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111.
García Ruano JL Alonso de Diego SA Martín MR Torrente E Martín Castro AM 《Organic letters》2004,6(26):4945-4948
[reaction: see text] Thermolysis of enantiopure sulfonyl pyrazolines 4 and 5, easily obtained from (Z)-3-p-tolylsulfinylacrylonitriles (1), afforded sulfonyl cyclopropanes (6, 7) in a completely stereoselective manner in almost quantitative yields. Both cyclopropanes and alkylidenecyclopropanes, containing one or two chiral carbon atoms, one of them being quaternary, were obtained by hydrogenolysis of the C-S bonding and under the conditions reported by Julia, respectively. The highly stereoselective extrusion of nitrogen suggests a concerted mechanism. 相似文献
112.
Lainez A del Burgo P Junquera E Aicart E 《Langmuir : the ACS journal of surfaces and colloids》2004,20(14):5745-5752
Speed of sound, density, conductivity, and fluorescence spectroscopy experiments were run to analyze the mixed aggregation process of a nonionic-cationic surfactant system in aqueous media at 298.15 K. The mixed system comprises a nonionic surfactant, n-octyl-beta-D-glucopyranoside (OBG), and a cationic surfactant, tetradecyltrimethylammonium bromide (C14TAB), with 8 and 14 carbon atoms on the hydrophobic tails, respectively. From these data, the total and partial critical micellar concentrations, the total and partial aggregation numbers, apparent molar volumes and isentropic compressibilities, hydration numbers, and the corresponding changes in the latest properties due to the mixed aggregation process were determined. Pure and mixed micelles were analyzed from a geometrical point of view by determining the packing parameter of the aggregates. Furthermore, the experimental characterization of both the monomeric and micellar phases was completed with a theoretical study of the mixed micellization phenomena studied herein, by means of some of the most relevant theoretical models. 相似文献
113.
Payne RJ Toscano MD Bulloch EM Abell AD Abell C 《Organic & biomolecular chemistry》2005,3(12):2271-2281
Aromatic analogues of chorismate were synthesised as potential inhibitors of anthranilate synthase. Molecular modelling using GOLD2.1 showed that these analogues docked into the active site of Serratia marcescens anthranilate synthase in the same conformation as chorismate. Most compounds were found to be micromolar inhibitors of S. marcescens anthranilate synthase. The most potent analogue, 3-(1-carboxy-ethoxy)-4-hydroxybenzoate (K(I) 3 microM), included a lactyl ether side chain. This appears to be a good replacement for the enol-pyruvyl side chain of chorismate. 相似文献
114.
G. Ellis C. Marco J. del Pino M. A. Gómez 《Journal of Thermal Analysis and Calorimetry》1998,52(3):683-695
The thermal stabilities of two thermotropic liquid crystal polyesters were analysed by means of thermogravimetric analysis
(TG), as a function of the chemical structure of the aliphatic spacer between the aromatic-triad mesogenic units. TG was combined
with mass spectrometry to confirm that the degradation mechanism previously observed in a Fourier transform infrared study
of the degrading polymers follows a β-cis-elimination process.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
115.
116.
Churruca F SanMartin R Carril M Urtiaga MK Solans X Tellitu I Domínguez E 《The Journal of organic chemistry》2005,70(8):3178-3187
Novel dibenzo[a,c]phenanthridines are prepared regioselectively by the application of a straightforward synthetic pathway, starting from new 3,4-diaryl- and 3,4-dihydro-3,4-diarylisoquinolines prepared via Ritter-type heterocyclization and the more classical two-step reductive amination/Bischler-Napieralski cyclization of triarylethanones, respectively. A comparative study of nonphenolic oxidative coupling methodologies provides a highly efficient procedure, based on the hypervalent iodine reagent phenyliodine(III) bis(trifluoroacetate) (PIFA), to accomplish the final coupling step. 相似文献
117.
Olivares M del Carmen Thomas M López-Barajas A Requena JM García-Pérez JL Angel S Alonso C López MC 《Electrophoresis》2000,21(14):2973-2982
We have analyzed the genomic distribution and organization of the long interspersed nucleotide element (LINE) L1Tc, a nonlong terminal repeat (LTR) retrotransposon of Trypanosoma cruzi. The results indicate that the L1Tc element is dispersed along the parasite genome and that in some regions it is organized in tandem repeats. The data allowed us to define the existence of short direct-repeated sequences flanking the genomic L1Tc elements. Relevant is the finding that the LINE L1Tc is located in genomic regions rich in short interspersed nucleotide elements (SINE)-like sequences. In particular, the L1Tc element is found associated to E13-related sequences, redefined in this work and renamed RS13Tc, and to a newly described RS1Tc sequence. The RS1Tc sequence is present, per haploid genome, in about 3,200 copies. Northern blot analysis showed that the RS1Tc is being transcribed into RNAs of different sizes. The analysis of the chromosomal distribution of these elements in various strains of T. cruzi suggested that this type of clustering might be a common feature of the genome of these parasites. 相似文献
118.
Esther María Costi María Dolores SiciliaSoledad Rubio 《Journal of chromatography. A》2010,1217(40):6250-6257
A multiresidue method was described for determining eight sulfonamides, SAs (sulfadiazine, sulfamerazine, sulfamethoxypyridazine, sulfachloropyridazine, sulfadoxine, sulfamethoxazole, sulfadimethoxine and sulfaquinoxaline) in animal muscle tissues (pork, chicken, turkey, lamb and beef) at concentrations below the maximum residue limit (100 μg kg−1) set by the European Commission. The method was based on the microextraction of SAs in 300-mg muscle samples with 1 mL of a supramolecular solvent made up of reverse micelles of decanoic acid (DeA) and posterior determination of SAs in the extract by LC/fluorescence detection, after in situ derivatization with fluorescamine. Recoveries were quantitative (98–109%) and matrix-independent, no concentration of the extracts was required, the microextraction took about 30 min and several samples could be simultaneously treated. Formation of multiple hydrogen bonds between the carboxylic groups of the solvent and the target SAs (hydrogen donor and acceptor sum between 9 and 11) were considered as the major forces driving microextraction. The method was validated according to the European Union regulation 2002/657/EC. Analytical performance in terms of linearity, selectivity, trueness, precision, stability of SAs, decision limit and detection capability were determined. Quantitation limits for the different SAs ranged between 12 μg kg−1 and 44 μg kg−1, they being nearly independent of matrix composition. Repeatability and reproducibility, expressed as relative standard deviation, were in the ranges 1.8–3.6% and 3.3–6.1%. The results of the validation process proved that the method is suitable for determining sulfonamide residues in surveillance programs. 相似文献
119.
Javier A. Cabeza Prof. Ignacio del Río Prof. Enrique Pérez‐Carreño Prof. Vanessa Pruneda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(18):5425-5436
The cationic cluster complexes [Ru3(μ‐H)(μ‐κ2N,C‐L1 Me)(CO)10]+ ( 1 +; HL1 Me=N‐methylpyrazinium), [Ru3(μ‐H)(μ‐κ2N,C‐L2 Me)(CO)10]+ ( 2 +; HL2 Me=N‐methylquinoxalinium), and [Ru3(μ‐H)(μ‐κ2‐N,C‐L3 Me)(CO)10]+ ( 3 +; HL3 Me=N‐methyl‐1,5‐naphthyridinium), which contain cationic N‐heterocyclic ligands, undergo one‐electron reduction processes to become short lived, ligand‐centered, trinuclear, radical species ( 1 – 3 ) that end in the formation of an intermolecular C? C bond between the ligands of two such radicals, thus leading to neutral hexanuclear derivatives. These dimerization processes are selective, in the sense that they only occur through the exo face of the bridging ligands of trinuclear enantiomers of the same configuration, as they only afford hexanuclear dimers with rac structures (C2 symmetry). The following are the dimeric products that have been isolated by using cobaltocene as reducing agent: [Ru6(μ‐H)2{μ6‐κ4N2,C2‐(L1 Me)2}(CO)18] ( 5 ; from 1 +), [Ru6(μ‐H)2{μ6‐κ4N2,C2‐(L2 Me)2}(CO)18] ( 6 ; from 2 +), and [Ru6(μ‐H)2{μ4‐κ8N2,C6‐(L3 Me)2}(CO)18] ( 7 ; from 3 +). The structures of the final hexanuclear products depend on the N‐heterocyclic ligand attached to the starting materials. Thus, although both trinuclear subunits of 5 and 6 are face‐capped by their bridging ligands, the coordination mode of the ligand of 5 is different from that of the ligand of 6 . The trinuclear subunits of 7 are edge‐bridged by its bridging ligand. In the presence of moisture, the reduction of 3 + with cobaltocene also affords a trinuclear derivative, [Ru3(μ‐H)(μ‐κ2N,C‐L3′ Me)(CO)10] ( 8 ), whose bridging ligand (L3′ Me) results from the formal substitution of an oxygen atom for the hydrogen atom (as a proton) that in 3 + is attached to the C6 carbon atom of its heterocyclic ligand. The results have been rationalized with the help of electrochemical measurements and DFT calculations, which have also shed light on the nature of the odd‐electron species, 1 – 3 , and on the regioselectivity of their dimerization processes. It seems that the sort of coupling reactions described herein requires cationic complexes with ligand‐based LUMOs. 相似文献
120.