Audibility and recognition of stop consonants in normal and hearing-impaired subjects

The purpose of this study was to examine the effect of spectral-cue audibility on the recognition of stop consonants in normal-hearing and hearing-impaired adults. Subjects identified six synthetic CV speech tokens in a closed-set response task. Each syllable differed only in the initial 40-ms consonant portion of the stimulus. In order to relate performance to spectral-cue audibility, the initial 40 ms of each CV were analyzed via FFT and the resulting spectral array was passed through a sliding-filter model of the human auditory system to account for logarithmic representation of frequency and the summation of stimulus energy within critical bands. This allowed the spectral data to be displayed in comparison to a subject's sensitivity thresholds. For normal-hearing subjects, an orderly function relating the percentage of audible stimulus to recognition performance was found, with perfect discrimination performance occurring when the bulk of the stimulus spectrum was presented at suprathreshold levels. For the hearing-impaired subjects, however, it was found in many instances that suprathreshold presentation of stop-consonant spectral cues did not yield recognition equivalent to that found for the normal-hearing subjects. These results demonstrate that while the audibility of individual stop consonants is an important factor influencing recognition performance in hearing-impaired subjects, it is not always sufficient to explain the effects of sensorineural hearing loss.     

Four-wave mixing with self-phase matching due to collective atomic recoil

We describe a method for nondegenerate four-wave-mixing in a cold sample of four-level atoms. An integral part of the four-wave-mixing process is a collective instability which spontaneously generates a periodic density modulation in the cold atomic sample with a period equal to half of the wavelength of the generated high-frequency optical field. Because of the generation of this density modulation, phase matching between the pump and scattered fields is not a necessary initial condition for this wave-mixing process to occur; rather the density modulation acts to "self-phase match" the fields during the course of the wave-mixing process. We describe a one-dimensional model of this process, and suggest a proof-of-principle experiment which would involve pumping a sample of cold Cs atoms with three infrared pump fields to produce blue light.     

Microwave-assisted acylation of 7-amino-5-aryl-6-cyanopyrido[2,3-d]pyrimidines

A microwave-assisted method is described for monoacylating 7-amino-5-aryl-6-cyanopyrido[2,3-d]pyrimidines using excess acid chlorides in pyridine. A diacylated intermediate is effectively deacylated to the product amide by a macroporous-Tris resin. A small library of 17 amides was prepared to validate the method. The integration of commercial microwave technology into the ArQule chemistry platform is also discussed.     

An electropneumatic‐heated nebulizer for enhancing spray ionization in PhotoSpray atmospheric pressure photoionization sources for liquid chromatography/mass spectrometry

We introduce a novel electropneumatic‐heated nebulizer (EPn‐HN), incorporating an electrified internal pneumatic nebulizer, to enhance the yield of sprayed ions from PhotoSpray? atmospheric pressure photoionization (APPI) sources for liquid chromatography/mass spectrometry (LC/MS). Spray ionization from the pneumatic‐heated nebulizers used in APPI sources provides a supplemental, complementary ionization method to be used for involatile and thermally labile compounds, otherwise intractable to APPI. Details of the construction and operation of the EPn‐HN device are provided. The performance of the EPn‐HN is demonstrated using two model compounds: substance P, a peptide used as a standard in studies of ion fragmentation mechanisms, and aztreonam, a thermally labile antibiotic. At the optimum voltage for spray ionization, improvements in sensitivity of two orders of magnitude are obtained relative to when the sprayer is grounded, the conventional case. Since both substance P and aztreonam cannot be detected using the APPI method alone, the results demonstrate how spray ionization from the EPn‐HN may be used to extend the range of compounds amenable to PhotoSpray sources. Copyright © 2009 John Wiley & Sons, Ltd.     

Poly(arylene sulfide)s by nucleophilic aromatic substitution polymerization of 2,7‐difluorothianthrene

Poly(thianthrene phenylene sulfide) and poly(thianthrene sulfide) have been prepared by nucleophilic aromatic substitution polymerization of the activated monomer 2,7‐difluorothianthrene with bis thiophenoxide and sulfide nucleophiles, respectively. The resulting polymers are thermally stable, amorphous materials that have been characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), gel permeation chromatography (GPC), matrix‐assisted laser desorption/ionization‐time‐of‐flight (MALDI‐TOF) mass spectrometry, UV‐Vis spectroscopy, refractometry, and intrinsic viscosity (IV) measurements. The polymers produced exhibit 5% weight loss values approaching 500 °C in inert and air atmospheres and glass transition temperatures that range from 149 to 210 °C. Poly(thianthrene phenylene sulfide) with a number average molecular weight of 22,100 g/mol has been synthesized with an IV in DMPU of 0.62 dL/g at 30 °C. Creasable films of this polymer have been prepared by solvent casting and melt pressing at 250 °C. Films of poly(thianthrene phenylene sulfide) exhibit transparencies greater than 50% at wavelengths exceeding 400 nm and a high refractive index value of 1.692 at a wavelength of 633 nm, making the polymer interesting for optical applications. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2453–2461, 2009     

Virtual reality in medicine: A personal perspective

This personal perspective is an attempt to look at the role and impact of virtual reality (VR) as related to medicine and medical practice over the past 10–15 years. A similar treatise was recently published (Robb, 2002) in much shorter form. This more complete version is still not intended to be, nor can it be, fully comprehensive and inclusive of all developments or viewpoints. It is primarily based on the author’s experience and opinion. Although such a review begs for many references to published works, that too is eschewed in the interest of preserving, for better or worse, the single view of the author in this article. Only seven references are included which contain copious other references to much of the material touched upon in this essay. To the extent that one can learn from history, this synopsis will also fall short, not so much due to lack of confirming references, but rather because the impact of VR in medicine has been an evolutionary culmination of digression and progression that has resulted in some success and useful contributions but also some wasted time and resources.     

Nonequilibrium Fermi golden rule for electronic transitions through conical intersections

We consider photoinduced electronic transitions through conical intersections in large molecules. Starting from the linear vibronic model Hamiltonian and treating linear diabatic couplings within the second order cumulant expansion, we have developed a simple analytical expression for the time evolution of electronic populations at finite temperature. The derived expression can be seen as a nonequilibrium generalization of the Fermi golden rule due to a nonequilibrium character of the initial photoinduced nuclear distribution. All parameters in our model are obtained from electronic structure calculations followed by a diabatization procedure. The results of our model are found to agree well with those of quantum dynamics for a test set of systems: fulvene molecule, 2,6-bis(methylene) adamantyl cation, and its dimethyl derivative.     

Estimating functions of canonical correlation coefficients

Let ρ²₁,…,ρ²_p be the squares of the population canonical correlation coefficients from a normal distribution. This paper is concerned with the estimation of the parameters δ₁,…,δ_p, where $\text{δ}{}_{\mathrm{i}}\text{=}\text{ρ}{}^2{}_{\mathrm{i}}\text{(1 ? ρ}{}^2{}_{\mathrm{i}}\text{)}$, i = 1,…,p, in a decision theoretic way. The approach taken is to estimate a parameter matrix Δ whose eigenvalues are δ₁,…,δ_p, given a random matrix F whose eigenvalues have the same distribution as $\text{r}{}^2{}_{\mathrm{i}}\text{(1 ? r}{}^2{}_{\mathrm{i}}\text{)}$, i = 1,…,p, where r₁,…,r_p are the sample canonical correlation coefficients.