compared. To acquire spectra with comparable signal-to-noise, both pulsed and rapid scan EPR require less time than conventional CW EPR. Rapid scan spectroscopy does not require the high power amplifiers that are needed for pulsed EPR. The pulsed spectra, and rapid scan spectra obtained by deconvolution of the experimental data, are free of passage effects.     

Relaxation times and line widths of isotopically-substituted nitroxides in aqueous solution at X-band

Optimization of nitroxides as probes for EPR imaging requires detailed understanding of spectral properties. Spin lattice relaxation times, spin packet line widths, nuclear hyperfine splitting, and overall lineshapes were characterized for six low molecular weight nitroxides in dilute deoxygenated aqueous solution at X-band. The nitroxides included 6-member, unsaturated 5-member, or saturated 5-member rings, most of which were isotopically labeled. The spectra are near the fast tumbling limit with T₁∼T₂ in the range of 0.50–1.1 μs at ambient temperature. Both spin–lattice relaxation T₁ and spin–spin relaxation T₂ are longer for ¹⁵N- than for ¹⁴N-nitroxides. The dominant contributions to T₁ are modulation of nitrogen hyperfine anisotropy and spin rotation. Dependence of T₁ on nitrogen nuclear spin state m_I was observed for both ¹⁴N and ¹⁵N. Unresolved hydrogen/deuterium hyperfine couplings dominate overall line widths. Lineshapes were simulated by including all nuclear hyperfine couplings and spin packet line widths that agreed with values obtained by electron spin echo. Line widths and relaxation times are predicted to be about the same at 250 MHz as at X-band.     

The mechanism of formation of N-formylkynurenine by heme dioxygenases

Heme dioxygenases catalyze the oxidation of L-tryptophan to N-formylkynurenine (NFK), the first and rate-limiting step in tryptophan catabolism. Although recent progress has been made on early stages in the mechanism, there is currently no experimental data on the mechanism of product (NFK) formation. In this work, we have used mass spectrometry to examine product formation in a number of dioxygenases. In addition to NFK formation (m/z = 237), the data identify a species (m/z = 221) that is consistent with insertion of a single atom of oxygen into the substrate during O(2)-driven turnover. The fragmentation pattern for this m/z = 221 species is consistent with a cyclic amino acetal structure; independent chemical synthesis of the 3a-hydroxypyrroloindole-2-carboxylic acid compound is in agreement with this assignment. Labeling experiments with (18)O(2) confirm the origin of the oxygen atom as arising from O(2)-dependent turnover. These data suggest that the dioxygenases use a ring-opening mechanism during NFK formation, rather than Criegee or dioxetane mechanisms as previously proposed.     

The Structure of Cellulose by Conformational Analysis. Part 5. The Cellulose Ii Water Sorption IsothermXS

Exact values of the sorption energies of single molecules of water on all available sorption sites of crystalline cellulose II have been obtained by conformational analysis. The sorption energies are equated to the total energy (E_tot ) of interaction between the water molecule and all the suitable atomic groups of the cellulose. E_tot is composed of van der Waals, H-bond, and electrostatic energies. The interferences of water molecules on vicinal sorption sites were obtained. Sites in which such interference can occur were identified for crystalline cellulose II. Sorption energy in crystalline cellulose II appears to depend only on the interaction of water with surface sorption sites of the crystal. There appears to be favorable sorption on 1) sites exerting high attractive forces, and 2) sites which are exposed and protrude from the crystal surface. Sites recessed from the crystal surface are generally repulsive due to strong interactions with neighboring groups. All the sorption energies of the “monolayer” were calculated. Very strong sorption sites cannot always form a second layer because of strong steric hindrance from vicinal groups. Sorption capacities of crystalline cellulose II were calculated, and the isotherm of the schematic five chain crystallite used was constructed by theoretical means. The results obtained were briefly compared with those for cellulose I crystallites and amorphous cellulose. The inflection points of the isotherm and the variability of Dent's k ₁ constant for the water monolayer with relative humidity for the cellulose I and II isotherms were also calculated by theoretical means.     

The application of (Z)-3-aryl-3-haloenoic acids to the synthesis of (Z)-5-benzylidene-4-arylpyrrol-2(5H)-ones

Studies directed at the synthesis of (Z)-5-benzylidene-4-arylpyrrol-2(5H)-ones from (Z)-3-aryl-3-haloenoic acids are described. The successful strategy relies on the preparation of (Z)-3-aryl-3-haloenoic acids from acetophenones through the corresponding (Z)-3-aryl-3-haloenals and the conversion of the (Z)-3-aryl-3-haloenoic acids to (Z)-5-benzylidene-4-aryl-5H-furan-2-ones. The furanones were subsequently treated with primary amines and dehydrated to the corresponding (Z)-5-benzylidene-4-arylpyrrol-2(5H)-ones.     

Electron spin relaxation in x-lithium phthalocyanine

Continuous-wave linewidths and spin susceptibilities, spin-spin relaxation rates (1/T2), and spin-lattice relaxation rates (1/T1) for two sources of x-LiPc were measured at 9.5 GHz between 15 and 298 K. Relaxation rates at 34 GHz were measured between 80 and 298 K. Room-temperature relaxation rates also were measured at 250 MHz, 1.9 GHz, and 2.76 GHz. The temperature dependences of linewidths and spin susceptibilities are characteristic of 1-D organic conductors. The ratio of populations of localized and delocalized electrons varies with sample preparation. For a single needle between 15 and about 200 K, 1/T2 is higher for the parallel orientation, but 1/T1 is higher for the perpendicular orientation, consistent with predictions based on dipolar interactions. Between about 60 and 150 K, which is the temperature regime in which spin susceptibility is changing rapidly with temperature, 1/T1 exhibits a non-monotonic dependence on temperature and is lower at 34 GHz than at 9.5 GHz. In other organic conductors, this dependence has been attributed to a bottleneck mechanism of relaxation. At higher temperatures, 1/T1 becomes less orientation-dependent. At room temperature, T1 increases rapidly between 250 MHz (3.0 micros) and 2.76 GHz (6.3 micros) and then shows less frequency dependence up to 34 GHz (9.8 micros). The relaxation rate near room temperature might have a substantial contribution from spin hopping perpendicular to the stacking axis of the molecules.