Shearing of oriented polyethylene and polypropylene

To learn more about the out-of-plane deformation of polymer lamellae during drawing, we have measured the resistance to shear along various planes in uniaxially oriented polyethylene and polypropylene. Fissures parallel to the orientation axis in oriented materials always cause too small an experimental value for the resistance of crystal glide parallel to the chain axes, but a rough estimate for the resistance to crystal glide is obtained using the elastic anisotropy. Also, the results suggest that kinking can be easier than glide when glide is inhibited by tie molecules.     

Surface photochemistry: The photo-chlorination of aromatic hydrocarbons with ferric chloride on alumina

Irradiation of a number of aromatic hydrocarbons adsorbed on alumina in the presence of ferric chloride leads to monochlorination.     

Structure elucidation with lanthanide-induced shifts. 4—Bound shifts vs relative shifts

The use of lanthanide shift reagents (LSR's) to obtain additional structural information from nuclear magnetic resonance studies has gained widespread acceptance. However, there has not been general agreement with regard to the most appropriate methodology for analysis of the shifted NMR spectra. We present arguments that only the bound shifts (Δ₁) corresponding to the LS complex should be used for correlation of lanthanide-induced shifts with molecular structure by means of the pseudocontact equation. Several examples are discussed of compounds for which the relative induced shifts are dependent on the concentration of LSR. For such cases it is not possible for both Δ₁ and Δ₂ (the bound shift corresponding to the LS₂ complex) to correlate successfully with the correct structure. Alternative methods of obtaining bound shifts are critically evaluated.     

When electron exchange is chemical exchange-assignment of 1H NMR spectra of paramagnetic cobalt(II)-2,2':6'2''-terpyridine complexes

Electron exchange between [Co(terpy)2]3+ and [Co(terpy)2]2+ can be monitored by 1H NMR exchange spectroscopy and allows the cobalt(II) spectra to be fully assigned.     

Anisotropic metal nanoparticles: Synthesis, assembly, and optical applications

This feature article highlights work from the authors' laboratories on the synthesis, assembly, reactivity, and optical applications of metallic nanoparticles of nonspherical shape, especially nanorods. The synthesis is a seed-mediated growth procedure, in which metal salts are reduced initially with a strong reducing agent, in water, to produce approximately 4 nm seed particles. Subsequent reduction of more metal salt with a weak reducing agent, in the presence of structure-directing additives, leads to the controlled formation of nanorods of specified aspect ratio and can also yield other shapes of nanoparticles (stars, tetrapods, blocks, cubes, etc.). Variations in reaction conditions and crystallographic analysis of gold nanorods have led to insight into the growth mechanism of these materials. Assembly of nanorods can be driven by simple evaporation from solution or by rational design with molecular-scale connectors. Short nanorods appear to be more chemically reactive than long nanorods. Finally, optical applications in sensing and imaging, which take advantage of the visible light absorption and scattering properties of the nanorods, are discussed.     

Relative contributions of spectral and temporal cues for phoneme recognition

Cochlear implants provide users with limited spectral and temporal information. In this study, the amount of spectral and temporal information was systematically varied through simulations of cochlear implant processors using a noise-excited vocoder. Spectral information was controlled by varying the number of channels between 1 and 16, and temporal information was controlled by varying the lowpass cutoff frequencies of the envelope extractors from 1 to 512 Hz. Consonants and vowels processed using those conditions were presented to seven normal-hearing native-English-speaking listeners for identification. The results demonstrated that both spectral and temporal cues were important for consonant and vowel recognition with the spectral cues having a greater effect than the temporal cues for the ranges of numbers of channels and lowpass cutoff frequencies tested. The lowpass cutoff for asymptotic performance in consonant and vowel recognition was 16 and 4 Hz, respectively. The number of channels at which performance plateaued for consonants and vowels was 8 and 12, respectively. Within the above-mentioned ranges of lowpass cutoff frequency and number of channels, the temporal and spectral cues showed a tradeoff for phoneme recognition. Information transfer analyses showed different relative contributions of spectral and temporal cues in the perception of various phonetic/acoustic features.