Level discrimination of sinusoids as a function of duration and level for fixed-level, roving-level, and across-frequency conditions

The ability of listeners to detect level differences between two sinusoidal stimuli in a two-interval forced-choice procedure was measured as a function of duration and level in three conditions: (1) the pedestal was fixed in level and the stimuli in the two intervals had the same frequency of either 1 or 2 kHz (fixed-level condition); (2) the pedestal was roved in level over a 20-dB range from trial to trial, but the stimuli still had the same frequency of either 1 or 2 kHz (roving-level condition); and (3) the pedestal was roved in level over a 20-dB range and the two stimuli differed in frequency, such that one was around 1 kHz while the other was around 2 kHz (across-frequency condition). In the fixed-level conditions, difference limens decreased (improved) with both increasing duration and level, as found in previous studies. In the roving-level conditions, difference limens increased and the dependence on duration and level decreased. Difference limens in the across-frequency conditions were generally highest and showed very little dependence on either stimulus duration or level. The results may be understood in terms of different internal noise components with additive variances: In the fixed-level conditions, sensation noise, which is dependent on stimulus attributes such as duration and level, is dominant. In more difficult conditions, where trace-memory and/or across-channel comparisons are required, a more central, stimulus-independent noise dominates.     

Efficient across-frequency integration: evidence from psychometric functions

Across-frequency integration of complex signals was investigated by measuring psychometric functions [log (d') versus signal level in dB SPL] for detection of brief and long signals presented in broadband noise. The signals were tones at 630, 1600, and 4000 Hz, and a nine-tone complex with components spaced at one-third-octave frequencies between 630 and 4000 Hz. The phase relationship of the components in the complex was varied such that adjacent components were in phase (at 0 degrees), 90, or 180 degrees out of phase. Signal durations (defined in terms of the number of cycles between the half-amplitude points of the Gaussian envelopes) of 4.7 and 150 cycles were tested. Results for six normal-hearing listeners showed that the slopes of the psychometric functions were steeper for the brief than for the long signals, and steeper for the tone complexes than for the tones, particularly for the brief signals. This suggests that the transformation from signal intensity to decision variable may be different for brief complex signals than for tonal signals and long complex signals. Thresholds obtained from the psychometric functions were in excellent agreement with those obtained with an adaptive procedure that employed three interleaved tracks. For the long signals, the threshold improvement for the tone complexes relative to a single tone was well described by a 5* log (n) integration rule. However, the threshold improvement for brief signals obeyed a more efficient integration rule of 7 to 8* log (n). A portion of this effect could be accounted for by the phase relationship of the tone complexes; thresholds for brief signals were lowest when the components were in phase at the envelope peak of the signal. This finding indicates that temporal synchrony across auditory channels may enhance detection of brief multi-tone complexes.     

Modeling the interactions of a peptide-major histocompatibility class I ligand with its receptors. I. Recognition by two αβ T cell receptors

A three-dimensional model of the complex between an Influenza Hemagglutinin peptide, Ha_255–262, and its restricting element, the mouse major histocompatibility complex (MHC) class I molecule, K^k, was built by homology modeling and subsequently refined by simulated annealing and restrained molecular dynamics. Next, three-dimensional models of two different T cell receptors (TCRs) both specific for the Ha_255–262/K^k complex were generated based on previously published TCR X-ray structures. Finally, guided by the recently published X-ray structures of ternary TCR/peptide/MHC-I complexes, the TCR models were successfully docked into the Ha_255–262/K^k model. We have previously used a systematic and exhaustive panel of 144 single amino acid substituted analogs to analyze both MHC binding and T cell recognition of the parental viral peptide. This large body of experimental data was used to evaluate the models. They were found to account well for the experimentally obtained data, lending considerable support to the proposed models and suggesting a universal docking mode for TCRs to MHC-peptide complexes. Such models may also be useful in guiding future rational experimentation.     

Using statistical decision theory to predict speech intelligibility. II. Measurement and prediction of consonant-discrimination performance.

The speech recognition sensitivity (SRS) model [H. Müsch and S. Buus, J. Acoust. Soc. Am. 109, 2896-2909 (2001)] was tested by applying it to consonant-discrimination data collected in this study. Normally hearing listeners' abilities to discriminate among 18 consonants were measured in 58 filter conditions using two test paradigms. In one paradigm, listeners chose among all 18 stimuli. In the other, response alternatives were restricted to the correct response and eight consonants that were randomly selected among the 17 incorrect response alternatives. The effect of the number of response alternatives on performance can be described by statistical decision theory. Most filter conditions included one or more sharply filtered narrow bands of speech. Depending on the selection of bands, listeners' performance in multi-band conditions falls short of, equals, or exceeds the performance expected from multiplication of the error rates in the individual bands. The performance advantage in multi-band conditions increases with average band separation. The SRS model provides a good fit to the data and predicts the data more accurately than does the speech intelligibility index.     

Breaking the barrier to fast electron transfer

A study of the electron transfer for a non-glycosylated redox variant of GOx is reported, immobilised onto an electrode via a polyhistidine tag. The non-glycosylated variant allows the enzyme to be brought closer to the electrode, and within charge transfer distances predicted by Marcus' theory. The enzyme-electrode-hybrid shows direct very fast reversible electrochemical electron transfer, with a rate constant of ~ 350 s^− 1 under anaerobic conditions. This is 2 orders of magnitude faster than the enzyme-free flavin adenine dinucleotide (FAD). These results are discussed in the context of the conformation of FAD in the active site of GOx. Further data, presented in the presence of oxygen, show a reduced electron transfer rate (~ 160 s^− 1) that may be associated with the oxygen interaction with the histidines in the active site. These residues are implicated in the proton transfer mechanism and thus suggest that the presence of oxygen may have a profound effect in attenuating the direct electron transfer rate and thus moderating ‘short-circuit’ incidental electron transfer between proteins.     

Donor‐Appended N,C‐Chelate Organoboron Compounds: Influence of Donor Strength on Photochromic Behaviour

Recently, four‐coordinated N,C‐chelate organoboron compounds have been found to show many interesting photochemical transformations depending on the nature of their chelating framework. As such, the effect of substitution on the chelate ligand has been well‐established and understood, but the impact of the aryl groups attached to the boron atom remains less clear. To investigate the effect of enhanced charge‐transfer character, a series of new N,C‐chelate organoboron compounds with donor‐functionalized aryl groups have been synthesized and characterized using NMR, UV/Vis, and electrochemical methods. These compounds were found to possess bright and tunable charge‐transfer luminescence which is dependent on the donor strength of the amino substituent. In addition, some of these compounds undergo photochromic switching, producing dark isomers of various colors. This work establishes that donor‐functionalization of the aryl groups in N,C‐chelate boron compounds is an effective strategy for tuning both the photophysical and photochemical properties of such systems. The new findings also help elucidate the influence of electronic structure on the photoreactivity of N,C‐chelate organoboron compounds which appears to be as important as steric crowding around the boron atom.     

Photochemical Generation of Chiral N,B,X‐Heterocycles by Heteroaromatic C−X Bond Scission (X=S,O) and Boron Insertion

Chiral organoboron compounds with a chelate backbone and mesityl/heterocycle substituents (thienyl, furyl, and derivatives thereof) undergo a quantitative phototransformation that yields rare, chiral N,B,X‐containing heterocycles, such as base‐stabilized 1,2‐thiaborinines and 1,2‐oxaborinines. Boriranes were observed as intermediates in some of these transformations. The oxaborinines display further reactivity, generating 4a,12b‐dihydrobenzo[h][1,2]oxaborinino[4,3‐f]quinolines through a sequential conrotatory electrocyclization and a [1,5]‐H shift. The N,B,X‐containing heterocycles display strong blue‐green to orange‐red emission in the solid state. Combined DFT//CASP2T calculations suggest that a common biradical intermediate is responsible for the formation of these compounds as well as their interconversion.     

Photoelectron spectroscopy of hydrated hexafluorobenzene anions

We present a synergetic experimental/theoretical study of hydrated hexafluorobenzene anions. Experimentally, we measured the anion photoelectron spectra of the anions, C6F6(-)(H2O)n (n=0-2). The spectra show broad peaks, which shift to successively higher electron binding energies with the addition of each water molecule to the hexafluorobenzene anion. Complementing these results, we also conducted density functional calculations which link adiabatic electron affinities to the optimized geometric structures of the negatively charged species and their neutral counterparts. Neutral hexafluorobenzene-water complexes are not thought to be hydrogen bonded. In the case of C6F6(-)(H2O)1, however, its water molecule was found to lie in the plane of the hexafluorobenzene anion, bound by two O-H...F ionic hydrogen bonds. Whereas in the case of C6F6(-)(H2O)2, both water molecules also lie in the plane of and are hydrogen bonded to the hexafluorobenzene anion but on opposite ends. This study and that of Schneider et al. [J. Chem. Phys. 127, 114311 (2007), preceding paper] are in agreement regarding the geometry of C6F6(-)(H2O)1.     

Using statistical decision theory to predict speech intelligibility. I. Model structure.

This article introduces a new model that predicts speech intelligibility based on statistical decision theory. This model, which we call the speech recognition sensitivity (SRS) model, aims to predict speech-recognition performance from the long-term average speech spectrum, the masking excitation in the listener's ear, the linguistic entropy of the speech material, and the number of response alternatives available to the listener. A major difference between the SRS model and other models with similar aims, such as the articulation index, is this model's ability to account for synergetic and redundant interactions among spectral bands of speech. In the SRS model, linguistic entropy affects intelligibility by modifying the listener's identification sensitivity to the speech. The effect of the number of response alternatives on the test score is a direct consequence of the model structure. The SRS model also appears to predict the differential effect of linguistic entropy on filter condition and the interaction between linguistic entropy, signal-to-noise ratio, and language proficiency.     

Interactions between test- and inducer-tone durations in induced loudness reduction

A tone usually declines in loudness when preceded by a more intense inducer tone. This phenomenon is called "loudness recalibration" or "induced loudness reduction" (ILR). The present study investigates how ILR depends on level, loudness, and duration. A 2AFC procedure was used to obtain loudness matches between 2500-Hz comparison tones and 500-Hz test tones at 60 and 70 dB SPL, presented with and without preceding 500-Hz inducer tones. For 200-ms test and comparison tones, the amount of ILR did not depend on inducer level (set at 80 dB SPL and above), but ILR was greater with 200- than with 5-ms inducers, even when both were equally loud. For 5-ms tones, ILR was as great with 5- as with 200-ms inducers and about as great as when test and inducer tones both lasted 200 ms. These results suggest that (1) neither the loudness nor the SPL of the inducer alone governs ILR, and (2) inducer duration must equal or exceed test-tone duration to yield maximal amounts of ILR. Further analysis indicates that the efferent system may be partly responsible for ILR of 200-ms test tones, but is unlikely to account for ILR of 5-ms tones.