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81.
Rosenthal SJ Tomlinson I Adkins EM Schroeter S Adams S Swafford L McBride J Wang Y DeFelice LJ Blakely RD 《Journal of the American Chemical Society》2002,124(17):4586-4594
To explore the potential for use of ligand-conjugated nanocrystals to target cell surface receptors, ion channels, and transporters, we explored the ability of serotonin-labeled CdSe nanocrystals (SNACs) to interact with antidepressant-sensitive, human and Drosophila serotonin transporters (hSERT, dSERT) expressed in HeLa and HEK-293 cells. Unlike unconjugated nanocrystals, SNACs were found to dose-dependently inhibit transport of radiolabeled serotonin by hSERT and dSERT, with an estimated half-maximal activity (EC(50)) of 33 (dSERT) and 99 microM (hSERT). When serotonin was conjugated to the nanocrystal through a linker arm (LSNACs), the EC(50) for hSERT was determined to be 115 microM. Electrophysiology measurements indicated that LSNACs did not elicit currents from the serotonin-3 (5HT(3)) receptor but did produce currents when exposed to the transporter, which are similar to those elicited by antagonists. Moreover, fluorescent LSNACs were found to label SERT-transfected cells but did not label either nontransfected cells or transfected cells coincubated with the high-affinity SERT antagonist paroxetine. These findings support further consideration of ligand-conjugated nanocrystals as versatile probes of membrane proteins in living cells. 相似文献
82.
Denning MS Watts ID Moussa SM Durand P Rosseinsky MJ Tanigaki K 《Journal of the American Chemical Society》2002,124(19):5570-5580
The high symmetry and resulting electronic degeneracy of the C(60)(3)(-) anion is viewed as the key molecular feature in the high superconducting transition temperatures of fulleride and oxidized fullerene systems. The experimental evaluation of this hypothesis requires the synthesis of face-centered cubic (fcc) trivalent fulleride anion salts derived from higher fullerenes such as C(70), which have thus far proved elusive with only stable A(1)C(70), A(4)C(70), and A(6)C(70) phases known. In this paper, we report the synthesis of fcc A(3)C(70) phases stabilized by size-matching the tetrahedral site with the sodium cation. The structures are strongly dependent on the cooling protocol due to the existence of metastable partially or completely orientationally disordered phases. EPR data indicate that the phases are metallic but not superconducting. The densities of states at the Fermi level appear too low to give superconductivity at above 5 K, consistent with recent observations that four electrons per C(70) anion are required for superconductivity. Size-matching on both the octahedral and tetrahedral sites is required for A(3)C(70) stability - K(2)CsC(70) is only stable at elevated temperature and Na(2)C(70) is unstable, the composition corresponding to C(70) and a sodium-rich trigonal phase. 相似文献
83.
Giancarlo Marconi Sandra Monti Francesco Manoli Alessandra DegliEsposti Andrea Guerrini 《Helvetica chimica acta》2004,87(9):2368-2377
The circular dichroism (CD) spectra of the powerful antimalarian active principle artemisinin (ART; 1 ) from Artemisia annua, and of epiartemisinin (EPI, 2), its C(7) epimer, were studied in solution in the presence and absence of β‐cyclodextrin (β‐cd). A significant inversion of sign in the region of the second electronic transition was detected. The rotational strengths were successfully calculated within the time‐dependent density functional theory (DFT), which enabled us to establish a correlation between the molecular recognition and the biological acitivities of the two isomers. 相似文献
84.
Analytical procedures for quantification of peptides in pharmaceutical research by liquid chromatography–mass spectrometry 总被引:6,自引:0,他引:6
John H Walden M Schäfer S Genz S Forssmann WG 《Analytical and bioanalytical chemistry》2004,378(4):883-897
Peptide quantification by liquid chromatography–mass spectrometry (LC–MS) combines the high resolving power of reversed-phase (RP) chromatography with the excellent selectivity and sensitivity of mass spectrometric detection. On the basis of comprehensive practical experience in the analysis of small molecules, pharmaceutical research is developing technologies for analysis of a growing number of peptidic drug candidates. This article is a detailed review of procedures based on LC–MS techniques for quantitative determination of peptides. With the focus on pharmaceutical applications several technologies for sample preparation, various aspects of peptide chromatography, important characteristics of ESI–MS, selectivity of MS-detection modes, the large variability of internal standards, and modern instrumentation are discussed. The demand for reliable, robust, sensitive, and accurate methods is discussed using numerous examples from the literature, complemented by experiments and results from our laboratory. 相似文献
85.
A solid-phase extraction (SPE) procedure that fractionates wine samples into 2 sub-samples containing sugars and organic acids (sub-sample 1) and low molecular weight polyphenols (sub-sample 2), respectively, together with rugged LC procedures for their analyses are described. Wine is adjusted to pH 2.5 and loaded on a styrene-divinylbenzene (SDB) cartridge. The organic acids and sugars are eluted with 20 mM sulphuric acid and the monomeric polyphenols with ethyl acetate. Glucose and fructose are analysed by normal phase LC with evaporative light scattering detection and the organic acids by ion exclusion chromatography with UV detection at 210 nm. Analysis of the phenolic fraction is performed by reversed phase LC with diode array detection. Recoveries and repeatabilitys for 27 standard compounds (2 sugars, 7 organic acids and 18 polyphenols) are presented. The method represents an improvement in terms of productivity and robustness compared to currently used procedures. 相似文献
86.
Magnani A Marchettini N Ristori S Rossi C Rossi F Rustici M Spalla O Tiezzi E 《Journal of the American Chemical Society》2004,126(37):11406-11407
The present work deals with the spatially extended oscillatory Belousov Zhabotinsky reaction-diffusion system carried out in an anisotropic environment of phosphatidylcholines/water binary system, which presents layered aqueous domains separated by lipid bilayers. We report the occurrence of stable Turing patterns, spiral waves, and other exotic structures in phospholipids bilayers that are generally used as a models for cell plasma membranes. 相似文献
87.
The retention behaviour of fatty alcohol ethoxylates and fatty acid methyl ester ethoxylates on various reversed-phase columns in acetone-water has been studied in the regime of liquid exclusion-adsorption chromatography at different temperatures. Straight lines were obtained in the van't Hoff plots. The entropy and enthalpy changes were found to be negative (at least in the range of lower oligomers) and showed a dependence of the number of oxyethylene units. For higher oligomers, both entropy and enthalpy changes approach a constant value. This can be explained by the existence of a rather thick layer of organic solvent close to the surface of the stationary phase. 相似文献
88.
Salter L Clifford T Morley N Gould D Campbell S Curnow A 《Journal of photochemistry and photobiology. B, Biology》2004,75(1-2):57-61
Comet assay data (tail DNA %) have been gathered for the concentration dependent role of three antioxidants (AOs); quercetin (Q), epigallocatechin gallate (EGCG) and N-acetylcysteine (NAC) in reducing UV-induced damage to DNA in normal fetal lung fibroblasts (MRC5). All three compounds demonstrate a concentration dependent reduction maximum with a pro-oxidant effect at higher (though not cytotoxic) concentrations. Manipulation of a simple 4-step reaction mechanism for free radical (FR) scavenging by AOs produced rate constant ratios which allowed the relative effectiveness (Q > EGCG > NAC) of the AOs to be evaluated. 相似文献
89.
Fritz SE Martin SM Frisbie CD Ward MD Toney MF 《Journal of the American Chemical Society》2004,126(13):4084-4085
Grazing incidence X-ray diffraction reveals that a pentacene monolayer, grown on an amorphous SiO2 substrate that is commonly used as a dielectric layer in organic thin film transistors (OTFTs), is crystalline. A preliminary energy-minimized model of the monolayer, based on the GIXD data, reveals that the pentacene molecules adopt a herringbone arrangement with their long axes tilted slightly from the substrate normal. Although this arrangement resembles the general packing features of the (001) layer in single crystals of bulk pentacene, the monolayer lattice parameters and crystal structure differ from those of the bulk. Because carrier transport in pentacene OTFTs is presumed to occur in the semiconductor layers near the dielectric interface, the discovery of a crystalline monolayer structure on amorphous SiO2 has important implications for transport in OTFTs. 相似文献
90.
Gouveia CA Oliveira A Pinho S Vasconcelos C Carvalho F Moreira RF Dinis-Oliveira RJ 《Biomedical chromatography : BMC》2012,26(8):1041-1047
The development of analytical techniques that enable the use of hair as an alternative matrix for the analysis of drugs of abuse is useful for confirming the exposure in a larger time window (weeks to months, depending on the length of the hair shaft). In the present study a methodology aimed at the simultaneous quantification of cocaine and morphine in human hair was developed and validated. After decontamination, hair samples (20?mg) were incubated with a mixture of methanol/hydrochloric acid (2:1) at 65?°C overnight (~16?h) in order to extract the drugs of the matrix. Purification was performed by solid-phase extraction using mixed-mode extraction cartridges. After derivatization with N-methyl-N-(trimethylsilyl) trifluoroacetamide, blank, standards and samples were analyzed by gas chromatography/electron impact-mass spectrometry (GC-EI/MS). The method proved to be selective, as there were no interferences of endogenous compounds with the same retention time as cocaine, morphine and ethylmorphine (internal standard). The regression analysis for both analytes showed linearity in the range 0.25-10.00?ng/mg with correlation coefficients ranging from 0.9989 to 0.9991. The coefficients of variation oscillated between 0.83 and 14.60%. The limits of detection were 0.01 and 0.02?ng/mg, and the limits of quantification were 0.03 and 0.06?ng/mg for cocaine and morphine, respectively. The proposed GC-EI/MS method provided an accurate and simple assay with adequate precision and recovery for the quantification of cocaine and morphine in hair samples. The proof of applicability was performed in hair samples obtained from drug addicts enrolled in a Regional Detoxification Treatment Center. The importance of hair samples is highlighted, since positives results were obtained when urine immunoassay analyses were negative. Copyright ? 2012 John Wiley & Sons, Ltd. 相似文献