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41.
Micellar electrokinetic capillary chromatography for the determination of Viagra and its metabolite (UK-103,320) in human serum 总被引:1,自引:0,他引:1
Berzas Nevado JJ Rodríguez Flores J Castañeda Peñalvo G Rodríguez Fariñas N 《Electrophoresis》2001,22(10):2004-2009
Micellar electrokinetic capillary chromatography (MEKC) was investigated for the determination of Viagra (sildenafil citrate, SC) and its metabolite (UK-103,320) in human serum in a concentration range of clinical interest. For MEKC, human serum samples spiked with SC and UK were obtained directly after elution with methanol from a tC18 cartridge. The extract was evaporated and regenerated in a solution 1 mM of phosphate buffer (pH 12.3) which contained a methanol percentage of 20% that was analyzed using phosphate buffer (pH 12.3, 10 mM) containing 30 mM sodium dodecyl sulfate (SDS) as separation electrolyte and a fused-silica capillary. This method gave satisfactory interday precision with respect to migration times relative standard deviation (RSD < 1%) and linear responses for the concentration ranges investigated (0.50-3.50 mg L(-1) for the compound SC and 0.90-4.60 mg L(-1) for UK). An intraday RSD (n = 5 graphs) between the slopes of the calibration graphs was acceptable (6.40%) for SC and (3.37%) for UK. A satisfactory interday precision between slopes was also obtained (RSD 4.10% for SC and a RSD 2.72% for UK) which demonstrated the ruggedness of this method. Detection limits (S/N = 3) were about 200 ng/mL for both compounds in human serum. MEKC was shown as a good method with regards to simplicity, precision and sensitivity. 相似文献
42.
Rodríguez-Cea A de la Campa MR Sanz-Medel A 《Analytical and bioanalytical chemistry》2005,381(2):388-393
Cytochromes P-450 are members of a superfamily of hemoproteins involved in the oxidative metabolism of various physiological and xenobiotic compounds in eukaryotes and prokaryotes. The multiplicity of this group of enzymes has been widely studied by chromatographic techniques, mainly high-performance liquid chromatography (HPLC). Because these enzymes are membrane-bound proteins, sample preparation for chromatographic separation of P-450 enzymes requires a solubilization step. The sample-preparation procedures are critical, because detergents affect not only the efficiency of protein solubilization but also their further chromatographic resolution. Trout liver microsomes have been taken here as a model sample to investigate iron speciation in cytochrome P-450. Trouts were treated intraperitoneally with -naphthoflavone, a potent inducer of some P-450 enzymes, and a microsomal suspension containing 7.4±0.1 nmol mL–1 P-450 enzymes was obtained by ultracentrifugation. Lubrol PX was selected as detergent for solubilization, resulting in about 90% solubilization recovery. The solubilized cytochromes P-450 were further separated by AE–FPLC, with UV detection, or coupled to ICP–MS with an octapole reaction system, ICP–(ORS)MS (monitoring Fe signals at masses 54, 56, and 57). A sampling procedure and chromatographic conditions are developed and were successfully applied to iron speciation in trout liver P-450 enzymes. ICP–(ORS)MS detection of P-450 enzymes is Fe-specific and so will give accurate information on the prosthetic group of the protein, which can constitute an advantageous alternative to classical methods for detection of these hemoproteins. 相似文献
43.
Cabaleiro-Lago EM Rodríguez-Otero J García-López RM Peña-Gallego A Hermida-Ramón JM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(20):5966-5974
A comprehensive B3LYP/6-31+G* study on the electrocyclization of 1,2,4,6-heptatetraene analogues was conducted. Starting from the cyclization of (2Z)-2,4,5-hexatrienal, a pericyclic disrotatory process favored by the assistance of a electron lone pair, we incorporated small modifications in its molecular structure to obtain a truly pseudopericyclic process. To this purpose electronegative atoms (fluorine and nitrogen) were added to give a more electrophilic character on the carbon atom which is attacked by the electron lone pair of the oxygen atom. The complete pathway for each reaction was determined, and changes in magnetic properties were monitored with a view to estimating the aromatization associated with each process. This information, together with the energetic and structural results, allowed us to classify the reactions as pseudopericyclic or pericyclic. Among all studied reactions only one was a truly pseudopericyclic process and another was a borderline case. The features of this unequivocally pseudopericyclic case were analyzed in depth. 相似文献
44.
Pulkkinen S Noguera M Rodríguez-Santiago L Sodupe M Bertran J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(23):4393-4399
The intramolecular proton transfer in cationized glycine and chlorine substituted derivatives with M = Na+, Mg2+, Ni+, Cu+, and Cu2+ has been studied with the three parameter B3LYP density functional method. The coordination of metal cations to the oxygens of the carboxylic group of glycine stabilizes the zwitterionic structure. For all monocations the intramolecular proton transfer occurs readily with small energy barriers (1-2 kcalmol(-1)). For the dication Mg2+ and Cu2+ systems, the zwitterionic structure becomes very stable. However, whereas for Mg2+, the proton transfer process takes place spontaneously, for Cu2+ the reaction occurs with an important energy barrier. The substitution of the hydrogens of the amino group by chlorine atoms decreases the basicity of nitrogen, which destabilizes the zwitterionic structure. For monosubstituted glycine complexed with Na+, the zwitterionic structure still exists as a minimum, but for disubstituted glycine no minimum appears for this structure. In contrast, for Mg2+ complexed to mono- and disubstituted glycine, the zwitterionic structure remains the only minimum, since the enhanced electrostatic interaction with the dication overcomes the destabilizing effect of the chlorine atoms. 相似文献
45.
Martínez-Alvarez R Martín N Seoane C Suárez M Pérez R Rodríguez H Kayali N 《Rapid communications in mass spectrometry : RCM》2001,15(10):758-762
The electrospray ionisation (ESI) in negative mode of the pharmacologically significant 3,5-disubstituted tetrahydro-2H-1,3,5-thiadiazin-2-thiones, and their subsequent fragmentations using an ion-trap mass spectrometer, have been investigated. Experiments on sequential product ion fragmentations (MS(n)) were performed in order to elucidate the degradation pathways for these compounds. The data presented show that the fragmentation of the even-electron [M - H](-) ions could proceed through an internal nucleophilic substitution displacement. Decarboxylation and extrusion of carbon disulfide are other fragmentations observed. 相似文献
46.
M. T. Fernández-Díaz J. Rodríguez-Carvajal J. L. Martínez G. Fillion F. Fernández R. Saez-Puche 《Zeitschrift für Physik B Condensed Matter》1991,82(2):275-282
Neutron powder diffraction and magnetization measurements have been performed in stoichiometric Pr2NiO4+(0), which at room temperature (RT) is orthorhombic (Bmab). Ni2+ becomes three dimensionally (3D) antiferromagnetically ordered atT
N
325K, with a propagation vectork=[100], and spins oriented along thea axis (parallel to the propagation vector). The magnetic structure belongs to the
7g
(––+)-representation (g
x
mode, Shubnikov groupB
pmab') ofBmab, and a magnetic moment of 1.5
B
is measured at 155K. This compound undergoes two different structural phase transitions. First, going down in temperature, Pr2NiO4 transforms by a first order phase transition from orthorhombic (Bmab) to tetragonal (P42/ncm) atT
c1115K. At high temperature, we can predict a transformation from orthorhombic (Bmab) to tetragonal (I4/mmm) in a continuous way. The extrapolated temperature for this second structural transition isT
c21500±100K. The low temperature structural transformation allows a change in the magnetic structure which forT<T
c1 is better described in the orthorhombic symmetry. Just belowT
c1 the magnetic structure is described by the:
3g
(–+)-representation ofPccn(gxcyfz mode, Shubnikov groupPccn), this magnetic phase begins to disappear going down in temperature and at the same time a new magnetic phase grows. This new magnetic structure is described by the
1g
ofPccn (c
xgyaz mode, Shubnikov groupPccn). Both magnetic structures coexist in a certain temperature range. At 1.5 K thec
xgyaz mode represents the total of the magnetic ordering. To reproduce the observed magnetic intensities we are forced to consider that Pr3+ is polarized below 40 K, with a magnetic structure which is coupled to the Ni sublattices (i.e.
1g
and
3g
). The magnetic moment at low temperature for Pr is about 1.28
B
. 相似文献
47.
Heart rate oscillates on several different time scales and has long-term variability in the form of 1/f noise. The physiological control of heart rate is briefly reviewed, and several typical patterns of heart rate variability, in health and sickness, are described. Considered briefly are some possible dynamical mechanisms for heart rate variability. 相似文献
48.
Giovanni Appendino Giancarlo Cravotto Gian Mario Nano Giovanni Palmisano Rita Annunziata 《Helvetica chimica acta》1993,76(3):1194-1202
The reaction of 4-hydroxycoumarin and certain aliphatic aldehydes affords 1:1 or complex 2:2 adducts besides (or in place) of the expected 2:1 bis(coumarin) adducts. Reaction with heptanal, cyclohexanecarbaldehyde, and pivalaldehyde are reported as representative. The structure of the reaction products was established by spectroscopical techniques, including X-ray analysis, and their formation was mechanistically rationalized. Some of the 1:1 adducts are synthetically useful for the preparation of 3-alkyl-4-hydroxycoumarins. 相似文献
49.
A. Villares S. Rodríguez C. Lafuente F. M. Royo M. C. López 《Journal of solution chemistry》2004,33(9):1119-1133
Experimental viscosities and the corresponding viscosity deviations for the binary mixtures of a cyclic ether (tetrahydrofuran, tetrahydropyran, 2-methyltetrahydrofuran, or 2,5-dimethyltetrahydrofuran) with benzene, toluene, fluorobenzene, or chlorobenzene are given at 25°C. The kinematic viscosities and the corresponding densities were measured with an uncertainty of ±10– 4 mm2-s– 1 and ±(5×10– 3) kg-m– 3, respectively. The viscosity data were correlated by the equations of Grunberg–Nissan, McAllister, and Heric. On the other hand, the results have been compared to the predictions, by the method proposed by Asfour. 相似文献
50.
The electron transfer spectra of adducts of the title metal halides with a series of ligands (nitriles, dialkylchalcogenides, phosphoryl and thiophosphoryl ligands and phosphines) have been studied. The effect of halogen substitution on the halogen metal transitions is discussed by comparing the spectra of the adducts with those of the hexahalometalates. The origin of the two ligand-metal transitions observed in most adducts is discussed, and the splitting of the metal d levels in these almost octahedral adducts is estimated. For each metal halide, the series of adducts with dialkyl chalcogenides show a linear relationship of slope one between the ligand ionisation potential and the ligand-metal charge transfer energy. The ligand optical electronegativities have been estimated. 相似文献