Catalytic oxidative cleavage of olefins promoted by osmium tetroxide and hydrogen peroxide

Hydrogen peroxide was employed as the terminal oxidant in the osmium tetroxide mediated oxidative cleavage of olefins, producing the corresponding aldehyde and ketone products. Aryl olefins are cleaved in good to excellent yield regardless of arene electronics. Alkyl olefins cleave in moderate to good yield for di- and tri-substituted alkenes.     

Metal ion complexing properties of dipyridoacridine, a highly preorganized tridentate homologue of 1,10-phenanthroline

DPA (dipyrido[4,3-b;5,6-b]acridine) may be considered as a tridentate homologue of phen (1,10-phenanthroline). In this paper some of the metal ion complexing properties of DPA in aqueous solution are reported. Using UV-visible spectroscopy to follow the intense π-π* transitions of DPA as a function of pH gave protonation constants at ionic strength (μ) = 0 and 25 °C of pK(1) = 4.57(3) and pK(2) = 2.90(3). Titration of 10(-5) M solutions of DPA with a variety of metal ions gave log K(1) values as follows: Zn(II), 7.9(1); Cd(II), 8.1(1); Pb(II), 8.3(1); La(III), 5.23(7); Gd(III), 5.7(1); Ca(II), 3.68; all at 25 °C and μ = 0. Log K(1) values at μ = 0.1 were obtained for Mg(II), 0.7(1); Sr(II), 2.20(1); Ba(II), 1.5(1). The log K(1) values show that the high level of preorganization of DPA leads to complexes 3 log units more stable than the corresponding terpyridyl complexes for large metal ions such as La(III) or Ca(II), but that for small metal ions such as Mg(II) and Zn(II) such stabilization is minimal. Molecular mechanics calculations (MM) are used to show that the best-fit M-N length for coordination with DPA is 2.60 ?, accounting for the high stability of Ca(II) or La(III) complexes of DPA, which are found to have close to this M-N bond length in their phen complexes.     

BEEM-π calculations for a series of pyridines and their 14N N.Q.R.

The ⁵⁷Fe Mössbauer spectrum of a powdered sample of phthalocyanine-iron(II) in an applied magnetic field of 3·0 teslas has been measured as a function of temperature in the range 4·2 K to 100 K. Measurements have also been made at 4·2 K with 6·0 teslas applied, and on a single crystal specimen at 4·2 K with 3·0 teslas applied. Independent computer fits to the three measurements taken at 4·2 K were found to be consistent with one another, and showed that detailed information concerning magnetic anisotropy can be obtained even from powdered samples of paramagnets by Mössbauer spectroscopy. Although the asymmetry parameter in the electric field gradient tensor was found to be small, there was a significant departure from tetragonal symmetry in the magnetic properties of the molecule. The magnetic hyperfine field at the ⁵⁷Fe nucleus was found to be positive in all directions, indicating that all three electronic g values are significantly greater than 2·0.     

GaAs multiple quantum well microresonator modulators grown on silicon substrates

We report new results on the modulation characteristics of GaAs/AlGaAs asymmetric Fabry-Perot modulators grown on silicon substrates. We discuss factors affecting device performance and evaluate these by growing p-i-n quantum well diodes, and multilayer reflector stacks on silicon. Using data from these test structures we have designed an asymmetric microresonator modulator and achieve, experimentally, a 40% reflection change with only 5 V and a contrast ratio of 7.4 dB, also with 5 V.Formerly at:Philips Research Laboratories, Redhill, UK     

On the generalized power moment problem

We present a method for solving the power moment problem in the general case where the given moments are arbitrary finite real numbers.     

Chromatic uniqueness and equivalence of K4 homeomorphs

We derive a new formula for the chromatic polynomial of any K₄ homeomorph. We obtain a large family of chromatically unique K₄ homeomorphs. We obtain seven infinite pairs of chromatically equivalent nonisomorphic K₄ homeomorphs.     

Evidence for two discrete sources of 2f1-f2 distortion-product otoacoustic emission in rabbit. II: Differential physiological vulnerability.

In a previous report, it was shown that, in normal rabbit ears, the amplitude and phase of 2f1-f2 distortion-product otoacoustic emissions (DPOAEs) elicited by low-level (< 60-70 dB SPL) stimuli display a differential dependence on stimulus parameters to those evoked by high-level (> 60-70 dB SPL) stimuli, indicating differences in the underlying generation mechanisms. In the present study, the physiological vulnerability of DPOAEs in each of the two 2f1-f2 DPOAE-response regions identified on the basis of differential parametric properties, was characterized. Thus emissions evoked using stimulus levels from 45-75 dB SPL were measured over time upon: (1) induction of lethal anoxia, (2) acute injection of ethacrynic acid, and (3) acute injection of ethacrynic acid 2 h after a single administration of gentamicin. The DPOAEs evoked by low-level stimuli (45 dB SPL) were abolished within 3-4 min of induction of anoxia, whereas DPOAEs evoked by high-level stimuli (75 dB SPL) were unchanged in this period. The high-level emissions decreased with a complex time course postmortem, and demonstrated behaviors, including evidence of susceptibility to fatigue, suggesting a dependence upon a cochlear energy supply. Low-level DPOAEs could be temporarily abolished, with complete recovery, by an acute administration of ethacrynic acid that had little effect on high-level DPOAEs. Treatment with the gentamicin and ethacrynic-acid combination, which would be expected to produce widespread hair-cell damage, eliminated low-level DPOAEs, and greatly reduced high-level emissions. In combination with previously published data, these findings strongly suggest that low- and high-level 2f1-f2 DPOAEs arise from discrete sources. The data are consistent with the proposal that the low-level DPOAE source is an active, micromechanical process, but suggest that the proposed origin of high-level DPOAEs exclusively in the passive macromechanics of the cochlear partition may be incorrect. The elimination of both low- and high-level DPOAEs revealed the presence of a third, residual 2f1-f2 DPOAE component, approximately 75-80 dB below the stimulus-tone levels, that may reflect the true passive-distortion response of the cochlea.     

Investigation of a novel solid-phase chemiluminescent analytical system, incorporating photographic detection, for the measurement of glucose

A method has been developed for the rapid determination of substances by use of solid-phase reagents and a luminescence indicator reaction coupled with photographic detection of the light. The viability of the assay has been demonstrated for glucose estimations. The method uses small sample sizes (5-20 mul) and shows good sensitivity, e.g., detection of glucose down to 28 nmole.