An acoustic anomaly at the phase transition in GeTeSnTe alloy single crystals

The ultrasonic wave velocities and attenuation have been measured in single crystals of 20 mole.% GeTeSnTe alloys between 90 and 373°K. The ultrasound velocities and thus the elastic constants show a step-like behaviour, which is accompanied by a peak in the attenuation, at the cubic to rhombohedral transformation temperature (240°K). In the vicinity of the transition a strong interaction occurs between the acoustic phonon modes and the soft TO mode.     

Active Raman sounding of the earth's water vapor field

The typically weak cross-sections characteristic of Raman processes has historically limited their use in atmospheric remote sensing to nighttime application. However, with advances in instrumentation and techniques, it is now possible to apply Raman lidar to the monitoring of atmospheric water vapor, aerosols and clouds throughout the diurnal cycle. Upper tropospheric and lower stratospheric measurements of water vapor using Raman lidar are also possible but are limited to nighttime and require long integration times. However, boundary layer studies of water vapor variability can now be performed with high temporal and spatial resolution. This paper will review the current state-of-the-art of Raman lidar for high-resolution measurements of the atmospheric water vapor, aerosol and cloud fields. In particular, we describe the use of Raman lidar for mapping the vertical distribution and variability of atmospheric water vapor, aerosols and clouds throughout the evolution of dynamic meteorological events. The ability of Raman lidar to detect and characterize water in the region of the tropopause and the importance of high-altitude water vapor for climate-related studies and meteorological satellite performance are discussed.     

Actions of Picture Groups on CAT(0) Cubical Complexes

A class of groups, called picture groups, is defined. Richard Thompsons groups F, T, and V are all picture groups. Each picture group is shown to act properly and isometrically on a CAT(0) cubical complex. In particular, all picture groups are a-T-menable.Mathematics Subject Classifications (2000). 20F65, 43A15.     

Variegated micelle surfaces: correlating the microstructure of mixed surfactant micelles with bulk solution properties

Electron paramagnetic resonance, viscosity, and small-angle neutron scattering (SANS) measurements have been used to study the interaction of mixed anionic/nonionic surfactant micelles with the polyampholytic protein gelatin. Sodium dodecyl sulfate (SDS) and the nonionic surfactant dodecylmalono-bis-N-methylglucamide (C12BNMG) were chosen as "interacting" and "noninteracting" surfactants, respectively; SDS micelles bind strongly to gelatin but C12BNMG micelles do not. Further, the two surfactants interact synergistically in the absence of the gelatin. The effects of total surfactant concentration and surfactant mole fraction have been investigated. Previous work (Griffiths et al. Langmuir 2000, 16 (26), 9983-9990) has shown that above a critical solution mole fraction, mixed micelles bind to gelatin. This critical mole fraction corresponds to a micelle surface that has no displaceable water (Griffiths et al. J. Phys. Chem. B 2001, 105 (31), 7465). On binding of the mixed micelle, the bulk solution viscosity increases, with the viscosity-surfactant concentration behavior being strongly dependent on the solution surfactant mole fraction. The viscosity at a stoichiometry of approximately one micelle per gelatin molecule observed in SDS-rich mixtures scales with the surface area of the micelle occupied by the interacting surfactant, SDS. Below the critical solution mole fraction, there is no significant increase in viscosity with increasing surfactant concentration. Further, the SANS behavior of the gelatin/mixed surfactant systems below the critical micelle mole fraction can be described as a simple summation of those arising from the separate gelatin and binary mixed surfactant micelles. By contrast, for systems above the critical micelle mole fraction, the SANS data cannot be described by such a simple approach. No signature from any unperturbed gelatin could be detected in the gelatin/mixed surfactant system. The gelatin scattering is very similar in form to the surfactant scattering, confirming the widely accepted picture that the polymer "wraps" around the micelle surface. The gelatin scattering in the presence of deuterated surfactants is insensitive to the micelle composition provided the composition is above the critical value, suggesting that the viscosity enhancement observed arises from the number and strength of the micelle-polymer contact points rather than the gelatin conformation per se.     

Suppression of auditory nerve responses. II. Suppression threshold and growth, iso-suppression contours

Two-tone "synchrony suppression" was studied in responses of single auditory nerve fibers recorded from anesthetized cats. Suppression thresholds for suppressor tones set to a fiber's characteristic frequency (CF) were approximately equal to discharge rate thresholds for CF tones. Suppression thresholds above and below CF were usually lower than the corresponding discharge rate thresholds. However, at all frequencies studied (including CF), suppression thresholds were higher than the corresponding thresholds for discharge synchronization. Across fibers, rates of suppression growth for suppressors at CF were greatest in low-CF fibers and least in high-CF fibers, and there was a systematic decrease in suppression growth rate at CF as CF increased. Within fibers, rates of suppression growth above CF were typically less than at CF, and slopes were monotonically decreasing functions of frequency. Within-fiber rates of suppression growth below CF were variable, but they usually were greater than rates of growth at CF. Iso-suppression contours (frequencies and intensities producing criterion amounts of suppression) indicated that tones near CF are the most potent suppressors at near-threshold intensities, and that the frequency producing the most suppression usually shifts downward as the amount of suppression increases. These data support the notion that synchrony suppression arises primarily as a passive consequence of hair cell activation.     

An ENDOR and DFT analysis of ‘solvatochromic’ effects in an oxovanadium (IV) complex

The ‘solvatochromic’ effects of a vanadyl salen complex [VO^IV(salen)] in frozen solution was studied by ENDOR and DFT calculations. In a non-coordinating solvent (dichloromethane), both ENDOR and DFT were in excellent agreement on the expected square pyramidal structure, where V^IV=O is positioned out of the equatorial ligand xy-plane (as determined from calculated VH distances). In a coordinating solvent (dimethylformamide), a subtle perturbation from the square pyramidal structure was observed, suggesting that DMF coordinates trans to the vanadyl oxo-ligand, pulling V^IV=O back into the ligand plane. The axial coordination of DMF was confirmed by ENDOR and in the DFT optimised [VO^IV(salen)]–DMF complex.     

Direct observation of enantiomer discrimination of epoxides by chiral salen complexes using ENDOR

Electron nuclear double resonance (ENDOR) spectroscopy was used to investigate the weak enantioselective binding between chiral salen complexes [VO(1)] ((R,R)- and (S,S)-vanadyl N,N'-bis(3,5-di-tert-butylsalcylidene)-1,2-cyclohexanediamine) and chiral epoxides (e.g., (R)-/(S)-propylene epoxide, 5) in frozen (10 K) solution. Differences in epoxide binding by enatiomers of [VO(1)] was evidenced by changes to the 1H epoxide derived peaks in the ENDOR spectra, such that (R,R)-[VO(1)] + (R)-5 and (R,R)-[VO(1)] + (S)-5 yield noticeably different spectra. These changes were assigned to the small structural differences between the diastereomeric metal-epoxide adducts. Simulation of the spectra revealed differences in the VO...1Hepoxide distances for the diastereomeric pairs, which was confirmed by a complementary set of density functional theory (DFT) calculations. While the epoxide molecule is very weakly coordinated, ENDOR measurements of the racemic complex in racemic epoxide nevertheless indicated the preferential coordination of the (R)-5 to (R,R)-[VO(1)] (likewise (S)-(5) to (S,S)-[VO(1)]), which is favored over the binding of (S)-5 epoxide to (R,R)-[VO(1)] (and likewise (R)-5 epoxide to (S,S)-[VO(1)]). This demonstrates the unique power of the ENDOR technique to resolve weak chiral interactions for which EPR spectroscopy alone lacks sufficient resolution.     

Reaction kinetics of nanometric aluminum and iodine pentoxide

Owing to increasing threats of biological attacks, new methods for the neutralization of spore-forming bacteria are currently being examined. Thermites may be an effective method to produce high-temperature reactions, and some compositions such as aluminum (Al) and iodine pentoxide (I₂O₅) also have biocidal properties. This study examines the thermal degradation behavior of I₂O₅ mixed with micron and nanometer scale aluminum (Al) particles. Differential scanning calorimetry (DSC) and thermogravimetric (TG) analyses were performed in an argon environment on both particle scales revealing a non-reaction for micron Al and a complex multistep reaction for the nanometer scale Al. Results show that upon I₂O₅ decomposition, iodine ion sorption into the alumina shell passivating Al particles is the rate-controlling step of the Al–I₂O₅ reaction. This pre-ignition reaction is unique to nano-Al mixtures and attributed to the significantly higher specific surface area of the nanometric Al particles which provide increased sites for I⁻ sorption. A similar pre-ignition reaction had previously been observed with fluoride ions and the alumina shell passivating Al particles.