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.     

Zinc porphyrin sensitized redox processes in microemulsions

Photoinduced electron transfer from Zn tetraphenylporphyrin to acceptors solubilized either in the lipid interior or aqueous bulk of anionic oil-in-water microemulsions has been investigated by nanosecond laser photolysis. While intimate cosolubilization appears to decrease the efficiency of electron transfer in the former, enhanced charge separation of the redox products has been observed in the latter.     

20世纪前期两次失败的中外合作科学考察及其原因

上世纪30年代初，由“中国学术团体协会”等组织的两次中外合作科学考察，因为经验不足，以及对外方的意图缺乏细致了解，因此无论准备工作还是成员的选择都存在各种问题，加上外方并无合作诚意，所以合作不成功。回顾这些学术史上的事件，对于了解近代我国学术界成长过程中遭遇的种种问题以及当时社会环境的影响，当有一些帮助。     

Lambda polarization in the K− fragmentation region

Results on Λ polarization in the inclusive reaction K^?p→Λ + X at 12 and 16 GeV/c for 0.6<x<1.0, are presented. These results, obtained with the CERN Omega Spectrometer, show that the polarization is important at large x and increases with p_t over the covered range 0<p_t<1.2 GeV/c. The average polarization for 31 857 lambdas with x>0.6 is P_Λ = 0.35 ± 0.02, along the direction $\text{K}{}^{\mathrm{?}}\text{×}\text{Λ}$. The polarization can be expressed as P(x, p_t) = (0.66±0.03)p_t independent of x in the range covered by the experiment.     

Bromures et ethers ortho- et para-acetoxybenzyliques: Hydrolyse alcaline et étude cinétique de leur réaction avec l'imidazole

A kinetic study of the alkaline hydrolysis and the imidazole-catalysed hydrolysis of a series of o - or p-acetoxybenzyl bromides and p-nitrophenyl ethers has been determined as a function of pH and temperature. The reactions were followed by disappearance of ester and by release of bromide or p-nitrophenolate anions. In both cases, the rates obtained were equal, and proportional to the ester and nucleophile concentrations. The formation of N- acetyl-imidazole intermediate, followed at 245 nm, as well as the observed deuterium isotope effect, correspond to a nucleophilic attack on the carbonyl group. When the acetoxy group is hindered, the reaction with hydroxide ion is slower, no catalysis can occur, and imidazole may react directly at the benzylic site of the molecule.     

Neutron diffraction evidence for anion sublattice disordering in alkali earth fluorides at high temperatures

High temperature powder neutron diffraction studies of calcium, strontium and barium fluorides indicate that there are large thermal motions associated with the anions. This suggests that the anion sublattice in these compounds with the fluoride structure may disorder at temperatures below the melting points. In S:F₂ this disordering appears at about 1370 K and for BaF₂ at about 1300 K. This is in good agreement with transitions of 1440 K and 1240 K, predicted from thermodynamic data.     

Efficient resolution of profen ethyl ester racemates by engineered Yarrowia lipolytica Lip2p lipase

Enzyme-catalyzed enantiomer discrimination is still a great challenge for the development of industrial pharmaceutical processes. For the resolution of ibuprofen, naproxen and ketoprofen racemates, three major anti-inflammatory drugs, only lipases from Candida rugosa present a high selectivity if solvent and surfactant use is discarded. However, their catalytic activities are too low. In the present work, we demonstrate that the lipase Lip2p from the yeast Yarrowia lipolytica has a higher catalytic activity than C. rugosa lipases to hydrolyze the ethyl esters of ibuprofen, naproxen and ketoprofen, but its selectivity is not sufficient [E = 52 (S); 11 (S) and 1.5 (R) respectively]. The enantioselectivity was further improved by site-directed mutagenesis, targeted at the substrate binding site and guided by molecular modelling studies. By investigating the binding modes of the (R)- and (S)-enantiomers in the active site, two amino acid residues located in the hydrophobic substrate binding site of the lipase, namely residues 232 and 235, were identified as crucial for enantiomer discrimination and enzyme activity. The (S) enantioselectivity of Lip2p towards ethyl ibuprofen esters was rendered infinite (E ? 300) by replacing V232 by an A or C residue. Substitution of V235 by C, M, S, or T amino acids led to a great increase in the (S)-enantioselectivity (E ? 300) towards naproxen ethyl ester. Finally, the variant V232F enabled the efficient kinetic resolution of ethyl ketoprofen ester enantiomers [(R)-enantiopreference; E ? 300]. In addition to the increase in selectivity, a remarkable increase in velocity by 2.6, 2.7 and 2.5 times, respectively, was found for ibuprofen, naproxen and ketoprofen ethyl esters.     

Biomass Valorization Using Natural Deep Eutectic Solvents: What’s New in France?

With the growing interest in more environmentally friendly solvents and processes, the introduction of Natural Deep Eutectic Solvents (NaDES) as low cost, non-toxic and biodegradable solvents represent a new opportunity for green and sustainable chemistry. Thanks to their remarkable advantages, NaDES are now arousing growing interest in many fields of research such as food, health, cosmetics and biofuels. Around the world, NaDES are seen as a promising alternative to commonly used petrochemical solvents. The objective of this review is to draw up a panorama of the existing skills on NaDES in French laboratories and industries for the valuation of natural products. This review therefore focuses on current applications, skills and perspectives, in order to analyze the place of French research in the use of NaDES for the valorization of biomass since 2015.     

Morphological Transition of Schooling in 19th-Century France

The transformation over time of level sets—the sets of states for which a given function takes a given value—has no reason to be regular, especially in social science, where the structure of these level sets of a given variable may be altered by a fluctuating demography or disrupted by unexpected events, and where the actors contribute to shaping their space through investment policies. The pioneering construction of graphic derivatives of set-valued maps renews the understanding of dynamic level sets in social science. The exemplary case of schooling in 19th-century France shows the set derivatives of level sets and illustrates how the Franco-Prussian War of 1870–1871 disturbed the directions taken in 1867. A comparison of the observed changes of level sets with those observed under rational theoretical policies leads to the conclusion that the actors behaved with the ambition of optimizing the overall schooling incidence while reducing the gap between boys and girls.