Discrimination of temporally asymmetric modulation with triangular envelopes on a broadband-noise carrier (L)

Highly detectable, time-reversed triangular amplitude modulation, with linear increases and decreases in amplitude, was used in an adaptive task to measure just-noticeable differences for changes in the direction of envelope temporal asymmetry for different modulation depths (m = 1.0 and 0.5) and rates (8, 16, and 32 Hz). Thresholds were analyzed using three different measures of the modulator's shape based on (1) the change in the position of the peak within a cycle, (2) the change in the slope of the modulator's increasing amplitude portion, and (3) the change in slope measured in units of amplitude per unit cycle rather than amplitude per unit time. The amplitude per unit cycle measure resulted in the best fit to all the data, and predicted additional data that were gathered with roved modulation frequency. The results suggest that a time normalization process may be involved in the perception and discrimination of envelope shape.     

On the mechanisms involved in the recovery of envelope information from temporal fine structure

Three experiments were designed to provide psychophysical evidence for the existence of envelope information in the temporal fine structure (TFS) of stimuli that were originally amplitude modulated (AM). The original stimuli typically consisted of the sum of a sinusoidally AM tone and two unmodulated tones so that the envelope and TFS could be determined a priori. Experiment 1 showed that normal-hearing listeners not only perceive AM when presented with the Hilbert fine structure alone but AM detection thresholds are lower than those observed when presenting the original stimuli. Based on our analysis, envelope recovery resulted from the failure of the decomposition process to remove the spectral components related to the original envelope from the TFS and the introduction of spectral components related to the original envelope, suggesting that frequency- to amplitude-modulation conversion is not necessary to recover envelope information from TFS. Experiment 2 suggested that these spectral components interact in such a way that envelope fluctuations are minimized in the broadband TFS. Experiment 3 demonstrated that the modulation depth at the original carrier frequency is only slightly reduced compared to the depth of the original modulator. It also indicated that envelope recovery is not specific to the Hilbert decomposition.     

The enhancement effect: evidence for adaptation of inhibition using a binaural centering task

The enhancement effect is consistently shown when simultaneously masked stimuli are preceded by the masker alone, with a reduction in the amount of masking relative to when that precursor is absent. One explanation for this effect proposed by Viemeister and Bacon [(1982). J. Acoust. Soc. Am. 71, 1502-1507] is the adaptation of inhibition, which predicts that an enhanced component (the "target") will be effectively more intense within the auditory system than one that has not been enhanced. Forward masking studies have indicated this effect of increased gain; however, other explanations of the enhancement effect have also been suggested. In order to provide an alternative measure of the amount of effective gain for an enhanced target, a subjective binaural centering task was used in which listeners matched the intensities of enhanced and unenhanced 2-kHz tones presented to opposite ears to produce a centered stimulus. The results showed that the enhancement effect produces an effective 4-5 dB increase in the level of the enhanced target. The enhancement effect was also measured using other enhancement paradigms which yielded similar results over a range of levels for the target, supporting an account based on adaptation of inhibition.     

Multilayer thin-film inspection through measurements of reflection coefficients

A vibration-insensitive interferometer is described to measure the thickness, refraction index and surface profile of thin-film stack at normal incidence. By satisfying the continuous boundary conditions of electric and magnetic fields at interfaces in a multilayer film stack, the reflection coefficient phase of the thin-film stack can be distinguished from the phase of spatial path difference, thus thickness and refraction index can be extracted. The experiment results showed that the measurement precision is significantly increased after the phase analysis was added into the reflectance analysis.     

Self-witnessing polynomial-time complexity and prime factorization

For a number of computational search problems, the existence of a polynomial-time algorithm for the problem implies that a polynomial-time algorithm for the problem is constructively known. Some instances of such self-witnessing polynomial-time complexity are presented. Our main result demonstrates this property for the problem of computing the prime factorization of a positive integer, based on a lemma which shows that a certificate for primality or compositeness can be constructed for a positive integer p in deterministic polynomial time given a complete factorization of p - 1.     

Spontaneous Reconstitution of Functional Transmembrane Proteins During Bioorthogonal Phospholipid Membrane Synthesis

Transmembrane proteins are critical for signaling, transport, and metabolism, yet their reconstitution in synthetic membranes is often challenging. Non‐enzymatic and chemoselective methods to generate phospholipid membranes in situ would be powerful tools for the incorporation of membrane proteins. Herein, the spontaneous reconstitution of functional integral membrane proteins during the de novo synthesis of biomimetic phospholipid bilayers is described. The approach takes advantage of bioorthogonal coupling reactions to generate proteoliposomes from micelle‐solubilized proteins. This method was successfully used to reconstitute three different transmembrane proteins into synthetic membranes. This is the first example of the use of non‐enzymatic chemical synthesis of phospholipids to prepare proteoliposomes.     

Scalable synthesis of 1-bicyclo[1.1.1]pentylamine via a hydrohydrazination reaction

The reaction of [1.1.1]propellane with di-tert-butyl azodicarboxylate and phenylsilane in the presence of Mn(dpm)(3) to give di-tert-butyl 1-(bicyclo[1.1.1]pentan-1-yl)hydrazine-1,2-dicarboxylate is described. Subsequent deprotection gives 1-bicyclo[1.1.1]pentylhydrazine followed by reduction to give 1-bicyclo[1.1.1]pentylamine. The reported route marks a significant improvement over the previous syntheses of 1-bicyclo[1.1.1]pentylamine in terms of scalability, yield, safety, and cost.     

Two metals are better than one in the gold catalyzed oxidative heteroarylation of alkenes

We present a detailed study of the mechanism for oxidative heteroarylation, based on DFT calculations and experimental observations. We propose binuclear Au(II)-Au(II) complexes to be key intermediates in the mechanism for gold catalyzed oxidative heteroarylation. The reaction is thought to proceed via a gold redox cycle involving initial oxidation of Au(I) to binuclear Au(II)-Au(II) complexes by Selectfluor, followed by heteroauration and reductive elimination. While it is tempting to invoke a transmetalation/reductive elimination mechanism similar to that proposed for other transition metal complexes, experimental and DFT studies suggest that the key C-C bond forming reaction occurs via a bimolecular reductive elimination process (devoid of transmetalation). In addition, the stereochemistry of the elimination step was determined experimentally to proceed with complete retention. Ligand and halide effects played an important role in the development and optimization of the catalyst; our data provides an explanation for the ligand effects observed experimentally, useful for future catalyst development. Cyclic voltammetry data is presented that supports redox synergy of the Au···Au aurophilic interaction. The monometallic reductive elimination from mononuclear Au(III) complexes is also studied from which we can predict a ~15 kcal/mol advantage for bimetallic reductive elimination.     

Ancillary nitrile substituents as convenient IR spectroscopic reporters for self-assembly of mercapto- and isocyanoazulenes on Au(111)

Synthesis and self-assembly of structurally related mercapto- and isocyanoazulenes, including novel 2-mercapto-1,3-dicyanoazulene (4) and 2-isocyano-1,3-dicyanoazulene (5), are reported. Exposing 5 adsorbed on Au(111) to a solution of 4 displaces the isocyanoazulene monolayer with that of the mercaptoazulene as judged by ν(C≡N) signatures of these films.