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51.
(S)-β-Bisabolene, (S)-1, was synthetized by a synthetic route in which (S)-4-methyl-3-cyclohexene carboxylic acid, (S)-10, which was the key intermediate, was prepared via a highly diastereoselective TiCl4-catalyzed Diels-Alder reaction between isoprene and the acrylate of commercial (R)-pantolactone, followed by hydrolysis. Compound (S)-10 was then converted into ketone (S)-13 using two different procedures. The best one of these, as regards the degree of stereospecificity, involved the reaction of (S)-10 with 2 equiv of 4-methyl-3-penten-1-yllithium, 14, in the presence of CeCl3, and gave (S)-13 having ca. 84% ee. The Zr-promoted methylenation of this ketone afforded highly enantiomerically enriched (S)-1. 相似文献
52.
Emanuele Aresu Laura CarrocciaStefania Fioravanti Simona GasbarriLucio Pellacani Fabio Sciubba 《Tetrahedron》2013
Chiral racemic α-diimines, tested in aziridination reactions with NsONHCO2Et, for the first time led to the synthesis of (±)-bidiaziridines, stereoselectively derived from the corresponding meso (E-s-trans-E)-α-diimines. Moreover, a minor bidiaziridine isomer, probably a meso form that was lost under classical work-up conditions, can be obtained by adding water to the crude mixtures at the end of amination reactions. The results definitively prove that the imine aziridination by carbamates is a two-step domino process. The structures of the compounds were determined using 2D NMR on purified bidiaziridines. 相似文献
53.
Laura E. Muresan Adrian I. Cadis Ioana Perhaita Emil Indrea 《Central European Journal of Chemistry》2014,12(10):1023-1031
Yttrium silicate doped with cerium (Y2SiO5:Ce) was obtained from Y-Ce-Si based precursors prepared by the simultaneous addition of reagents (SimAdd) technique. The synthesis of the precursors was done in well controlled conditions using ammonium oxalate, ammonium carbonate or urea as precipitating agents. Results regarding the influence of precipitating agents on the morpho structural and photoluminescent characteristics of Y2SiO5:Ce are reported. The TG analysis in correlation with EGA, FT-IR and XRD investigations reveals the formation of oxalate, hydroxy-carbonate or hydroxy-nitrate based compounds, the same as the conversion of the precursors to well crystallized yttrium silicate. XRD patterns show that the precursors are amorphous except for the sample prepared with ammonium oxalate. Depending on the precipitation conditions, the phosphors phase composition varies from single phase (X2-Y2SiO5) to a mixture of phases (X2-Y2SiO5, X1-Y2SiO5, Y2O3). Under UV excitation, phosphors exhibit the specific blue emission of cerium with an intensity that varies from 175.8% (urea) to 96.0% (ammonium carbonate) and to 78.5% (ammonium oxalate). The emission intensity depends on the phase purity and order degree of the phosphors. PACS Classification codes:78.55 Hx, 81.20Fw 相似文献
54.
Antonio Doménech-Carbó Monserrat Lastras Francisco Rodríguez Emilio Cano Juan Piquero-Cilla Laura Osete-Cortina 《Journal of Solid State Electrochemistry》2014,18(2):399-409
A methodology for monitoring washing procedures applied to stabilize archaeological iron is described. It is based on the combination of voltammetry of microparticles (VMP) with electrochemical impedance spectroscopy (EIS). A semi-empirical approach is used where the impedances at low and high frequencies were related with the fraction areas of passive and corrosion layers generated during the stabilizing treatment, the thickness, and the porosity of the corrosion layer. The variation of such parameters with the time of washing was determined from EIS data for four types of desalination procedures using concentrated NaOH and/or Na2SO3 aqueous solutions on archaeological iron artifacts. After 2 months of treatment, EIS data indicate that an essentially identical “stable” state was attained in all cases, as confirmed by the formation of a passive magnetite layer identified in VMP measurements while the rate of variation of corroded surface and porosity at short washing times varied significantly from one stabilization procedure to another. 相似文献
55.
Laura L. Adduci Dr. Matthew P. McLaughlin Trandon A. Bender Dr. Jennifer J. Becker Prof. Dr. Michel R. Gagné 《Angewandte Chemie (International ed. in English)》2014,53(6):1646-1649
The conversion of readily available cellulosic biomass to valuable feedstocks and fuels is an attrative goal but a challenging transformation that requires the cleavage of multiple nonactivated C? O bonds. Herein, the Lewis acid trispentafluorophenylborane (B(C6F5)3) is shown to catalyze the metal‐free hydrosilylative reduction of monosaccharides and polysaccharides to give hydrocarbons with reduced oxygen content. The choice of the silane reductant influences the degree of deoxygenation, with diethylsilane effecting the complete reduction to produce hexanes while tertiary silanes give partially deoxygenated tetraol and triol products. 相似文献
56.
Laura Hoffmeister Peter Persich Prof. Alois Fürstner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(15):4396-4402
In an attempt to study the ability of the latest generation of alkyne metathesis catalysts to process sterically hindered substrates, two different routes to the bacterial metabolite kendomycin ( 1 ) were explored. Whereas the cyclization of the overcrowded arylalkyne 39 and related substrates turned out to be impractical or even impossible, ring closure of the slightly relaxed diyne 45 was achieved in excellent yield under notably mild conditions with the aid of the molybdenum alkylidyne 2 endowed with triphenylsilanolate ligands. The resulting cycloalkyne 46 was engaged into a gold‐catalyzed hydroalkoxylation, which led to benzofuran 47 that had already previously served as a late‐stage intermediate en route to 1 . 相似文献
57.
Laura Sinatra Jan J. Bandolik Dr. Martin Roatsch Melf Sönnichsen Dr. Clara T. Schoeder Dr. Alexandra Hamacher Andrea Schöler Prof. Dr. Arndt Borkhardt Prof. Dr. Jens Meiler Dr. Sanil Bhatia Prof. Dr. Matthias U. Kassack Prof. Dr. Finn K. Hansen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(50):22681-22687
58.
Roman Schowner Dr. Iris Elser Mathis Benedikter Mohasin Momin Dr. Wolfgang Frey Tanja Schneck Dr. Laura Stöhr Prof. Dr. Michael R. Buchmeiser 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(2):961-968
The origin of hydroxyl group tolerance in neutral and especially cationic molybdenum imido alkylidene N-heterocyclic carbene (NHC) complexes has been investigated. A wide range of catalysts was prepared and tested. Most cationic complexes can be handled in air without difficulty and display an unprecedented stability towards water and alcohols. NHC complexes were successfully used with substrates containing the hydroxyl functionality in acyclic diene metathesis polymerization, homo-, cross and ring-opening cross metathesis reactions. The catalysts remain active even in 2-PrOH and are applicable in ring-opening metathesis polymerization and alkene homometathesis using alcohols as solvent. The use of weakly basic bidentate, hemilabile anionic ligands such as triflate or pentafluorobenzoate and weakly basic aromatic imido ligands in combination with a sterically demanding 1,3-dimesitylimidazol-2-ylidene NHC ligand was found essential for reactive and yet robust catalysts. 相似文献
59.
Diana Trujillo-Benítez Myrna Luna-Gutirrez Guillermina Ferro-Flores Blanca Ocampo-García Clara Santos-Cuevas Gerardo Bravo-Villegas Enrique Morales-vila Pedro Cruz-Nova Lorenza Díaz-Nieto Janice García-Quiroz Erika Azorín-Vega Antonio Rosato Laura Melndez-Alafort 《Molecules (Basel, Switzerland)》2022,27(1)
Fibroblast activation protein (FAP) is expressed in the microenvironment of most human epithelial tumors. 68Ga-labeled FAP inhibitors based on the cyanopyrrolidine structure (FAPI) are currently used for the detection of the tumor microenvironment by PET imaging. This research aimed to design, synthesize and preclinically evaluate a new FAP inhibitor radiopharmaceutical based on the 99mTc-((R)-1-((6-hydrazinylnicotinoyl)-D-alanyl) pyrrolidin-2-yl) boronic acid (99mTc-iFAP) structure for SPECT imaging. Molecular docking for affinity calculations was performed using the AutoDock software. The chemical synthesis was based on a series of coupling reactions of 6-hidrazinylnicotinic acid (HYNIC) and D-alanine to a boronic acid derivative. The iFAP was prepared as a lyophilized formulation based on EDDA/SnCl2 for labeling with 99mTc. The radiochemical purity (R.P.) was verified via ITLC-SG and reversed-phase radio-HPLC. The stability in human serum was evaluated by size-exclusion HPLC. In vitro cell uptake was assessed using N30 stromal endometrial cells (FAP positive) and human fibroblasts (FAP negative). Biodistribution and tumor uptake were determined in Hep-G2 tumor-bearing nude mice, from which images were acquired using a micro-SPECT/CT. The iFAP ligand (Ki = 0.536 nm, AutoDock affinity), characterized by UV-Vis, FT-IR, 1H–NMR and UPLC-mass spectroscopies, was synthesized with a chemical purity of 92%. The 99mTc-iFAP was obtained with a R.P. >98%. In vitro and in vivo studies indicated high radiotracer stability in human serum (>95% at 24 h), specific recognition for FAP, high tumor uptake (7.05 ± 1.13% ID/g at 30 min) and fast kidney elimination. The results found in this research justify additional dosimetric and clinical studies to establish the sensitivity and specificity of the 99mTc-iFAP. 相似文献
60.
Christopher Hernandez Laura Cadenillas Cline Mathieu Jean-Denis Bailly Vanessa Durrieu 《Molecules (Basel, Switzerland)》2022,27(2)
Mimosa tenuiflora aqueous extract (MAE) is rich in phenolic compounds. Among them, condensed tannins have been demonstrated to exhibit a strong antioxidant and antiaflatoxin B1 activities in Aspergillus flavus. Since antioxidant capacity can change with time due to environmental interactions, this study aimed to evaluate the ability of encapsulation by spray-drying of Mimosa tenuiflora aqueous extract to preserve their biological activities through storage. A dry formulation may also facilitate transportation and uses. For that, three different wall materials were used and compared for their efficiency. Total phenolic content, antioxidant activity, antifungal and antiaflatoxin activities were measured after the production of the microparticles and after one year of storage at room temperature. These results confirmed that encapsulation by spray-drying using polysaccharide wall materials is able to preserve antiaflatoxin activity of Mimosa tenuiflora extract better than freezing. 相似文献