The effect of iodine on the peroxidation of carbonyl compounds

Peroxidation of ketones and aldehydes with iodine as a catalyst was studied. Ketones reacted with 30% aq hydrogen peroxide in the presence of 10 mol % of iodine to yield gem-dihydroperoxides in acetonitrile and hydroperoxyketals in methanol. The yield of hydroperoxidation of various cyclic ketones was 60-98%, including androstane-3,17-dione, while acyclic ketones were converted with a similar efficiency. Aromatic aldehydes were also converted to gem-dihydroperoxides with hydrogen peroxide and iodine as catalyst in acetonitrile and to hydroperoxyacetal in methanol, while the reactivity of aliphatic ones remained the same as in noncatalyzed reactions. tert-Butylhydroperoxide reacted in a similar manner, giving the corresponding perether derivatives. A study was also made of the relative kinetics of dihydroperoxidation from which the Hammet equation gave a reaction constant (rho) of -2.76, indicating the strong positive charge development in the transition state and the important role of rehybridization in the conversion of hydroperoxyhemiketal to gem-dihydroperoxide. In acetonitrile, the iodine catalyst is apparently able to discriminate between the elimination of a hydroxy, methoxy, and hydroperoxy group and addition of water, methanol, and H2O2 to a carbonyl group.     

Higgs portal,fermionic dark matter,and a Standard Model like Higgs at 125 GeV

We show that fermionic dark matter (DM) which communicates with the Standard Model (SM) via the Higgs portal is a viable scenario, even if a SM-like Higgs is found at around 125 GeV. Using effective field theory we show that for DM with a mass in the range from about 60 GeV to 2 TeV the Higgs portal needs to be parity violating in order to be in agreement with direct detection searches. For parity conserving interactions we identify two distinct options that remain viable: a resonant Higgs portal, and an indirect Higgs portal. We illustrate both possibilities using a simple renormalizable toy model.     

STEREOCHEMISTRY OF THE ADDITION OF PENTAFLUOROTHIOPHENOL TO ALKENES AND ACETYLENES

Abstract

Leong and Peach (J. Fluorine Chem., 6, 145 (1975) have shown that at room temperature pentafluorothiophenol readily reacted with 1-hexene and phenylacetylene forming adducts, the reactions following anti-Markovnik type regio-selectivity, and suggested a free radical mechanism.     

Application of fourier analysis to the laser based interferometric strain/displacement gage

The laser based interferometric Strain/Displacement Gage (ISDG) measures the in-plane surface deformation between two small reflecting surface markers. When illuminated with a coherent beam of light, the reflected beams from the two markers form an interference pattern, and monitoring the shift of the fringe pattern allows strain in the gage section of a specimen to be directly measured. A minimum on the fringe pattern can be isolated and tracked as the test proceeds, but this technique utilizes only a small part of the optical signal and often requires a complex programming scheme. This paper presents the application of Fourier transform and phase shifting techniques to the use of the ISDG during microsample tensile testing. The Fourier transform samples the entire fringe pattern and greatly improves the optical signal to noise ratio, and the phase shifting fringe pattern analysis has proven to be more robust and less affected by speckle or optical noise than fringe pattern minimum tracking. This results in the ability to measure larger deformations with a system resolution of ∼5 microstrain and an uncertainty of ±15.5 microstrain. An example involving the microsample tensile testing of a MEMS related LIGA Ni specimen is included to demonstrate the utility of these new techniques.     

Effect of oxygen content and microstructure on the thermo-mechanical response of three Ti–6Al–4V alloys: Experiments and modeling over a wide range of strain-rates and temperatures

Results from a series of experiments on three different titanium alloys, under quasi-static and dynamic loading conditions are presented. The Ti–6Al–4V titanium alloys include the ELI version and two with higher oxygen contents. The strain-rates are varied from 10⁻⁶ to 3378 s⁻¹ while observations are made at temperatures from 233 to 755 K. The alloys initial and deformed photomicrographs and various deformation mechanisms responsible for the induced plastic deformation, are presented and discussed. Differences in the responses of these alloys are observed in terms of thermal softening, work hardening, and strain-rate and temperature sensitivities. The Khan–Huang–Liang (KHL) model is used to effectively simulate the observed responses obtained from these experiments. The model, with the constants determined from these experiments, is then used to predict strain-rate jump experimental results, and also high temperature dynamic experiments for one of the alloys; the predictions are found to be very close to the observations.