B−B Cleavage and Ring-Expansion of a 1,4,2,3-Diazadiborinine with N-Heterocyclic Carbenes

A 1,4,2,3-diazadiborinine derivative was found to form Lewis adducts with strong two-electron donors such as N-heterocyclic and cyclic (alkyl)(amino)carbenes. Depending on the donor, some of these Lewis pairs are thermally unstable, converting to sole B,N-embedded products upon gentle heating. The products of these reactions, which have been fully characterized by NMR spectroscopy, elemental analysis, and single-crystal X-ray diffraction, were identified as B,N-heterocycles with fused 1,5,2,4-diazadiborepine and 1,4,2-diazaborinine rings. Computational modelling of the reaction mechanism provides insight into the formation of these unique structures, suggesting that a series of B−H, C−N, and B−B bond activation steps are responsible for these “intercalation” reactions between the 1,4,2,3-diazadiborinine and NHCs.     

Measuring cellulase activity

An approach is presented for obtaining relative filter paper activities for enzyme preparations having activities below that required for application of the traditional International Union of Pure and Applied Chemistry filter paper assay. The approach involves the utilization of protein stabilizers to retard the time-dependent enzyme inactivation that may occur under traditional filter paper assay conditions. Enzyme stabilization allows extended reaction times and the calculation of relative activities based on the time required for saccharification of 3.6% of the traditional substrate, making results proportional to those obtained in the traditional International Union of Pure and Applied Chemistry assay. The assay is demonstrated using a commercial cellulase preparation along with KCl and bovine serum albumin as protein stabilizers.     

Temporal integration of loudness in listeners with hearing losses of primarily cochlear origin.

To investigate how hearing loss of primarily cochlear origin affects the loudness of brief tones, loudness matches between 5- and 200-ms tones were obtained as a function of level for 15 listeners with cochlear impairments and for seven age-matched controls. Three frequencies, usually 0.5, 1, and 4 kHz, were tested in each listener using a two-interval, two--alternative forced--choice (2I, 2AFC) paradigm with a roving-level, up-down adaptive procedure. Results for the normal listeners generally were consistent with published data [e.g., Florentine et al., J. Acoust Soc. Am. 99, 1633-1644 (1996)]. The amount of temporal integration--defined as the level difference between equally loud short and long tones--varied nonmonotonically with level and was largest at moderate levels. No consistent effect of frequency was apparent. The impaired listeners varied widely, but most showed a clear effect of level on the amount of temporal integration. Overall, their results appear consistent with expectations based on knowledge of the general properties of their loudness-growth functions and the equal-loudness-ratio hypothesis, which states that the loudness ratio between equal-SPL long and brief tones is the same at all SPLs. The impaired listeners' amounts of temporal integration at high SPLs often were larger than normal, although it was reduced near threshold. When evaluated at equal SLs, the amount of temporal integration well above threshold usually was in the low end of the normal range. Two listeners with abrupt high-frequency hearing losses (slopes > 50 dB/octave) showed larger-than-normal maximal amounts of temporal integration (40 to 50 dB). This finding is consistent with the shallow loudness functions predicted by our excitation-pattern model for impaired listeners [Florentine et al., in Modeling Sensorineural Hearing Loss, edited by W. Jesteadt (Erlbaum, Mahwah, NJ, 1997), pp. 187-198]. Loudness functions derived from impaired listeners' temporal-integration functions indicate that restoration of loudness in listeners with cochlear hearing loss usually will require the same gain whether the sound is short or long.     

On computing the pressure by thep version of the finite element method for Stokes problem

Summary This paper introduces and analyzes two ways of extracting the hydrostatic pressure when solving Stokes problem using thep version of the finite element method. When one uses a localH ¹ projection, we show that optimal rates of convergence for the pressure approximation is achieved. When the pressure is not inH ¹. or the value of the pressure is only needed at a few points, one may extract the pressure pointwise using e.g. a single layer potential recovery. Negative, zero, and higher norm estimates for the Stokes velocity are derived within the framework of thep version of the F.E.M.Partially supported by ONR grants N00014-87-K-0427 and N00014-90-J-1238     

Temporal integration in normal hearing, cochlear impairment, and impairment simulated by masking

To assess temporal integration in normal hearing, cochlear impairment, and impairment simulated by masking, absolute thresholds for tones were measured as a function of duration. Durations ranged from 500 ms down to 15 ms at 0.25 kHz, 8 ms at 1 kHz, and 2 ms at 4 and 14 kHz. An adaptive 2I, 2AFC procedure with feedback was used. On each trial, two 500-ms observation intervals, marked by lights, were presented with an interstimulus interval of 250 ms. The monaural signal was presented in the temporal center of one observation interval. The results for five normal and six impaired listeners show: (1) normal listeners' thresholds decrease by about 8 to 10 dB per decade of duration, as expected; (2) listeners with cochlear impairments generally show less temporal integration than normal listeners; and (3) listeners with impairments simulated using masking noise generally show the same amount of temporal integration as normal listeners tested in the quiet. The difference between real and simulated impairments indicates that the reduced temporal integration observed in impaired listeners probably is not due to splatter of energy to frequency regions where thresholds are low, but reflects reduced temporal integration per se.     

Decision rules in detection of simple and complex tones

Detection of simple and complex tones in the presence of a 64-dB SPL uniformly masking noise was examined in two experiments. In both experiments, the signals were either pure tones (220, 1100, or 3850 Hz) or an 18-tone complex consisting of equally intense components between 110 and 7260 Hz. In experiment 1, psychometric functions were obtained for detection in a 2I, 2AFC task. Results for eight normal listeners show that the psychometric functions are parallel for simple and complex tones. As expected, the masked thresholds for the pure tones are 43-44 dB SPL independent of frequency; the masked threshold for the complex tone is about 37 dB SPL per tone. These results indicate that the simultaneous presence of signal energy in many auditory channels aids detection. In experiment 2, psychometric functions were obtained with all four signals presented in random order within a block of trials. Results for four normal listeners show that the psychometric functions are parallel to one another and to those obtained in experiment 1. The thresholds are elevated to about 46 dB for the pure tones and to 40.5 dB for the complex tone. These results are nearly, but not quite, consistent with a multiband energy-detector model using an optimum decision rule; it appears that listeners may only make an unweighted sum of decision variables across an optimum selection of channels.     

β-Lactose in the View of a CFF-Optimized Force Field

Abstract

A recently developed force field PEF95SAC, based on Consistent Force Field (CFF) optimized potential energy parameters for alcohols and most of the naturally occurring carbohydrates, is applied to and tested on β-lactose. The properties of the potential energy surface of this disaccharide are compared to X-ray structures, NMR coupling constants and optical rotation data. The overall performance indicates good extrapolative power for the modeling of oligo- and polysaccharide structures. A new glycosidic linkage geometry region is proposed for β-lactose as being important in both solid state and water solutions. This finding is supported by calculated J _H,C coupling constants and calculated optical rotation values.

In relation to the spectral calculations on β-lactose, the error of the use of relative energies (ΔE) in place of the Gibbs free energy (ΔG) as the basis for calculating Boltzmann distributed properties is demonstrated. In the β-lactose case it is shown that the conformational entropy is neither negligible nor uniformly distributed over the potential energy surface.     

A comparison of psychophysical procedures for level-discrimination thresholds

Five different psychophysical procedures were used to measure level-discrimination (also called intensity discrimination) thresholds for 1-kHz tones at two levels (30 and 90 dB SPL) and two durations (10 and 500 ms). The procedures were the classic transformed up-down staircase method with a two-alternative forced-choice (2AFC) paradigm (UPD), 15- and 50-trial implementations of the method of maximum likelihood (MML) with a cued yes-no paradigm, and 18-trial implementations of ZEST using both cued yes-no and 2AFC paradigms. Results obtained from nine normal listeners show that estimates of level-discrimination thresholds for the four conditions are similar across all five procedures when different points of convergence are accounted for. The variance of threshold estimates within listener and condition was smallest for UPD, largest for the MML with 15 trials, and statistically indistinguishable among the others. The sweat factors ranged from 5.5 for MML with 50 trials to about 1.4 for UPD and ZEST. Simulations show that ideal performance of procedures may be far from real-life experience and that these deviations are likely to depend on complex interactions between listener behavior and parameter choices used for implementing the procedures. Therefore, empirical verification is important for judging the effectiveness of psychophysical procedures.     

Level discrimination of frozen and random noise

This paper examines how the difference limen for level, delta L, is affected by stimulus bandwidth and variability. The delta L's were measured in three normal listeners using an adaptive two-interval, forced-choice procedure. The 30-ms stimuli were a 3-kHz tone and nine noise bands with half-power bandwidths ranging from 50 Hz-12 kHz. Except for the 12-kHz bandwidth, which was a low-pass noise, the noise bands were centered at 3 kHz. The delta L's were measured for both frozen and random noises presented at 30, 60, or 90 dB SPL overall. For frozen noises, the same sample of noise was presented throughout a block of 50 trials; for the random noises, different samples of noise were used in each interval of the trials. Results show that the delta L's are higher for random than for frozen noises at narrow bandwidths, but not at wide bandwidths. The delta L's for frozen narrow-band noises decrease with increasing level and are similar to those for the pure tone, whereas the delta L's for wideband noises are only slightly smaller at 90 than at 30 dB SPL. An unexpected finding is that the delta L's are larger at 60 than at 30 dB SPL for both frozen and random noises with bandwidths greater than one critical band. The effect of bandwidth varies with level: The delta L's decrease with increasing bandwidth at low levels, but are nearly independent of bandwidth at 90 dB SPL. The interaction of bandwidth and level is consistent with the multiband excitation-pattern model, but the nonmonotonic behavior of delta L as a function of level suggests modifications to the model.     

Confabulation Theory

Confabulation Theory [Hecht-Nielsen R. Confabulation theory. Springer-Verlag; 2007] is the first comprehensive theory of human and animal cognition. Here, we briefly describe Confabulation Theory and discuss experimental results that suggest the theory is correct. Simply put, Confabulation Theory proposes that thinking is like moving. In humans, the theory postulates that there are roughly 4000 thalamocortical modules, the “muscles of thought”. Each module performs an internal competition (confabulation) between its symbols, influenced by inputs delivered via learned axonal associations with symbols in other modules. In each module, this competition is controlled, as in an individual muscle, by a single graded (i.e., analog) thought control signal. The final result of this confabulation process is a single active symbol, the expression of which also results in launching of action commands that trigger and control subsequent movements and/or thought processes. Modules are manipulated in groups under coordinated, event-contingent control, in a similar manner to our 700 muscles. Confabulation Theory hypothesizes that the control of thinking is a direct evolutionary outgrowth of the control of movement. Establishing a complete understanding of Confabulation Theory will require launching and sustaining a massive new phalanx of confabulation neuroscience research.