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101.
Twenty-one R2R′2N+X− -type (R=methyl or ethyl, R′=alkyl, X=Br or I) quaternary ammonium (QA) halides have been prepared by using a novel one-pot synthetic route in which a formamide (dimethyl-, diethylformamide, etc.) is treated with alkyl halide in the presence of sodium or potassium carbonate. The formation of QA halides was verified with 1H-NMR, 13C-NMR, MS and elemental analysis. The crystal structures of four QA halides (two bromide and two iodide) were determined using X-ray single crystal diffraction, and the powder diffraction method was used to study the structural similarities between the single crystal and microcrystalline bulk material. The thermal properties of all compounds were studied using TG/DTA and DSC methods. The smallest compounds decomposed during or before melting. The decreasing trend of melting points was observed when the alkyl chain length was increased. The liquid ranges of 120-180 °C were observed for compounds with 5-6 carbon atoms in the alkyl chain. The low melting points and wide liquid ranges suggest potential applicability of these compounds for example as ionic liquids precursors. 相似文献
102.
Muñoz-Hernández MA Montiel-Palma V Huitrón-Rattinger E Cortés-Llamas S Tiempos-Flores N Grevy JM Silvestru C Power P 《Dalton transactions (Cambridge, England : 2003)》2005,(1):193-199
Dichloro and chloromethyl Ga(III) complexes of general formulae [XClGa-eta2-{R2P(E)NP(E'R'2-E,E'}](X = Cl, R, R'= Ph, E, E'= O (1), S (2), Se (3); R = Ph, R'= OEt, E = O, E'= S (4); R = Me, R'= Ph, E, E'= S (5) and X = Me, E, E'= O (6), S (7), Se (8)) were synthesised by either metathesis reactions between GaCl3 and the potassium salt of the ligand (X = Cl) or by methane eliminations from in situ prepared GaMe2Cl and the protonated ligands LH (X = Me). Redistribution reaction of (3) in either CDCl3 or THF afforded the solvent-free tetracoordinate gallium spirocycle cation [Ga-{eta2-{Ph2P(Se)NP(Se)Ph2-Se,Se'})2]+ (9+). The molecular structures of complexes 2, 4, 5, 7 and 9(+) show non-planar gallacycle rings. 相似文献
103.
Michele Menotta Sara Biagiotti Laura Streppa Luigia Rossi Mauro Magnani 《Analytica chimica acta》2015
In the present paper we describe an atomic force microscopy (AFM)-based method for the quantitative analysis of FK506 (Tacrolimus) in whole blood (WB) samples. Current reference methods used to quantify this immunosuppressive drug are based on mass spectrometry. In addition, an immunoenzymatic assay (ELISA) has been developed and is widely used in clinic, even though it shows a small but consistent overestimation of the actual drug concentration when compared with the mass spectrometry method. The AFM biosensor presented herein utilises the endogen drug receptor, FKBP12, to quantify Tacrolimus levels. The biosensor was first assayed to detect the free drug in solution, and subsequently used for the detection of Tacrolimus in blood samples. The sensor was suitable to generate a dose–response curve in the full range of clinical drug monitoring. A comparison with the clinically tested ELISA assay is also reported. 相似文献
104.
Andressa H. de Morais Batista Francisco F. de Sousa Sara B. Honorato Alejandro P. Ayala Josue M. Filho Francisco W. de Sousa Antonio N. Pinheiro J.C.S. de Araujo Ronaldo F. Nascimento Antoninho Valentini Alcineia C. Oliveira 《Journal of molecular catalysis. A, Chemical》2010,315(1):86-98
Isomorphously substituted (MeDM) and impregnated metal-containing MCM-41 (MeOx/IM) catalysts, in which Me = Co, Cu, Cr, Fe or Ni, have been prepared. Structural and textural characterizations of the catalysts were performed by means of X-ray diffraction (XRD), chemical analysis, Raman spectroscopy, electron paramagnetic resonance (EPR), N2 adsorption isotherms and temperature programmed reduction (TPR). Cu2+, Co2+, and Cr4+/Cr3+ species were found over the catalysts as cations incorporated in the MCM-41 structure (MeDM) or highly dispersed oxides on the surface (MeOx/IM). The MeDM catalysts exhibited a good performance in the dehydrogenation of ethylbenzene with CO2. However, MeOx/IM catalysts had a low performance in styrene production (activity less than 15 × 10?3 mmol h?1 and selectivity for styrene less than 80%) due to the high reducibility of the metals species. However, Ni2+ or Fe3+ coordinated with the MCM-41 framework, as well as NiOx and Fe2O3 extra-framework species, is continuously oxidized by the CO2 to maintain the active sites for dehydrogenating ethylbenzene. Deactivation studies on the FeDM sample showed that Fe3+ species produced active sp2 carbon compounds, which are removed by CO2; the referred sample is catalytically selective for styrene and stable over 24 h of reaction. In contrast, highly active Ni2+ and Ni0 species produced a large amount of polyaromatic carbonaceous deposits from styrene, as identified by TPO, TG and Raman spectroscopy. An acid–base mechanism is proposed to operate to adsorb ethylbenzene and abstract the β-hydrogen. CO2 plays a role in furnishing the lattice oxygen to maintain the Fe3+ active sites in the dehydrogenation of ethylbenzene to form styrene. 相似文献
105.
Jean-Ulrich Mullot Sara Karolak Anne Fontova Bruno Huart Yves Levi 《Analytical and bioanalytical chemistry》2009,394(8):2203-2212
Pollution of the environment by pharmaceuticals is a subject of growing scientific and societal concern. However, few quantitative
data have been reported concerning hospital wastewater contamination. Among the different molecules used at hospital, antineoplastic
drugs appear to be of special interest, and 5-fluorouracil (5-FU) can be considered as a key compound of this therapeutic
class. To monitor this pharmaceutical in hospital wastewater, a highly specific and selective method was developed using gas
chromatography tandem mass spectrometry after solid-phase extraction. This sensitive method (limit of quantification = 40 ng L−1) was then applied to assess sewage contamination of a middle-size hospital with oncology service located in Paris, France.
Native 5-FU was detectable in 12 of the 14 analysed samples. In positive samples, concentration range was measured from 0.09
to 4.0 μg L−1. Finally, a predicting model for the hospital wastewater concentrations is presented, and results of this model are discussed. 相似文献
106.
107.
Znabet A Blanken S Janssen E de Kanter FJ Helliwell M Turner NJ Ruijter E Orru RV 《Organic & biomolecular chemistry》2012,10(5):941-944
An efficient combination of MAO-N-catalyzed desymmetrization of cyclic meso-amines with Ugi-Smiles multicomponent chemistry produced optically pure N-aryl proline amides. This method represents the first report of a fully asymmetric Ugi-Smiles process. 相似文献
108.
Sara Mattsson 《Tetrahedron letters》2007,48(14):2497-2499
When treated with amine bases such as triethylamine and various lithium salts in wet solvents, esters are efficiently hydrolyzed to the corresponding acids in good yields. Esters incorporating an α- or β-heteroatom with respect to the ester carbonyl group are hydrolyzed rapidly even at room temperature. To further demonstrate the usefulness of this method, one example is provided where hydrolysis of acetylated camphorsultam is mediated by LiBr. 相似文献
109.
Electrostatic interactions in proteins can be probed experimentally through determination of residue-specific acidity constants. We describe here triple-resonance NMR techniques for direct determination of lysine and arginine side-chain protonation states in proteins. The experiments are based on detection of nonexchangeable protons over the full range of pH and temperature and therefore are well suited for pKa determination of individual amino acid side chains. The experiments follow the side-chain 15Nzeta (lysine) and 15Nepsilon or 13Czeta (arginine) chemical shift, which changes due to sizable changes in the heteronuclear electron distribution upon (de)protonation. Since heteronuclear chemical shifts are overwhelmed by the charge state of the amino acid side chain itself, these methods supersede 1H-based NMR in terms of accuracy, sensitivity, and selectivity. Moreover, the 15Nzeta and 15Nepsilon nuclei may be used to probe changes in the local electrostatic environment. Applications to three proteins are described: apo calmodulin, calbindin D9k, and FKBP12. For apo calmodulin, residue-specific pKa values of lysine side chains were determined to fall between 10.7 and 11.2 as a result of the high net negative charge on the protein surface. Ideal two-state titration behavior observed for all lysines indicates the absence of significant direct charge interactions between the basic residues. These results are compared with earlier studies based on chemical modification. 相似文献
110.