Quantitative aspects of internal reflection spectroscopy: Polymer surface composition measurement

The use of band-ratioing techniques in internal reflection spectroscopy (IRS) for a wide variety of polymer surface composition and orientation measurements is discussed. It is shown that quantitative data can be obtained under a wide range of experimental conditions. The effects of variations in sample contact, internal reflection element, and angle of incidence are considered in detail. The applicability and limitations of calibration procedures for the determination of surface composition under various experimental conditions are considered. The requirements for obtaining quantitative results by IRS are shown to be far more lenient than is typically assumed.     

Acoustic radiation from a fluid-filled, subsurface vascular tube with internal turbulent flow due to a constriction

The vibration of a thin-walled cylindrical, compliant viscoelastic tube with internal turbulent flow due to an axisymmetric constriction is studied theoretically and experimentally. Vibration of the tube is considered with internal fluid coupling only, and with coupling to internal-flowing fluid and external stagnant fluid or external tissue-like viscoelastic material. The theoretical analysis includes the adaptation of a model for turbulence in the internal fluid and its vibratory excitation of and interaction with the tube wall and surrounding viscoelastic medium. Analytical predictions are compared with experimental measurements conducted on a flow model system using laser Doppler vibrometry to measure tube vibration and the vibration of the surrounding viscoelastic medium. Fluid pressure within the tube was measured with miniature hydrophones. Discrepancies between theory and experiment, as well as the coupled nature of the fluid-structure interaction, are described. This study is relevant to and may lead to further insight into the patency and mechanisms of vascular failure, as well as diagnostic techniques utilizing noninvasive acoustic measurements.     

All-optical switching in silicon photonic crystal waveguides by use of the plasma dispersion effect

Silicon photonic crystals offer new ways of controlling the propagation of light as well as new tools for the realization of high-density optical integration on monolithic substrates. However, silicon does not possess the strong nonlinearities that are commonly used in the dynamic control of optical devices. Such dynamic control is nevertheless essential if silicon is to provide the higher levels of functionality that are required for optical integration. We demonstrate that the combination of the refractive index change caused by the presence of photoexcited carriers, or so-called plasma dispersion, and photonic crystal properties such as photonic bandgaps, constitutes a powerful tool for active control of light in silicon integrated devices. We show close to 100% modulation depth near the photonic crystal band edge.     

Nucleophilic displacement at benzhydryl centers: asymmetric synthesis of 1,1-diarylalkyl derivatives

[reaction: see text] Activation of substituted 1,1-diarylmethanols as their corresponding toluenesulfonates and subsequent displacement with a range of carbon, nitrogen, oxygen, and sulfur nucleophiles proceeds in 81-96% yield. Enantiomerically enriched diarylmethanols 8a-c were activated and displaced with pyridine acetate enolate with complete stereochemical inversion at carbon to yield 1,1-diarylalkyl derivatives 10a-c without loss of optical purity.     

Stimulus presentation order and the perception of lexical tones in Cantonese

Listeners' auditory discrimination of vowel sounds depends in part on the order in which stimuli are presented. Such presentation order effects have been argued to be language independent, and to result from psychophysical (not speech- or language-specific) factors such as the decay of memory traces over time or increased weighting of later-occurring stimuli. In the present study, native Cantonese speakers' discrimination of a linguistic tone continuum is shown to exhibit order of presentation effects similar to those shown for vowels in previous studies. When presented with two successive syllables differing in fundamental frequency by approximately 4 Hz, listeners were significantly more sensitive to this difference when the first syllable was higher in frequency than the second. However, American English-speaking listeners with no experience listening to Cantonese showed no such contrast effect when tested in the same manner using the same stimuli. Neither English nor Cantonese listeners showed any order of presentation effects in the discrimination of a nonspeech continuum in which tokens had the same fundamental frequencies as the Cantonese speech tokens but had a qualitatively non-speech-like timbre. These results suggest that tone presentation order effects, unlike vowel effects, may be language specific, possibly resulting from the need to compensate for utterance-related pitch declination when evaluating fundamental frequency for tone identification.     

Accuracy and variability of acoustic measures of voicing onset

Five commonly used methods for determining the onset of voicing of syllable-initial stop consonants were compared. The speech and glottal activity of 16 native speakers of Cantonese with normal voice quality were investigated during the production of consonant vowel (CV) syllables in Cantonese. Syllables consisted of the initial consonants /ph/, /th/, /kh/, /p/, /t/, and /k/ followed by the vowel /a/. All syllables had a high level tone, and were all real words in Cantonese. Measurements of voicing onset were made based on the onset of periodicity in the acoustic waveform, and on spectrographic measures of the onset of a voicing bar (f0), the onset of the first formant (F1), second formant (F2), and third formant (F3). These measurements were then compared against the onset of glottal opening as determined by electroglottography. Both accuracy and variability of each measure were calculated. Results suggest that the presence of aspiration in a syllable decreased the accuracy and increased the variability of spectrogram-based measurements, but did not strongly affect measurements made from the acoustic waveform. Overall, the acoustic waveform provided the most accurate estimate of voicing onset; measurements made from the amplitude waveform were also the least variable of the five measures. These results can be explained as a consequence of differences in spectral tilt of the voicing source in breathy versus modal phonation.     

Shear viscosity of langmuir monolayers in the low-density limit

We have measured the shear viscosity in the liquid phase of several Langmuir monolayers with an accuracy better than 30%. The method is based on the optical monitoring of the Brownian diffusion of submicron latex spheres floating at the air-water interface. The values are between 1 and 11x10(-10) N s m(-1), which is 10 to 100 times lower than previous data on similar systems. For N-palmitoyl-6-n-penicillanic acid and L-alpha-dipalmitoylphosphatidylcholine, the variation of the shear viscosity with surface density agrees with a classical free area model, whereas for pentadecanoic acid we observe a compensation effect.