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31.
Multifunctional Supramolecular Dendrimers with an s‐Triazine Ring as the Central Core: Liquid Crystalline,Fluorescence and Photoconductive Properties 下载免费PDF全文
Madalina Bucoş Dr. Teresa Sierra Dr. Attilio Golemme Dr. Roberto Termine Dr. Joaquín Barberá Dr. Raquel Giménez Prof. Dr. José Luis Serrano Dr. Pilar Romero Dr. Mercedes Marcos 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(32):10027-10037
Novel liquid crystal (LC) dendrimers have been synthesised by hydrogen bonding between an s‐triazine as the central core and three peripheral dendrons derived from bis(hydroxymethyl)propionic acid. Symmetric acid dendrons bearing achiral promesogenic units have been synthesised to obtain 3:1 complexes with triazine that exhibit LC properties. Asymmetric dendrons that combine the achiral promesogenic unit and an active moiety derived from coumarin or pyrene structures have been synthesised in order to obtain dendrimers with photophysical and electrochemical properties. The formation of the complexes was confirmed by IR and NMR spectroscopy data. The liquid crystalline properties were investigated by differential scanning calorimetry, polarising optical microscopy and X‐ray diffractometry. All complexes displayed mesogenic properties, which were smectic in the case of symmetric dendrons and their complexes and nematic in the case of asymmetric dendrons and their dendrimers. A supramolecular model for the lamellar mesophase, based mainly on X‐ray diffraction studies, is proposed. The electrochemical behaviour of dendritic complexes was investigated by cyclic voltammetry. The UV/Vis absorption and emission properties of the compounds and the photoconductive properties of the dendrons and dendrimers were also investigated 相似文献
32.
Enthalpies (Δisom
H
(g)o), Gibbs free energies (Δisom
G
(g)o), and equilibrium constants (log K
isom) for the trans → cis isomerization of various 3,3′-, 4,4′-, and 5,5′- disubstituted 2,2′-diphenoquinones with a range of electron withdrawing
and releasing moieties (methyl, fluoro, chloro, bromo, trifluoromethyl, and amino) were calculated in the gas phase and in
the solvent phase (n-hexane, benzene, n-octanol, acetonitrile, and water). In the gas phase, the trans isomer of the parent and all substituted 2,2′-diphenoquinones is predicted to be more thermodynamically stable than the cis configuration, with log K
isom ranging from −2.8 to −7.0. For all compounds, increasing solvent polarity/proticity progressively favors shifting the cis/trans equilibrium towards greater contributions of the cis configuration and substantially increases the log K
isom by up to 5.1 units relative to the gas phase. In polar protic and polar aprotic solvents, the estimated log K
isom ranges as low as −0.4, indicating significant populations of the cis isomers should be present. The findings support the polar solvent phase mechanistic predictions for a cis configuration of 2,2′-diphenoquinones participating in the thermal transformation of trans-2,2′-diphenoquinones to oxepino[2,3-b]benzofurans. With limited exceptions for some amino derivatives, the cis-2,2′-diphenoquinone to oxepino[2,3-b]benzofuran isomerization is expected to be thermodynamically favorable for all substituents/phases
under consideration. The cis-2,2′-diphenoquinone to oxepino[2,3-b]benzofuran rearrangement is predicted to become less thermodynamically favored with
increasing solvent polarity/proticity. 相似文献
33.
Validation of a gas chromatographic method for determination of fatty alcohols in 10 mg film-coated tablets of policosanol 总被引:3,自引:0,他引:3
A gas chromatographic method using a packed column and 1-eicosanol as an internal standard was validated for the determination of the fatty alcohols that compose policosanol in 10 mg film-coated tablets. The alcohols were determined as trimethylsilyl derivatives, prepared with N-methyl-N-trimethylsilyltrifluoroacetamide. The method can detect degradation products with high retention times, without interfering with the peaks of the active principle. Good linearity (correlation coefficient = 0.9992) and accuracy (mean recovery -100.27 +/- 1.66%) were proven over a range of 25-200% of the nominal concentration. Within- and between-day precision at the nominal 100% value met the acceptance criteria (<2%). Ruggedness was examined through an intralaboratory experimental study in which 6 operational changes were made; the changes were found to have no effect on quantitation, repeatability, resolution, and relative retention time. The method is suitable for the quality control process and stability studies of these tablets. 相似文献
34.
Soares CR Camargo IM Morganti L Gimbo E Ezequiel de Oliveira J Legoux R Ferrara P Bartolini P 《Journal of chromatography. A》2002,955(2):229-236
Reversed-phase high-performance liquid chromatography methodology for the determination of human prolactin (hPRL) in bacterial periplasmic space or in purified preparations has been developed. The technique, based on the high hydrophobicity of the hPRL molecule, allows its separation from the bulk of bacterial proteins. The precision for periplasmic shock fluid analysis was characterized by relative standard variations of 3-7% for intra-day and of 3-25% for inter-day determinations. Accuracy, evaluated by recovery tests, was of the order of 90%, a calibration curve being constructed with the use of a lyophilized osmotic shock fluid extract, which provided a stable, readily prepared internal reference. Sensitivity was of the order of 0.5 microg of hPRL. The methodology developed also provided a tool for comparing the hydrophobicity of glycosylated and non-glycosylated prolactin molecules obtained from several different species and of different preparations of native or biosynthetic human prolactin. 相似文献
35.
36.
Benito Alcaide Rafael Prez-Ossosio Joaquin Plumet Miguel A. Sierra 《Tetrahedron letters》1982,23(52):5585-5586
The monoimine easily formed bydirect condensation between benzil and 2-aminopyridine adds alcohols and amines to the imine bond without catalysis. A concerted mechanism is proposed. 相似文献
37.
38.
A set of experiments, using model compounds, was carried out in order to evaluate the influence of amide linkages on acidity measurements of humic substances (HS). Three benzene-carboxylic acids (2,4-dihydroxybenzoic acid; 3,5-dihydroxybenzoic acid, and phthalic acid) and two peptides (dl-alanyl-dl-alanine, and glycil-l-leucine) were employed to simulate the major acidic functional groups present in humic material. The acidity of the samples was measured, using the Schnitzer and Gupta methods, for each compound separately, as well as for selected mixtures with different compound combinations. General results showed that, in the absence of peptides, phenolic groups with high pKa values are not detected in the barium hydroxide reaction and the data so obtained do not represent the real concentrations of the acidic groups. For the mixtures containing peptides, the presence of amide linkages distorts the results relative to the total acidity (TA) mainly because under the extreme conditions of the reaction with Ba(OH)2 hydrolysis of the peptide occurs, consuming extra hydroxyl groups and increasing artificially the phenolic content. Such a condition is minimized by the reduction of the reaction time. 相似文献
39.
40.
A. Jilek A. Ryánek A. del Campe F. Sierra F. Feigl P. Krumholz L. Guglialmelli J. Lukas Marianne Papafil R. Cernatesco I. Itaka Y. Aoki und W. Stahl 《Fresenius' Journal of Analytical Chemistry》1934,98(7-8):292-298
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