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31.
The (17R,20S,22S,24S) C20-C29 segment of contignasterol has been stereoselectively prepared in 8 steps and 40% overall yield from (S)-carvone. Synthetic studies towards contignasterol's C/D ring functionalization/isomerization are also reported. 相似文献
32.
Jorge M. Seminario Monica C. Concha Peter Politzer 《Journal of computational chemistry》1992,13(2):177-182
The structures and relative stabilities of furoxan and some of its isomers, e.g., the 1,2-dinitrosoethylenes, have been determined by means of ab initio Hartee–Fock and Møller–Plesset calculations. Geometries were optimized at the HF/3-21G, HF/6-31G* and MP2/6-31G* levels, and subsequently used for computing MP2/6-31G*, MP3/6-31G*, and MP4/6-31G* energies. The results are markedly affected by the inclusion of electronic correlation, which renders three of the isomers unstable. It also emphasizes the importance of a zwitterionic contribution to the structure of furoxan, which promotes ring-opening through a cis 1,2-dinitrosoethylene intermediate/transition state that has an MP4/6-31G*//MP2/6-31G* energy that is 31.6 kcal/mol above furoxan. 相似文献
33.
Benjamin Ruiz Philippe Sistat Patrice Huguet Gérald Pourcelly Monica Araya-Farias Laurent Bazinet 《Journal of membrane science》2007
Electrodialysis (ED) is a membrane process used on a large scale. However, one of the common problems is fouling of ion-exchange membranes stacked in the cell. The use of pulsed power, consisting in applying a constant current density during a fixed time of application (Ton) followed by a pause duration (Toff), was demonstrated recently as an effective fouling mitigation method for electrodialysis. Up until now, no work has investigated the potential of electrodialysis using pulsed electric field on protein fouling. The aim of the present work was to study the influence of pulsed electric field (PEF) with a low frequency square shaped periodic signal (Ton = 10 s–Toff = 10 s, Ton = 10 s–Toff = 40 s) in comparison with dc current during electrodialysis of a casein solution at different current densities (10, 20 and 30 mA/cm2) on membrane fouling. It appeared from these results that PEF, under certain conditions of pulse, would avoid fouling on anion-exchange membranes. For 10 s–40 s pulsed electric field conditions, no fouling was observed with any density, while for 10 s–10 s PEF conditions, fouling appeared only at current density over 10 mA/cm2. dc current, whatever the current density conditions, led to a fouling on the diluate side of the AEM. Furthermore, when fouling occurred, magnitude layer thickness and dry weight increased with the applied current density. The nature of the fouling was identified as 97% protein. The protein fouling would be due to the dissociation of water molecules and/or heat increase at the anion-exchange membrane interface. The relaxation time of the pulse would limit both phenomena on the membrane. 相似文献
34.
Gadolinium‐Decorated Silica Microspheres as Redox‐Responsive MRI Probes for Applications in Cell Therapy Follow‐Up 下载免费PDF全文
Dr. Monica Muñoz Úbeda Dr. Fabio Carniato Dr. Valeria Catanzaro Sergio Padovan Dr. Cristina Grange Dr. Stefano Porta Dr. Carla Carrera Prof. Lorenzo Tei Dr. Giuseppe Digilio 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(23):7716-7720
The redox microenvironment within a cell graft can be considered as an indicator to assess whether the graft is metabolically active or hypoxic. We present a redox‐responsive MRI probe based on porous silica microparticles whose surface has been decorated with a Gd‐chelate through a disulphide bridge. Such microparticles are designed to be interspersed with therapeutic cells within a biocompatible hydrogel. The onset of reducing conditions within the hydrogel is paralleled by an increased clearance of Gd, that can be detected by MRI. 相似文献
35.
Andrzej Chmura Sven Rustler Monica Paravidino Fred van Rantwijk Andreas Stolz Roger A. Sheldon 《Tetrahedron: Asymmetry》2013,24(19):1225-1232
Enantiomerically pure (S)-mandelic acid was synthesised from benzaldehyde by sequential hydrocyanation and hydrolysis in a bienzymatic cascade at starting concentrations up to 0.25 M. A cross-linked enzyme aggregate (CLEA) composed of the (S)-selective oxynitrilase from Manihot esculenta and the non-selective nitrilase from Pseudomonas fluorescens EBC 191 was employed as the biocatalyst. The nitrilase produces approx. equal amounts of (S)-mandelic acid and (S)-mandelic amide from (S)-mandelonitrile under standard conditions, but we surprisingly found that high (up to 0.5 M) concentrations of HCN induced a marked drift towards amide production. By including the amidase from Rhodococcus erythopolis in the CLEA we obtained (S)-mandelic acid as the sole product in 90% yield and >99% enantiomeric purity. 相似文献
36.
Laura Pop Pierrik Lassalas László Csaba Bencze Monica Ioana Toşa Botond Nagy Florin Dan Irimie Christophe Hoarau 《Tetrahedron: Asymmetry》2012,23(6-7):474-481
Stereoselective preparative enzymatic acylation and hydrolysis/methanolysis of various C-substituted rac-thiazol-2-yl-methanols were achieved for the preparation of enantiopure or enantiomerically enriched, naturally occurring 2-hydroxymethylthiazoles. The absolute configurations of the resulting secondary alcohols were determined by a detailed 1H NMR study of Mosher’s derivatives. 相似文献
37.
38.
Gabriel Hancu Daniela Lupu Andreea Milan Monica Budu Enik Barabs‐Hajdu 《Biomedical chromatography : BMC》2021,35(1)
Venlafaxine (VFX) is a serotonin and norepinephrine reuptake inhibitor chiral drug used in therapy as an antidepressant in the form of a racemate consisting of R‐ and S‐VFX. The two enantiomers of VFX exhibit different pharmacological activities: R‐VFX inhibits both norepinephrine and serotonin synaptic reuptake, whereas S‐VFX inhibits only the serotonin one. R‐ and S‐VFX are metabolized in the liver to the respective R‐ and S‐O‐desmethylvenlafaxine (ODVFX), R‐ and S‐N‐desmethylvenlafaxine (NDVFX), and R‐ and S‐N,O‐didesmethylvenlafaxine (NODVFX). The pharmacological profile of ODVFX is close to that of VFX, whereas the other two chiral metabolites (NDVFX and NODVFX) have lower affinity for the receptor sites. The pharmacokinetics of the VFX enantiomers appear stereoselective, including the metabolism process. In the past 20 years, several studies describing the enantioselective analysis of R‐ and S‐VFX in pharmaceutical formulations and its chiral metabolites in biological matrices were published. These methods encompass liquid chromatography coupled with UV detection, mass spectrometry, or tandem mass spectrometry, and capillary electrophoresis. This paper reviews the published methods used for the determination of the individual enantiomers of VFX and its chiral metabolites in different matrices. 相似文献
39.
Monica Roşiu 《复变函数与椭圆型方程》2015,60(2):181-190
We extend the notion and basic properties of quadratic differential divisors to a Klein surface, using the corresponding form’s divisors from the double cover of the Klein surface. 相似文献
40.
Paul Barvinschi Oana Stefanescu Thomas Dippong Simona Sorescu Mircea Stefanescu 《Journal of Thermal Analysis and Calorimetry》2013,112(1):447-453
The study reports the preparation of CoFe2O4/SiO2 nanocomposites by a new modified sol–gel method starting from cobalt nitrate, iron nitrate, and diols: 1,2-ethanediol (EG), 1,3-propanediol (1,3PG), and tetraethylorthosilicate (TEOS), for final compositions of 30 %CoFe2O4/70 %SiO2 and 50 %CoFe2O4/50 %SiO2. The method is based on the formation of a Co(II), Fe(III)—carboxylate precursors mixture, during the redox reaction between the NO 3 ? ion and the diol (~140 °C) within the silica gels. The thermal decomposition of these complex combinations takes place at ~300 °C leading to the corresponding amorphous metal oxides within the pores of the hybrid gels. Depending on the subsequent thermal treatment, CoFe2O4 can be obtained as single phase or in a mixture with Co2SiO4. The CoFe2O4 crystallites sizes are in the nanometer range (3–10 nm). The obtained nanocomposites have a hard magnet behavior, as a result of the high anisotropy of CoFe2O4 having large hysteresis cycles. 相似文献