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Biomedical subjects

G Asensio

Publications and source records attributed to G Asensio.

4 recordsLinked to original sources

Antimicrobial susceptibility and pneumococcal serotypes.

The increase in antibiotic resistance and the possible changes in serotype prevalence as a consequence of a new conjugated vaccine have contributed to renewed interest in the study of pneumococcal serotypes and their antibiotic resistances. Spain still has one of the highest penicillin resistance rates, but in the past 4-5 years a slight decrease has been observed. The level of resistance has not increased either, 12.7% of the 11 165 isolates studied showed high-level penicillin resistance but 94% of these had an MIC of only 2 mg/L. Serotypes 6, 9, 14, 19 and 23 included 83% of the penicillin-resistant pneumococci; the remaining 17% belonged to 18 different serotypes. We analysed these minor penicillin-resistant serotypes in view of their potential increase following a possible child vaccination programme. Four of these serotypes (11, 15, 21 and 35) were the most prevalent, and among them serotype 15 was particularly frequent with >50% of its strains resistant. The effective control of these minor penicillin-resistant serotypes should be based on continuous surveillance of pneumococcal epidemiology.

Drug Resistance, Bacterial↗

Influence of remote substituents on the equatorial/axial selectivity in the monooxygenation of methylene C--H bonds of substituted cyclohexanes.

The reactivity of individual C--H bonds in the methyl(trifluoromethyl)dioxirane TFDO oxygenation of stereogenic methylene groups in conformationally homogeneous monosubstituted cyclohexanes (2) has been determined. The unexpectedly high occurrence of O-atom insertion into C--H(ax) bonds suggests an in plane trajectory attack in the oxygenation while the diastereoselectivity of the reaction is qualitatively interpreted on the basis of the distinct hyperconjugative stabilization by the substituent of diastereomeric transition states due to long-range through bond interactions.

Journal Article↗

Hyperconjugative Control by Remote Substituents of Diastereoselectivity in the Oxygenation of Hydrocarbons.

The oxidation of 2-substituted adamantanes (2) with TFDO (1) is reported. The data show a stereodifferentiation of the chemical environments induced by remote electron-withdrawing substituents which produces remarkable Z/E diastereoselectivity in the oxidation of the tertiary C(5)-H and C(7)-H bonds. The results show a bell-shaped correlation between the Z/E stereoselectivity and the substituent constant sigma(I), which is interpreted in terms of hyperconjugative stabilization of the diastereomeric transition states.

Journal Article↗

C(5)H(7)O(2)(+) ions: the correlation between their thermochemistry in acidic solution and their chemistry in the gas phase

Each of a series of C(5)H(6)O(2) isomeric carboxylic acid and unsaturated lactones (1-7) was protonated in both concentrated sulfuric acid and trifluoromethanesulfonic acid. The thermally induced transformations of the protonated species were then studied over a temperature range of -30 to +160 degrees C. In the case of alpha,beta-unsaturated lactones, protonation took place on the carbonyl oxygen and gave the corresponding stable O-protonated species. Conversely, unconjugated lactones and acetylenic acid 7 were converted even at low temperature into the diprotonated ketoacid 8H(2)()o(+2)() by the acid-catalyzed addition of water to the C-protonated precursor. Upon being heated at 160 degrees C, this acid gave protonated 1,3-cyclopentanedione. In the absence of water, decarbonylation followed by polymerization was observed in lactones 4 and 5. The CIMS spectra of compounds 1-7 were recorded using methane, ammonia, and moist air as reagent gases to determine the correlation between the fragmentation routes in the gas phase and the transformations observed in solution. Ammonia and moist air enabled us to determine the different proton affinities of these compounds. The data obtained in strong acids were used to assign reasonable structures to the gas-phase ions.

Journal Article↗