Rearrangements of the carbanions derived from allyl benzyl thioether

The metalation of allyl benzyl thioether involves the benzylic or the allylic hydrogens. The benzylic carbanion undergoes a rapid[2,3] sigmatropic shift whereas the allylic carbanion gives rise to various rearrangements, among them migration of the allylic unit to the para position with allylic inversion. The temperature dependence of the ratio of products arising from the benzylic carbanion vs those from the allylic carbanion shows that the allylic-to-benzylic carbanion transformation occurs only under special conditions: (a) with slow addition of the base; (b) with thioether in excess relative to the base, and (c) on raising the temperature of the reaction medium from ?78° to ?15°. In the last instance, the proton transfer is intramolecular as shown with labeled thioethers. The extent of the different rearrangements depends on the temperature and solvent. A choice of mechanism cannot be made at this time for the para migration 5→9a. A leaving group effect on the reaction regioselectivity of the carbanion from allyl methyl thioether with benzyl halides has been noticed. The presence of dibenzyl indicates that, in addition to S_N2 reactions, some electron transfer process is occurring.     

Interaction of kerogen and mineral matrix of an oil shale in an oxidative atmosphere

The effects of the inorganic matrix of the oil shale on the oxidation of the kerogen at temperatures up to 1000°C in an air atmosphere were investigated Kerogen was isolated by successive HCl, HF and LiAlH₄ treatments. The initial shale and each product of every demineralization process were oxidized in a thermogravimetric system in an air atmosphere. The oxidation products were analyzed by Fourier transform infrared spectroscopy. Changes in the chemical structure of the organic material of the shale were correlated with the separated constituents of the inorganic matrix. Oxidation of the kerogen occurred in two stages. The first stage was complete at about 400°C. The oxidized product after the first stage contained a char of an aromatic ring system substituted with some aliphatic material and carbonyl groups. Calcium minerals increased the reactivity of the aromatic part of the organic material towards the oxidation reactions. Where calcium minerals were absent, mainly the aliphatic and the carbonyl groups decomposed. Silicates and pyrites did not affect the reactivity of the organic material in oxidation reactions.     

Vibrational relaxation of compressed nD2 fluid

Experimental observations of the vibrational population relaxation time of ⁿD₂ fluid under pressures of up to 500 atm in the 25–85 K range are presented and described in terms of a semi-classical model for energy transfer in liquids. For comparison with the parameters of this model, a classical equivalent potential for quantum systems is derived from the “real” intermolecular potential.     

The Effects of Different Doses of ROCK Inhibitor,Antifreeze Protein III,and Boron Added to Semen Extender on Semen Freezeability of Ankara Bucks

In the presented study, the effects of ROCK inhibitor Y-27632, antifreeze protein III, and boron at two different doses were investigated on the spermatological parameters of Ankara buck semen after freeze–thawing. Ejaculates were collected from bucks using an electroejaculator during the breeding season. The ejaculates that showed appropriate characteristics were pooled and used in the dilution and freezing of semen. The extender groups were formed by adding two different doses of three different additives (ROCK inhibitor Y-27632, 5 and 20 µM; antifreeze protein III, 1 and 4 µg/mL; boron, 0.25 and 1 mM) to the control extender. The semen was diluted with the different extenders at 35–37 °C and loaded into straws. Sperm samples frozen in liquid nitrogen vapors, following equilibration, were stored in liquid nitrogen. It was observed that extender supplementation improved post-thaw motility of Ankara buck semen after freeze–thawing. Differences were significant (p < 0.01) for 5 and 10 µM doses of ROCK inhibitor (71.82% and 74.04 % motility), as well as for 0.25 and 1 mM doses of boron (76.36% and 72.08% motility), compared to the control group (66.15% motility). With respect to the evaluation of acrosomal integrity and mitochondrial activity after freeze–thawing, although supplementation provided protection at all doses, the efficacy was not statistically significant (p > 0.05). It was observed that DNA damage was improved by antifreeze protein III at 1 µg/mL (1.23% ± 0.23%) and by boron at all doses (0.25 mM: 1.83% and 1 mM: 1.18%) compared to the control group (3.37%) (p < 0.01), following the thawing process. In the present study, it was determined that some additives added to the extender provided significant improvements in buck spermatozoa motility and DNA damage after thawing.