Measured rates of fluoride/metal association correlate with rates of superoxide/metal reactions for Fe(III)EDTA(H2O)- and related complexes

The effects of 10 paramagnetic metal complexes (Fe(III)EDTA(H2O)-, Fe(III)EDTA(OH)2-, Fe(III)PDTA-, Fe(III)DTPA2-, Fe(III)2O(TTHA)2-, Fe(III)(CN)6(3-), Mn(II)EDTA(H2O)2-, Mn(II)PDTA2-, Mn(II)beta-EDDADP2-, and Mn(II)PO4(-)) on F- ion 19F NMR transverse relaxation rates (R2 = 1/T2) were studied in aqueous solutions as a function of temperature. Consistent with efficient relaxation requiring formation of a metal/F- bond, only the substitution inert complexes Fe(III)(CN)6(3-) and Fe(III)EDTA(OH)2- had no measured effect on T2 relaxation of the F- 19F resonance. For the remaining eight complexes, kinetic parameters (apparent second-order rate constants and activation enthalpies) for metal/F- association were determined from the dependence of the observed relaxation enhancements on complex concentration and temperature. Apparent metal/F- association rate constants for these complexes (k(app,F-)) spanned 5 orders of magnitude. In addition, we measured the rates at which O2*- reacts with Fe(III)PDTA-, Mn(II)EDTA(H2O)2-, Mn(II)PDTA2-, and Mn(II)beta-EDDADP2- by pulse radiolysis. Although no intermediate is observed during the reduction of Fe(III)PDTA- by O2*-, each of the Mn(II) complexes reacts with formation of a transient intermediate presumed to form via ligand exchange. These reactivity patterns are consistent with literature precedents for similar complexes. With these data, both k(app,O2-) and k(app,F-) are available for each of the eight reactive complexes. A plot of log(k(app,O2-)) versus log(k(app,F-)) for these eight showed a linear correlation with a slope approximately 1. This correlation suggests that rapid metal/O2*- reactions of these complexes occur via an inner-sphere mechanism whereas formation of an intermediate coordination complex limits the overall rate. This hypothesis is also supported by the very low rates at which the substitution inert complexes (Fe(III)(CN)6(3-) and Fe(III)EDTA(OH)2-) are reduced by O2*-. These results suggest that F- 19F NMR relaxation can be used to predict the reactivities of other Fe(III) complexes toward reduction by O2*-, a key step in the biological production of reactive oxygen species.     

Pitch strength and pitch dominance of iterated rippled noises in hearing-impaired listeners.

Reports using a variety of psychophysical tasks indicate that pitch perception by hearing-impaired listeners may be abnormal, contributing to difficulties in understanding speech and enjoying music. Pitches of complex sounds may be weaker and more indistinct in the presence of cochlear damage, especially when frequency regions are affected that form the strongest basis for pitch perception in normal-hearing listeners. In this study, the strength of the complex pitch generated by iterated rippled noise was assessed in normal-hearing and hearing-impaired listeners. Pitch strength was measured for broadband noises with spectral ripples generated by iteratively delaying a copy of a given noise and adding it back into the original. Octave-band-pass versions of these noises also were evaluated to assess frequency dominance regions for rippled-noise pitch. Hearing-impaired listeners demonstrated consistently weaker pitches in response to the rippled noises relative to pitch strength in normal-hearing listeners. However, in most cases, the frequency regions of pitch dominance, i.e., strongest pitch, were similar to those observed in normal-hearing listeners. Except where there exists a substantial sensitivity loss, contributions from normal pitch dominance regions associated with the strongest pitches may not be directly related to impaired spectral processing. It is suggested that the reduced strength of rippled-noise pitch in listeners with hearing loss results from impaired frequency resolution and possibly an associated deficit in temporal processing.     

An Algebraic Characterization of Vacuum States in Minkowski Space. II. Continuity Aspects

An algebraic characterization of vacuum states in Minkowski space is given which relies on recently proposed conditions of geometric modular action and modular stability for algebras of observables associated with wedge-shaped regions. In contrast to previous work, continuity properties of these algebras are not assumed but derived from their inclusion structure. Moreover, a unique continuous unitary representation of spacetime translations is constructed from these data. Thus, the dynamics of relativistic quantum systems in Minkowski space is encoded in the observables and state and requires no prior assumption about any action of the spacetime symmetry group upon these quantities.     

Effects of noise on speech production: acoustic and perceptual analyses

Acoustical analyses were carried out on a set of utterances produced by two male speakers talking in quiet and in 80, 90, and 100 dB SPL of masking noise. In addition to replicating previous studies demonstrating increases in amplitude, duration, and vocal pitch while talking in noise, these analyses also found reliable differences in the formant frequencies and short-term spectra of vowels. Perceptual experiments were also conducted to assess the intelligibility of utterances produced in quiet and in noise when they were presented at equal S/N ratios for identification. In each experiment, utterances originally produced in noise were found to be more intelligible than utterances produced in the quiet. The results of the acoustic analyses showed clear and consistent differences in the acoustic-phonetic characteristics of speech produced in quiet versus noisy environments. Moreover, these accounts differences produced reliable effects on intelligibility. The findings are discussed in terms of: (1) the nature of the acoustic changes that taken place when speakers produce speech under adverse conditions such as noise, psychological stress, or high cognitive load: (2) the role of training and feedback in controlling and modifying a talker's speech to improve performance of current speech recognizers; and (3) the development of robust algorithms for recognition of speech in noise.     

On Bell's inequalities and algebraic invariants

Some algebraic invariants associated with Bell's inequalities are defined for inclusions of von Neumann algebras and studied within the context of general algebraic quantum theory. More special results are proven for quantum field theory which establish that these invariants take infinitely many values. Sharp short-distance bounds on the Bell correlations are also demonstrated in the context of relativistic quantum field theory.     

Effects of stress and final-consonant voicing on vowel production: articulatory and acoustic analyses

Durations of the vocalic portions of speech are influenced by a large number of linguistic and nonlinguistic factors (e.g., stress and speaking rate). However, each factor affecting vowel duration may influence articulation in a unique manner. The present study examined the effects of stress and final-consonant voicing on the detailed structure of articulatory and acoustic patterns in consonant-vowel-consonant (CVC) utterances. Jaw movement trajectories and F 1 trajectories were examined for a corpus of utterances differing in stress and final-consonant voicing. Jaw lowering and raising gestures were more rapid, longer in duration, and spatially more extensive for stressed versus unstressed utterances. At the acoustic level, stressed utterances showed more rapid initial F 1 transitions and more extreme F 1 steady-state frequencies than unstressed utterances. In contrast to the results obtained in the analysis of stress, decreases in vowel duration due to devoicing did not result in a reduction in the velocity or spatial extent of the articulatory gestures. Similarly, at the acoustic level, the reductions in formant transition slopes and steady-state frequencies demonstrated by the shorter, unstressed utterances did not occur for the shorter, voiceless utterances. The results demonstrate that stress-related and voicing-related changes in vowel duration are accomplished by separate and distinct changes in speech production with observable consequences at both the articulatory and acoustic levels.     

Micro and surface analysis with fast heavy ions

The desorption of atomic and molecular species from surfaces bombarded by fast heavy ions (Z ? 20; E ? 0.5 MeV/amu) is attractive for surface and microscopic characterization. Only a low-intensity probe beam is needed, the escape depth of desorbed species is shallow (ca. 10 Å), and desorbed ions are efficiently detected with a time-of-flight mass spectrometer. Thus, particle-induced desorption mass spectrometry (PDMS) maintains sample integrity and charging effects are avoided. PDMS is useful for surface analysis of glasses and plastics by using californium-252 fission fragments for bombardment. Inorganic and organic surface constituents can be detected simultaneously; mass resolution is good. For lithium in glass, the detection limit is about 1 pg (ca. 100 μg g^?1. The PDMS technique can be combined with sequential ion etching for depth profiling. The feasibility of PDMS for microscopic analysis with a collimated 84-MeV Kr⁷⁺ beam (target diameter ca. 11 μm) is discussed.     

Electron-phonon interactions in ce3+-doped yttrium aluminum garnet nanophosphors

Ce 3+-doped yttrium aluminum garnet nanophosphors with sizes near 30 and 250 nm have been synthesized by using chemical gelation and solvothermal methods, respectively. The size-dependent electron-longitudinal-optical-phonon coupling is investigated by fitting measured photoluminescence spectra within the framework of the Brownian oscillator model. Results show that the coupling strength is in a decreasing order from the bulk material to the nanophosphors of much smaller sizes.