The site of Cr+ attachment to gas-phase aniline from infrared spectroscopy

Infrared spectroscopy of gas-phase Cr+ complexes of aniline was studied using the FELIX free electron laser interfaced to a Fourier transform ion cyclotron resonance spectrometer. For both the monomer complex Cr+(aniline) and the dimer complex Cr+(aniline)2 the spectra showed features indicating binding of the metal ion to the aromatic pi cloud, as opposed to the nitrogen atom. Agreement with DFT-calculated infrared absorption spectra for the ring-bound complexes was good using the MPW1PW91 functional, but the B3LYP functional predicted the wrong binding site. The spectroscopic results resolve the ambiguity in computational prediction of the preferred binding site and support the use of the MPW1PW91 functional for these systems.     

Direct mass measurements of neutron-deficient xenon isotopes using the ISOLTRAP mass spectrometer

The masses of the noble-gas Xe isotopes with have been directly measured for the first time. The experiments were carried out with the ISOLTRAP triple trap spectrometer at the on-line mass separator ISOLDE/CERN. A mass resolving power of the Penning trap spectrometer of of close to a million was chosen resulting in an accuracy of keV for all investigated isotopes. Conflicts with existing, indirectly obtained, mass data by several standard deviations were found and are discussed. An atomic mass evaluation has been performed and the results are compared to information from laser spectroscopy experiments and to recent calculations employing an interacting boson model.PACS: 07.75. + h Mass spectrometers - 21.10.Dr Binding energies and masses - 27.60. + j - 32.10.Bi Atomic masses, mass spectra, abundances, and isotopes     

Effects of ultraviolet B exposure on the expression of proliferating cell nuclear antigen in murine skin

Proliferating cell nuclear antigen (PCNA) is an active nuclear protein involved in DNA replication, recombination and repair. PCNA is found throughout the basal layer in normal skin and in all layers of the epidermis in malignancy. This study evaluates PCNA's expression after acute and chronic UV-B irradiation. Skh-1 hairless mice exposed to 1.5 and 4.5 kJ/m2 of UV-B were sacrificed at 6, 12, 24, 48, 72 and 168 h. Immunohistochemical analysis revealed PCNA expression throughout the basal layer of untreated skin, with diminished expression at 6 h, indicative of immediate UV damage, and evidenced by the observable upregulation in pyrimidine dimer formation early on. Subsequently, PCNA immunoreactivity progressively increased, demonstrating an aberrant upward epidermal migratory pattern in association with chronic exposure. The 4.5 kJ/m2 group exhibited prolonged recovery in staining and also demonstrated this altered migratory pattern with chronic exposure. Progressive reactivation of PCNA expression occurs with repair. PCNA migration to upper layers of the epidermis indicates proliferation and possibly a subsequent increased malignant potential. We conclude that PCNA can serve as a marker of DNA repair and indirectly as an indicator of UV-B-induced damage, expression being time dependent and dose related. Specific immunoreactivity patterns and the observable atypia in keratinocytes are relevant in elucidating malignant potentiation.     

Prototype reflectivity analyses of hydrogen storage levels in single-walled carbon nanotubes

A prototype case study is presented that examines the level of hydrogen content in H-SWNTs using the Surface Plasmon Resonance technique. The damping effect and the angular shift in the resonance minimum of an SWNT-gold interface due to the presence of hydrogen is analyzed using a parametric model, which is based on the concept of an effective permittivity. The new approach provides for a non-invasive analysis of the level of hydrogen content in H-SWNTs and is potentially extendable to other carbon-based hydrogen storage materials.     

The effects of real and illusory glides on pure-tone frequency discrimination

Experiment 1 measured pure-tone frequency difference limens (DLs) at 1 and 4 kHz. The stimuli had two steady-state portions, which differed in frequency for the target. These portions were separated by a middle section of varying length, which consisted of a silent gap, a frequency glide, or a noise burst (conditions: gap, glide, and noise, respectively). The noise burst created an illusion of the tone continuing through the gap. In the first condition, the stimuli had an overall duration of 500 ms. In the second condition, stimuli had a fixed 50-ms middle section, and the overall duration was varied. DLs were lower for the glide than for the gap condition, consistent with the idea that the auditory system contains a mechanism specific for the detection of dynamic changes. DLs were generally lower for the noise than for the gap condition, suggesting that this mechanism extracts information from an illusory glide. In a second experiment, pure-tone frequency direction-discrimination thresholds were measured using similar stimuli as for the first experiment. For this task, the type of the middle section hardly affected the thresholds, suggesting that the frequency-change detection mechanism does not facilitate the identification of the direction of frequency changes.     

Auditory processing of real and illusory changes in frequency modulation (FM) phase

Auditory processing of frequency modulation (FM) was explored. In experiment 1, detection of a tau-radians modulator phase shift deteriorated as modulation rate increased from 2.5 to 20 Hz, for 1- and 6-kHz carriers. In experiment 2, listeners discriminated between two 1-kHz carriers, where, mid-way through, the 10-Hz frequency modulator had either a phase shift or increased in depth by deltaD% for half a modulator period. Discrimination was poorer for deltaD = 4% than for smaller or larger increases. These results are consistent with instantaneous frequency being smoothed by a time window with a total duration of about 110 ms. In experiment 3, the central 200-ms of a 1-s 1-kHz carrier modulated at 5 Hz was replaced by noise, or by a faster FM applied to a more intense 1-kHz carrier. Listeners heard the 5-Hz FM continue at the same depth throughout the stimulus. Experiments 4 and 5 showed that, after an FM tone had been interrupted by a 200-ms noise, listeners were insensitive to the phase at which the FM resumed. It is argued that the auditory system explicitly encodes the presence, and possibly the rate and depth, of FM in a way that does not preserve information on FM phase.     

Hot dense capsule-implosion cores produced by Z-pinch dynamic Hohlraum radiation

Hot dense capsule implosions driven by Z-pinch x rays have been measured using a approximately 220 eV dynamic Hohlraum to implode 1.7-2.1 mm diameter gas-filled CH capsules. The capsules absorbed up to approximately 20 kJ of x rays. Argon tracer atom spectra were used to measure the T(e) approximately 1 keV electron temperature and the n(e) approximately 1-4 x 10(23) cm(-3) electron density. Spectra from multiple directions provide core symmetry estimates. Computer simulations agree well with the peak emission values of T(e), n(e), and symmetry, indicating reasonable understanding of the Hohlraum and implosion physics.     

Investigation of modified basal plane pyrolytic graphite electrodes: definitive evidence for the electrocatalytic properties of the ends of carbon nanotubes

The basis of the electrocatalytic nature of multi-wall carbon nanotubes is suggested to reside in electron transfer from the ends of nanotubes, which structurally resemble the behaviour of edge plane (as opposed to basal plane) graphite, and is demonstrated via the comparison of the electrochemical oxidation of epinephrine and the electrochemical reduction of ferricyanide at nanotube-modified electrodes using different types of graphite electrodes and with C(60)-modified electrodes.     

Louder sounds can produce less forward masking: effects of component phase in complex tones

The influence of the degree of envelope modulation and periodicity on the loudness and effectiveness of sounds as forward maskers was investigated. In the first experiment, listeners matched the loudness of complex tones and noise. The tones had a fundamental frequency (F0) of 62.5 or 250 Hz and were filtered into a frequency range from the 10th harmonic to 5000 Hz. The Gaussian noise was filtered in the same way. The components of the complex tones were added either in cosine phase (CPH), giving a large crest factor, or in random phase (RPH), giving a smaller crest factor. For each F0, subjects matched the loudness between all possible stimulus pairs. Six different levels of the fixed stimulus were used, ranging from about 30 dB SPL to about 80 dB SPL in 10-dB steps. Results showed that, at a given overall level, the CPH and the RPH tones were louder than the noise, and that the CPH tone was louder than the RPH tone. The difference in loudness was larger at medium than at low levels and was only slightly reduced by the addition of a noise intended to mask combination tones. The differences in loudness were slightly smaller for the higher than for the lower F0. In the second experiment, the stimuli with the lower F0s were used as forward maskers of a 20-ms sinusoid, presented at various frequencies within the spectral range of the maskers. Results showed that the CPH tone was the least effective forward masker, even though it was the loudest. The differences in effectiveness as forward maskers depended on masker level and signal frequency; in order to produce equal masking, the level of the CPH tone had to be up to 35 dB above that of the RPH tone and the noise. The implications of these results for models of loudness are discussed and a model is presented based on neural activity patterns in the auditory nerve; this predicts the general pattern of loudness matches. It is suggested that the effects observed in the experiments may have been influenced by two factors: cochlear compression and suppression.     

Effect of the speed of a single-channel dynamic range compressor on intelligibility in a competing speech task

Using a "noise-vocoder" cochlear implant simulator [Shannon et al., Science 270, 303-304 (1995)], the effect of the speed of dynamic range compression on speech intelligibility was assessed, using normal-hearing subjects. The target speech had a level 5 dB above that of the competing speech. Initially, baseline performance was measured with no compression active, using between 4 and 16 processing channels. Then, performance was measured using a fast-acting compressor and a slow-acting compressor, each operating prior to the vocoder simulation. The fast system produced significant gain variation over syllabic timescales. The slow system produced significant gain variation only over the timescale of sentences. With no compression active, about six channels were necessary to achieve 50% correct identification of words in sentences. Sixteen channels produced near-maximum performance. Slow-acting compression produced no significant degradation relative to the baseline. However, fast-acting compression consistently reduced performance relative to that for the baseline, over a wide range of performance levels. It is suggested that fast-acting compression degrades performance for two reasons: (1) because it introduces correlated fluctuations in amplitude in different frequency bands, which tends to produce perceptual fusion of the target and background sounds and (2) because it reduces amplitude modulation depth and intensity contrasts.