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31.
Rodeschini V Van de Weghe P Salomon E Tarnus C Eustache J 《The Journal of organic chemistry》2005,70(6):2409-2412
[reaction: see text] Enantioselective deprotonation of 4-substituted cyclohexanones and highly stereoselective conjugate addition of higher order mixed cuprates were the key steps in a concise synthesis of fumagalone-related molecules. The origin of the (low) biological activity of the new compounds as compared to fumagalone is briefly discussed. 相似文献
32.
Hodgson DM Buxton TJ Cameron ID Gras E Kirton EH 《Organic & biomolecular chemistry》2003,1(23):4293-4301
Enantioselective alpha-deprotonation of achiral epoxides 1, 21, and 26 using organolithiums in the presence of (-)-sparteine 2 and subsequent electrophile trapping gives access to enantioenriched trisubstituted epoxides 9-17, 22, 23, 27 and 28 (in up to 86% ee). 相似文献
33.
Osei-Twum EY Litorja LA Darkwa J Maisela LL Lesimple A Mamer O 《Journal of the American Society for Mass Spectrometry》2005,16(1):94-99
The mass spectral behavior of a number of organometallic complexes containing the Group 10 metals Ni, Pd, and Pt, together with various thiolate ligands were studied. For Pd, two main types of complexes, differing by the substituents on the phosphorus atom were studied. Types I and II were substituted with bis(diphenylphosphino)ferrocene and bis(diisopropylphosphino)ferrocene ligands, respectively. The Ni complexes, except for one, and the Pd Type I complexes had no molecular radical cations (M(+.)) in their EI spectra. On the other hand, all the Pt complexes showed intense M(+.) ions in their EI spectra indicating that these complexes were more stable as radical cations than those of Ni and Pd. The FAB and MALDI spectra of all the complexes displayed intense quasi-molecular ions (MH(+)) and the fragmentations in both modes were similar. The MALDI spectra of several complexes displayed only M(+.) ions while one gave evidence of both MH(+) and M(+.) ions. Several Pd Type II complexes yielded intense M(+.) in their EI spectra. 相似文献
34.
An amperometric biosensor was prepared by in situ deposition of horseradish peroxidase (HRP) enzyme on a polyaniline (PANI)-doped platinum disk electrode. The PANI film was electrochemically deposited on the electrode at 100 mV s−1/Ag-AgCl. Cyclic voltammetric characterization of the PANI film in 1 M HCl showed two distinct redox peaks, which prove that the PANI film was electroactive and exhibited fast reversible electrochemistry. The surface concentration and film thickness of the adsorbed electroactive species was estimated to be 1.85×10−7 mol cm−2 and approximately 16 nm, respectively. HRP was electrostatically immobilized onto the surface of the PANI film, and voltammetry was used to monitor the electrocatalytic reduction of hydrogen peroxide under diffusion-controlled conditions. Linear responses over the concentration range 2.5×10−4 to 5×10−3 M were observed. Spectroelectrochemistry was used to monitor the changes in UV-vis properties of HRP, before and after the catalysis of H2O2. The biosensor surface morphology was characterized by scanning electron microscopy (SEM) using PANI-doped screen-printed carbon electrodes (SPCEs) in the presence and absence of (i) peroxidase and (ii) peroxide. The SEM images showed clear modifications of the conducting film surface structure when doped with HRP, as well as the effect of hydrogen peroxide on the morphology of biosensor. 相似文献
35.
Jaqueline Cornejo-Campos Yenny Adriana Gmez-Aguirre Jos Rodolfo Velzquez-Martínez Oscar Javier Ramos-Herrera Carolina Estefanía Chvez-Murillo Francisco Cruz-Sosa Carlos Areche Emmanuel Cabaas-García 《Molecules (Basel, Switzerland)》2022,27(12)
Acanthocereus tetragonus (L.) Hummelinck is used as an alternative food source in some Mexican communities. It has been shown that the young stems of A. tetragonus provide crude protein, fiber, and essential minerals for humans. In this work, we analyzed the phytochemical profile, the total phenolic content (TPC), and the antioxidant activity of cooked and crude samples of A. tetragonus to assess its functional metabolite contribution to humans. The phytochemical profile was analyzed using Ultra-High-Performance Liquid Chromatography coupled to High-Resolution Mass Spectrometry (UHPLC-PDA-HESI-Orbitrap-MS/MS). Under the proposed conditions, 35 metabolites were separated and tentatively identified. Of the separated metabolites, 16 occurred exclusively in cooked samples, 6 in crude samples, and 9 in both crude and cooked samples. Among the detected compounds, carboxylic acids, such as threonic, citric, and malic acids, phenolic acids, and glycosylated flavonoids (luteolin-O-rutinoside) were detected. The TPC and antioxidant activity were analyzed using the Folin–Ciocalteu method and the 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical inhibition method, respectively. The TPC and antioxidant activity were significantly reduced in the cooked samples. We found that some metabolites remained intact after the cooking process, suggesting that A. tetragonus represents a source of functional metabolites for people who consume this plant species. 相似文献
36.
Dionysios Raptis Charalampos Livas George Stavroglou Rafaela Maria Giappa Emmanuel Tylianakis Taxiarchis Stergiannakos George E. Froudakis 《Molecules (Basel, Switzerland)》2022,27(11)
The interaction strength of nitrogen dioxide (NO2) with a set of 43 functionalized benzene molecules was investigated by performing density functional theory (DFT) calculations. The functional groups under study were strategically selected as potential modifications of the organic linker of existing metal–organic frameworks (MOFs) in order to enhance their uptake of NO2 molecules. Among the functional groups considered, the highest interaction energy with NO2 (5.4 kcal/mol) was found for phenyl hydrogen sulfate (-OSO3H) at the RI-DSD-BLYP/def2-TZVPP level of theory—an interaction almost three times larger than the corresponding binding energy for non-functionalized benzene (2.0 kcal/mol). The groups with the strongest NO2 interactions (-OSO3H, -PO3H2, -OPO3H2) were selected for functionalizing the linker of IRMOF-8 and investigating the trend in their NO2 uptake capacities with grand canonical Monte Carlo (GCMC) simulations at ambient temperature for a wide pressure range. The predicted isotherms show a profound enhancement of the NO2 uptake with the introduction of the strongly-binding functional groups in the framework, rendering them promising modification candidates for improving the NO2 uptake performance not only in MOFs but also in various other porous materials. 相似文献
37.
Multi‐stage high order semi‐Lagrangian schemes for incompressible flows in Cartesian geometries 下载免费PDF全文
Efficient transport algorithms are essential to the numerical resolution of incompressible fluid‐flow problems. Semi‐Lagrangian methods are widely used in grid based methods to achieve this aim. The accuracy of the interpolation strategy then determines the properties of the scheme. We introduce a simple multi‐stage procedure, which can easily be used to increase the order of accuracy of a code based on multilinear interpolations. This approach is an extension of a corrective algorithm introduced by Dupont & Liu (2003, 2007). This multi‐stage procedure can be easily implemented in existing parallel codes using a domain decomposition strategy, as the communication pattern is identical to that of the multilinear scheme. We show how a combination of a forward and backward error correction can provide a third‐order accurate scheme, thus significantly reducing diffusive effects while retaining a non‐dispersive leading error term. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
38.
Véronique Pignon Roger Jeannot Emmanuel Sauvard 《International journal of environmental analytical chemistry》2013,93(4):345-366
Abstract The coupling between liquid chromatography and mass spectrometry with an APCI or ESI interface (in positive or negative mode) is used here for multi-residue analyses in natural waters, covering basic and neutral pesticides as well as acid pesticides. The methods developed are applied to drinking and, river waters after the samples are concentrated by liquid-liquid extraction or solid phase extraction on C18 cartridges. Comparisons are made between UV detection and mass spectrometry and between two chromatographic methods for acid substances. The quantitation limits range from 0.01 to 0.1 μg/l according to the substance. 相似文献
39.
Dr. Peter Wick Dr. Anna E. Louw‐Gaume Dr. Melanie Kucki Prof. Harald F. Krug Prof. Kostas Kostarelos Prof. Bengt Fadeel Prof. Kenneth A. Dawson Dr. Anna Salvati Prof. Ester Vázquez Dr. Laura Ballerini Dr. Mauro Tretiach Dr. Fabio Benfenati Dr. Emmanuel Flahaut Dr. Laury Gauthier Prof. Maurizio Prato Dr. Alberto Bianco 《Angewandte Chemie (International ed. in English)》2014,53(30):7714-7718
40.
Alexander J. Nichols Emmanuel Roussakis Oliver J. Klein Conor L. Evans 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(14):3745-3748
Hypoxia is an important contributing factor to the development of drug‐resistant cancer, yet few nonperturbative tools exist for studying oxygenation in tissues. While progress has been made in the development of chemical probes for optical oxygen mapping, penetration of such molecules into poorly perfused or avascular tumor regions remains problematic. A click‐assembled oxygen‐sensing (CAOS) nanoconjugate is reported and its properties demonstrated in an in vitro 3D spheroid cancer model. The synthesis relies on the sequential click‐based ligation of poly(amidoamine)‐like subunits for rapid assembly. Near‐infrared confocal phosphorescence microscopy was used to demonstrate the ability of the CAOS nanoconjugates to penetrate hundreds of micrometers into spheroids within hours and to show their sensitivity to oxygen changes throughout the nodule. This proof‐of‐concept study demonstrates a modular approach that is readily extensible to a wide variety of oxygen and cellular sensors for depth‐resolved imaging in tissue and tissue models. 相似文献