Indices de refraction et birefringence spontanee de l'orthophosphate de plomb ferroelastique

Refraction indices at room temperature and the temperature dependence of the spontaneous birefringence have been measured in ferroelastic lead orthophosphate. The 180°C phase transition in this material has been determined as a thermodynamic first order transition.     

Parallel synthesis and high throughput dissolution testing of biodegradable polyanhydride copolymers

We have demonstrated that polycondensation reactions can be carried out in a combinatorial fashion and that the polymer library can be screened at high throughput using a rapid prototyping technique to fabricate multiwell substrates. A linearly varying compositional library of 100 different biodegradable polyanhydride random copolymers that are promising carriers for controlled drug delivery was designed, fabricated, and characterized by IR microscopy within a few hours. The polyanhydride copolymer library was based on 1,6-bis(p-carboxyphenoxy)hexane (CPH) and sebacic anhydride (SA) and was characterized with infrared microspectroscopy to determine the composition within each well. Since degradation and release rates depend on copolymer composition, we also developed new high-throughput methods to investigate drug release from this library of copolymers by designing specific wells for each task. A subset of this library was chosen, and a substrate was designed and fabricated to enable the synthesis and monitoring of dye dissolution from a range of polyanhydride copolymers in a parallel fashion using a CCD camera. Multisample substrates were fabricated with a novel rapid prototyping method that consists of an organic solvent-resistant array of 10 x 10 microwells of 2-muL volume each. The libraries were deposited with a custom-built liquid dispensing system consisting of a series of computer-controlled volume-dispensing pumps and XYZ motion stages. The parallel dye dissolution study displayed a decreasing rate of release with increasing CPH content. This result agrees with previously published data for dye release from poly(CPH-co-SA) copolymers. The methodology described in this work is amenable to numerous applications in the arenas of high-throughput polymer synthesis and characterization.     

Estimation of frequency-averaged loss factors by the power injection and the impulse response decay methods

This paper describes a comparison, both analytically and experimentally, between two widely used loss factor estimation techniques frequently used in statistical energy analysis. Analytical models of simple spring/mass/damper systems were created to compare frequency-averaged loss factor values from the single subsystem power injection method and the impulse response decay method. The parameters of the analytical models were varied to study the effects of the total number of modes, amount of damping, location of modes within frequency bands, and the width of the frequency bands on loss factor estimation. The analytical study shows that both methods give accurate loss factor values as long as the damping values remain realistic for linear systems and at least one modal resonance is present in each frequency band. These analytical results were verified experimentally by measuring the loss factors of simple steel plates, with and without damping treatments applied.     

Underwater temporary threshold shift in pinnipeds: effects of noise level and duration

Behavioral psychophysical techniques were used to evaluate the residual effects of underwater noise on the hearing sensitivity of three pinnipeds: a California sea lion (Zalophus californianus), a harbor seal (Phoca vitulina), and a northern elephant seal (Mirounga angustirostris). Temporary threshold shift (TTS), defined as the difference between auditory thresholds obtained before and after noise exposure, was assessed. The subjects were exposed to octave-band noise centered at 2500 Hz at two sound pressure levels: 80 and 95 dB SL (re: auditory threshold at 2500 Hz). Noise exposure durations were 22, 25, and 50 min. Threshold shifts were assessed at 2500 and 3530 Hz. Mean threshold shifts ranged from 2.9-12.2 dB. Full recovery of auditory sensitivity occurred within 24 h of noise exposure. Control sequences, comprising sham noise exposures, did not result in significant mean threshold shifts for any subject. Threshold shift magnitudes increased with increasing noise sound exposure level (SEL) for two of the three subjects. The results underscore the importance of including sound exposure metrics (incorporating sound pressure level and exposure duration) in order to fully assess the effects of noise on marine mammal hearing.     

Bifunctional, conjugated oligomers for orthogonal self-assembly: selectivity varies from planar substrates to nanoparticles

A diphenylacetylene containing two different end groups (isonitrile and thioacetate) was synthesized, showing that the chemistry used to install each end group is compatible with that of the others. The isonitrile group binds preferentially to platinum, and the thiol group binds preferentially to gold. However, the selectivity was different when nanoparticles were compared to planar substrates.     

Auditory masking in three pinnipeds: aerial critical ratios and direct critical bandwidth measurements

This study expands the limited understanding of pinniped aerial auditory masking and includes measurements at some of the relatively low frequencies predominant in many pinniped vocalizations. Behavioral techniques were used to obtain aerial critical ratios (CRs) within a hemianechoic chamber for a northern elephant seal (Mirounga angustirostris), a harbor seal (Phoca vitulina), and a California sea lion (Zalophus californianus). Simultaneous, octave-band noise maskers centered at seven test frequencies (0.2-8.0 kHz) were used to determine aerial CRs. Narrower and variable bandwidth masking noise was also used in order to obtain direct critical bandwidths (CBWs). The aerial CRs are very similar in magnitude and in frequency-specific differences (increasing gradually with test frequency) to underwater CRs for these subjects, demonstrating that pinniped cochlear processes are similar both in air and water. While, like most mammals, these pinniped subjects apparently lack specialization for enhanced detection of specific frequencies over masking noise, they consistently detect signals across a wide range of frequencies at relatively low signal-to-noise ratios. Direct CBWs are 3.2 to 14.2 times wider than estimated based on aerial CRs. The combined masking data are significant in terms of assessing aerial anthropogenic noise impacts, effective aerial communicative ranges, and amphibious aspects of pinniped cochlear mechanics.     

Amine-catalyzed coupling of aldehydes and ketenes derived from Fischer carbene complexes: formation of beta-lactones and enol ethers

Aldehydes react with ketenes generated from photolysis of Fischer chromium carbene complexes to generate either beta-lactones or enol ethers resulting from decarboxylation of beta-lactones. The reaction is catalyzed by tertiary amines and can occur with diastereoselectivity greater than 20:1 with DMAP as the catalyst.