Efficient Preparation of γ-Hydroxynitriles via Nitrile Enolate-Epoxide Reactions: Scope and Diastereoselectivity

The nucleophilic opening of epoxides by nitrile enolates using an efficient, convenient protocol is described. The diastereoselectivity of this reaction was explored and found to give syn:anti ratios ranging from 1.1:1.0 to 4.8:1.0.

     

The structure of linear codes of constant weight

In this paper we determine completely the structure of linear codes over of constant weight. Namely, we determine exactly which modules underlie linear codes of constant weight, and we describe the coordinate functionals involved. The weight functions considered are: Hamming weight, Lee weight, two forms of Euclidean weight, and pre-homogeneous weights. We prove a general uniqueness theorem for virtual linear codes of constant weight. Existence is settled on a case by case basis.

     

Benefit of modulated maskers for speech recognition by younger and older adults with normal hearing

To assess age-related differences in benefit from masker modulation, younger and older adults with normal hearing but not identical audiograms listened to nonsense syllables in each of two maskers: (1) a steady-state noise shaped to match the long-term spectrum of the speech, and (2) this same noise modulated by a 10-Hz square wave, resulting in an interrupted noise. An additional low-level broadband noise was always present which was shaped to produce equivalent masked thresholds for all subjects. This minimized differences in speech audibility due to differences in quiet thresholds among subjects. An additional goal was to determine if age-related differences in benefit from modulation could be explained by differences in thresholds measured in simultaneous and forward maskers. Accordingly, thresholds for 350-ms pure tones were measured in quiet and in each masker; thresholds for 20-ms signals in forward and simultaneous masking were also measured at selected signal frequencies. To determine if benefit from modulated maskers varied with masker spectrum and to provide a comparison with previous studies, a subgroup of younger subjects also listened in steady-state and interrupted noise that was not spectrally shaped. Articulation index (AI) values were computed and speech-recognition scores were predicted for steady-state and interrupted noise; predicted benefit from modulation was also determined. Masked thresholds of older subjects were slightly higher than those of younger subjects; larger age-related threshold differences were observed for short-duration than for long-duration signals. In steady-state noise, speech recognition for older subjects was poorer than for younger subjects, which was partially attributable to older subjects' slightly higher thresholds in these maskers. In interrupted noise, although predicted benefit was larger for older than younger subjects, scores improved more for younger than for older subjects, particularly at the higher noise level. This may be related to age-related increases in thresholds in steady-state noise and in forward masking, especially at higher frequencies. Benefit of interrupted maskers was larger for unshaped than for speech-shaped noise, consistent with AI predictions.     

Hydrolysis of a sulfonamide by a novel elimination mechanism generated by carbanion formation in the leaving group

The alkaline hydrolysis of N-alpha-methoxycarbonyl benzyl-beta-sultam occurs 10(3) times faster than the corresponding carboxylate and with rapid D-exchange at the alpha-carbon: the pH rate profile indicates pre-equilibirum CH ionisation and together with formation of benzoyl formate as a product this suggests a novel mechanism for hydrolysis.     

The History of Skunk Defensive Secretion Research

The striped skunk (Mephitis mephitis) is widely known for the highly odoriferous defensive secretion it uses to repel predators. Chemists have sporadically investigated the chemical composition of this secretion for many years. In this research, a number of chemicals have been incorrectly attributed to this secretion and the errors incorporated into the chemical literature. The major component in skunk spray was erroneously believed to be l-butanethiol, until it was later shown that the actual compound was (E)-2-butene-l-thiol. More recently, two studies identified the third major compound in the secretion as either (E)-2-butenyl methyl disulfide or (E)-2-butenyl propyl sulfide. These structural assignments were incorrect and the compound was later shown to be (E)-2-butenyl thioacetate. Two investigations have reported chemicals that could not be confirmed in a later study, so these compounds may have been artifacts produced during isolation or analysis. The striped skunks secretion is similar to, but different from, the defensive secretions of two other skunk species, the spotted skunk (Spilogale gracilis) and the hog-nosed skunk (Conepatus mesoleucus).Folklore asserts that tomato juice will neutralize the odor of skunk spray, but human olfactory fatigue can explain the apparent disappearance of the odor on sprayed pets. The odoriferous thiols in skunk spray can easily be neutralized by oxidation to sulfonic acids.     

A fluidized bed process for electron sterilization of powders

A small capacity (100 g.s⁻¹) pilot system is described for presentation of powders and fine aggregates at high velocity, to an electron beam. Electron beam dose rate is continuously monitored in real time, while the thickness of the fluidized bed used to pneumatically transport the product can be monitored and controlled using beta-gauge techniques. Using electron paramagnetic resonance (EPR) techniques, alanine power mixed with the product is used for precise determination of dose delivered to the powder stream. Thin film dosimeters transported in the bed are also used for dose determination. Results with a variety of products are presented using both dose rate and velocity as the independent variables. Lethality data for the bioburdens present in several powdered foodstuffs are discussed.     

Electroclinic effects in a homogeneously aligned smectic A cell

The electroclinic effect, in a material having a first order S_A to S_C* transition, is studied using the half leaky guided mode geometry. Using an approximately 1 μm thick, homogeneously aligned cell, the voltage induced director twist is characterized at a few temperatures in the S_A phase. The mean field theory readily explains the data recorded at low fields where a linear dependence on voltage is found. However, at higher fields, an unexpected saturation occurs which is most likely caused by the influence of strong surface anchoring forces.