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61.
G. J. Dear D. N. Mallett D. M. Higton A. D. Roberts S. A. Bird H. Young R. S. Plumb I. M. Ismail 《Chromatographia》2002,55(3-4):177-184
Summary In this paper we investigate the potential of alkyl-bonded silica monolithic columns for the isolation and identification
of drug-related components in biological fluids. Up to 6 columns have been connected in series to produce a chromatographic
system with up to 40,000 plates. This high-resolution chromatography system has been coupled to both MS and NMR to enable
efficient detection and characterisation of drug-related components in biological fluids. The use of six coupled columns has
been shown to give enhanced resolution over a high quality silica particulate column packed with 3 μm material which exhibits
the same back pressure. The effect of volume and mass load on the performance of monolithic columns for semi-preparative chromatography
of biological fluids has also been investigated. In these studies it was possible to inject up to 100 mL of neat urine with
no loss of chromatographic performance. Furthermore, upon re-testing, the columns showed similar chromatographic performance.
Again several columns were serially connected, producing enhanced resolution in the semi-preparative mode. 相似文献
62.
Fluorescein has an extremely low luminescence intensity in acidic aqueous media. However, when it was bound to proteins, subsequent increase of luminescence intensity took place. Furthermore, when a hydrophobic tail, such as aliphatic hydrocarbons, was introduced to fluorescein, more dramatic increase of luminescence intensity was observed upon binding to proteins. In the present study, by utilizing this luminescence enhancement, three hydrophobic fluorescein dyes (5-dodecanoyl amino fluorescein, 5-hexadecanoyl amino fluorescein, and 5-octadecanoyl amino fluorescein) were examined as noncovalent fluorescent stains of protein bands in sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). Effective incorporation of the dyes to proteins in gels was accomplished either simply by adding dyes at the protein fixation step, or by treating gels with a staining solution after the fixation. The sensitivity of this staining method using the fluorescein derivatives was approximately 1 ng/band for most proteins. For some cases, protein bands containing as low as 0.1 ng were successfully visualized. In addition, the detection sensitivity showed much less protein-to-protein variation than silver staining. This new staining method was also successfully applied to two-dimensional electrophoresis of rat brain proteins. Its overall sensitivity was comparable to that of silver staining. 相似文献
63.
Chemistry related to three catalytic carbonylation reactions is discussed. Synthesis of diphenylurea from nitrobenzene, aniline,
and CO gives isolated yields above 98% at 100–120 °C and 15–60 bar of CO in the presence of a palladium (II) complex, PPh3 and NEt4Cl. Experimental evidence was provided to prove a new reaction stoichiometry and involvement of a carbamoyl intermediate.
In carbonylation of HCHO over ion exchange resin catalysts, reaction temperature, time, pressure, and solvent were important
variables to obtain high yields of methyl glycolate. Carbonylation of isobutylphenylethanol at 120°C and 40 bar of CO in the
presence of PdCl2−PPh3−HCl gives 98% yield of α-(4-isobutylphenyl) propionic acid (ibuprofen). Each catalyst component had a definite role that
is indispensable for an efficient overall reaction. 相似文献
64.
David T. Connor Patricia A. Young Maximillian Von Strandtmann 《Journal of heterocyclic chemistry》1977,14(1):139-141
The reaction of 2-picoline N-Oxide anion with o-substituted henzoates and isatoic anhydrides to give synthetically useful l-(2-methoxyphenyl)-2-(2-pyridinyl)ethanone N-oxides, I-(2-hydroxy-phenyJ)-2-(2-pyridinyl)ethanone N-oxides and I -(2-arninopheny])-2-(2-pyridinyl)ethanone N-oxides is described. 相似文献
65.
Rauter AP Martins A Borges C Ferreira J Jorge J Bronze MR Coelho AV Choi YH Verpoorte R 《Journal of chromatography. A》2005,1089(1-2):59-64
The anti-hyperglycemic flavonoid extract obtained from Genista tenera was first studied by liquid chromatography (LC)-diode array detection (DAD) which showed the presence of two major compounds. One of them was identified as genistein-7-O-glucoside. Luteolin-7-O-glucoside was detected as a minor constituent, while luteolin-7,3'-di-O-glucoside and rutin were found in trace amounts. LC-DAD-ESI-MS and NMR were used to confirm the structure of these compounds and allowed the elucidation of the structure of the unknown major compound, which is the flavonoid 5,7,4'-trihydroxyisoflavone-8-C-glucoside. 相似文献
66.
Residual stress in the epoxy plate during a rapid cooling process was measured by the layer removal method and calculated by the linear thermoviscoelastic theory considering specific volume relaxation. The relaxations of the tensile modulus and specific volume were measured by an Instron thermomechanical analyzer. When the starting temperature of the cooling process was near the glass transition temperature of the cured epoxy, the residual stress in the epoxy plate was smaller than when the starting temperature was higher than the glass transition temperature. However, the transient stress in the cured epoxy plate was higher when the starting temperature was near the glass transition temperature than when the starting temperature was higher than the glass transition temperature. The quenched epoxy plate was compressed in the direction parallel to the surface and expanded in the thickness direction. 相似文献
67.
Desmond A. Young Daneel Ferreira David G. Roux 《Journal of polymer science. Part A, Polymer chemistry》1986,24(5):835-849
The structure and stereochemistry of four synthetic “angular” tetraflavanoid-condensed tannin derivatives are examined by high-resolution variable temperature 1H NMR. spectroscopy, and hence correlated with their dynamic behavior. Three “angular” oligomers exist as stable rotational isomers at ambient temperatures, thus contrasting with the mobility about their interflavanoid bonds of most natural profisetinidin “trimeric” and “tetrameric” homologs. A “linear” tetraflavanoid analog results from one of these regioselectively controlled condensations. 相似文献
68.
Geneviéve Cerveau Ernesto Colomer Robert J.P. Corriu J.Colin Young 《Journal of organometallic chemistry》1981,205(1):31-45
We report the chemical behavior of cobalt-stabilized carbenes, R3M(CO)3CoC(OEt)R′, and their parent anions, R3M(CO)3CoC(O?)R′, where M = Si or Ge. The anions where M = Si, R′ = Ph decompose thermally into the corresponding benzoylsilanes; when the silicon atom is chiral (R3 = MePh-1-Np) optically active R3SiCOPh is obtained with complete retention of configuration. 相似文献
69.
The pyridinium bisretinoid A2E, an autofluorescent pigment that accumulates in retinal pigment epithelial cells with age and in some retinal disorders, can mediate a detergent-like perturbation of cell membranes and light-induced damage to the cell. The photodynamic events initiated by the sensitization of A2E include the generation of singlet oxygen and the oxidation of A2E at carbon-carbon double bonds. To assess the ability of plant-derived anthocyanins to modulate adverse effects of A2E accumulation on retinal pigment epithelium (RPE) cells, these flavylium salts were isolated from extracts of bilberry. Nine anthocyanin fractions reflecting monoglycosides of delphinidin, cyanidin, petunidin and malvidin were obtained and all were shown to suppress the photooxidation of A2E at least in part by quenching singlet oxygen. The anthocyanins tested exhibited antioxidant activity of variable efficiency. The structural characteristics relevant to this variability likely included the ability to form a stable quinonoidal anhydro base at neutral pH, a conjugated diene structure in the C (pyrane) ring, the presence of hydroxyl groups on the B (benzene) ring and the relative hydrophobicity conferred by the arrangement of substituents on the B ring. Cells that had taken up anthocyanins also exhibited a resistance to the membrane permeabilization that occurs as a result of the detergent-like action of A2E. 相似文献
70.
Sequence-specific phenylacetylene oligomers consisting of functionalized monomers (hexyl benzoate, hexyl phenyl ether, benzonitrile, and tert-butylphenyl) are synthesized in gram quantities using solid-phase methods. Growing oligomers are attached to a divinylbenzene cross-linked polystyrene support by the 1-aryl-3-propyl-3-(benzyl-supported) triazene moiety. This linkage is obtained by reaction of arenediazonium tetrafluoroborate salts with a n-propylamino-modified Merrifield resin. Condensation strategies are described, producing oligomers with higher yields and simplified procedures compared to solution-phase methods. Terminal acetylene is protected with a trimethylsilyl group. After deprotection of the resin-bound terminal acetylene, an aryl iodide monomer or an aryl iodide-terminated oligomer is coupled to the supported oligomer using a palladium(0) catalyst. The cycle can be repeated to produce sequence-specific oligomers of varying length and functionality. The resulting oligomers are liberated from the polymer support by cleavage of the 1-aryl-3-propyl-3-(benzyl-supported) triazene group by reaction with iodomethane producing an aryl iodide. 相似文献