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21.
Brunetto R Gutiérrez L Delgado Y Gallignani M Burguera JL Burguera M 《Analytical and bioanalytical chemistry》2003,375(4):534-538
A column-switching high-performance liquid chromatographic method with UV detection for the determination of cocaine (COC) and benzoylecgonine (BZE) in human blood plasma samples is described. The method uses an alkyl-diol-silica ADS-C18 extraction precolumn. A 50- micro L plasma sample was introduced to the ADS precolumn in order to separate the analytes from proteins and endogenous compounds. The fraction containing COC and BZE was back-flushed and transferred to an Alltech mixed-mode C(18)/cation-exchange analytical column for final separation. The validation of the method revealed quantitative recoveries from 95.0 to 99.0% for COC at three different concentrations (0.5, 1.0 and 2.0 micro g mL(-1)), and from 96.0 to 99.0% for BZE at the same concentration levels with coefficients of variation <4.00% (n=5). The detection limit (signal to noise ratio (S/N)>3) was 0.03 micro g mL(-1) for all the compounds with an injection volume of 50 micro L. However, it was possible to enhance the sensitivity further by injecting larger plasma volumes, up to 200 micro L, at the same optimal conditions. The overlap of sample preparation, analysis and reconditioning of the extraction column, increase the overall sample throughput to 5 samples h(-1). The developed method has been applied to human blood plasma samples from subjects suspected of cocaine abuse. 相似文献
22.
Water adsorption and absorption on crystalline polyvinylidene fluoride with 30% trifluoroethylene, P(VDF-TrFE, 70:30), was examined by thermal desorption spectroscopy. Two distinctly different water adsorption sites are identified: one adsorbed species that resembles ice and another species that interacts more strongly with the polymer thin film. The existence of the latter species is consistent with X-ray diffraction studies of water absorbed into the bulk of copolymers of polyvinylidene fluoride with trifluoroethylene crystalline thin films. There are strong steric effects observed in the angle-resolved thermal desorption that may be a result of the large polymer thin film surface dipoles. 相似文献
23.
Jos R. Ascenso Maria de Deus Carvalho Alberto R. Dias Carlos C. Romo Maria J. Calhorda Luis F. Veiros 《Journal of organometallic chemistry》1994,470(1-2):147-152
The metallocene thioether derivatives [Cp2M(MeSCH2CH2SMe)][PF6]2 (1, M = MO; 2, M = W), [Cp2Mo(SCH2CH2SMe)][PF6] (3) and [Cp2M(SCH2CH2S)] (4, M = Mo; 5, M = W) exhibit temperature-dependent fluxional behavior in solution, owing to the pyramidal sulfur inversion process. The activation energies for this process were determined from proton band-shape analysis in the cases of 1 (54.9 ± 2 kJ mol−1), 2 (51.2 ± 4.6 kJ mol−1) and 3 (30.0 ± 3.1 kJ mol−1). Extended Hückel calculations on related model complexes suggest that local inversion at the sulfur atoms, rather that an inversion of the complete S---C---C---S chain, is responsible for the observed fluxional behaviour. 相似文献
24.
The syntheses of 2,3,5-trimethylidenebicyclo[2.2.1]heptane ( 1 ) and 2,3,5,6,7-pentamethylidenebicyclo[2.2.2]-octane ( 2 ) are reported. The Diels-Alder additions of the diene moieties of these polyenes can be regioselective, probably because of a possible transannular interaction between the homoconjugated methylidene and s-cis-buta-diene groups. 相似文献
25.
Orte A Bermejo R Talavera EM Crovetto L Alvarez-Pez JM 《The journal of physical chemistry. A》2005,109(12):2840-2846
The presence of excited-state buffer-mediated proton exchange reactions influences the steady-state fluorescence signals from dyes in solution. Since biomolecules in general have some chemical groups that can act as proton acceptors/donors and are usually dissolved in buffer solutions which can also behave as appropriate proton acceptors/donors, the excited-state proton exchange reactions may result in distorted steady-state fluorescence signals. In a previous paper (J. Phys. Chem. A 2005, 109, 734-747), we evaluated kinetic and other pertinent parameters for the excited-state proton reactions of the prototropic forms of 2',7'-difluorofluorescein (Oregon Green 488, OG488), recording a fluorescence decay surface at different pH values and acetate buffer concentrations, analyzed by means of global compartmental analysis. In this article we use the rate constants and the corrected pre-exponential factors from the previously recorded fluorescence decay traces to simulate the decay times and associated pre-exponentials at different acetate buffer concentrations and constant pH and compare these theoretically calculated values with new experimental data. We also calculate the steady-state fluorescence intensity vs pH and vs acetate buffer concentration (at constant pH) and compare these calculated emission values with the experimental data previously published. The agreement between the experimental and simulated data is excellent. 相似文献
26.
In this work we have studied the stabilizing effect of the lignin, obtained as a by-product of the acid hydrolysis of sugar cane bagasse, herein called sugar cane bagasse lignin, on the thermal and environmental degradation of butadiene rubber. This stabilizer was investigated in various concentrations in the pure form and as a substitute for a hindered phenol, in a commercially used formulation also containing a p-phenylene-diamine. For thermal degradation the stabilization level of the commercial sample is reached with 1·3% of pure lignin and the substitution of the hindered phenol in the commercial formulation increased the stabilization by a factor of 1·2. In the environmental ageing experiments the performance of the rubber stabilized with lignin was poorer than that of the commercial sample. This behaviour is assigned to the strong degradative effect of light on the rubber. 相似文献
27.
Elena Almaraz Luengo Marcos Brian Leiva Cerna Luis Javier García Villalba Julio Hernandez-Castro Darren Hurley-Smith 《Entropy (Basel, Switzerland)》2022,24(5)
This work presents an analysis of the existing dependencies between the tests of the FIPS 140-2 battery. Two main analytical approaches are utilized, the first being a study of correlations through the Pearson’s correlation coefficient that detects linear dependencies, and the second one being a novel application of the mutual information measure that allows detecting possible non-linear relationships. In order to carry out this study, the FIPS 140-2 battery is reimplemented to allow the user to obtain p-values and statistics that are essential for more rigorous end-user analysis of random number generators (RNG). 相似文献
28.
Vernica Herrera-Mayorga Jos Alfredo Guerrero-Snchez Domingo Mndez-lvarez Francisco A. Paredes-Snchez Luis Víctor Rodríguez-Duran Nohemí Nio-García Alma D. Paz-Gonzlez Gildardo Rivera 《Molecules (Basel, Switzerland)》2022,27(10)
Spodoptera frugiperda (S. frugiperda) remains a global primary pest of maize. Therefore, new options to combat this pest are necessary. In this study, the insecticidal activity of three crude foliar extracts (ethanol, dichloromethane, and hexane) and their main secondary metabolites (quercetin and chlorogenic acid) of the species Solidago graminifolia (S. graminifolia) by ingestion bioassays against S. frugiperda larvae was analyzed. Additionally, the extracts were phytochemically elucidated by ultra-performance liquid chromatography-mass spectrometry (UPLC-MS) analysis. Finally, an in silico study of the potential interaction of quercetin on S. frugiperda acetylcholinesterase was performed. Organic extracts were obtained in the range from 5 to 33%. The ethanolic extract caused higher mortality (81%) with a half-maximal lethal concentration (LC50) of 0.496 mg/mL. Flavonoid secondary metabolites such as hyperoside, quercetin, isoquercetin, kaempferol, and avicularin and some phenolic acids such as chlorogenic acid, solidagoic acid, gallic acid, hexoside, and rosmarinic acid were identified. In particular, quercetin had an LC50 of 0.157 mg/mL, and chlorogenic acid did not have insecticidal activity but showed an antagonistic effect on quercetin. The molecular docking analysis of quercetin on the active site of S. frugiperda acetylcholinesterase showed a −5.4 kcal/mol binding energy value, lower than acetylcholine and chlorpyrifos (−4.45 and −4.46 kcal/mol, respectively). Additionally, the interactions profile showed that quercetin had π–π interactions with amino acids W198, Y235, and H553 on the active site. 相似文献
29.
Genista monspessulana (L.) L.A.S. Johnson (Fabaceae) is a Mediterranean plant introduced to South America and other regions for ornamental purposes. However, it is considered an invasive shrub due to its reproductive vigor in many areas. Unlike other Genista plants, G. monspessulana has few studies disclosing its biologically active components, particularly cytotoxic agents against cancer cells. Thus, as part of our research on anti-proliferative bioactives, a set of ethanolic seed extracts from ten accessions of G. monspessulana, collected in the Bogotá plateau, were evaluated against four cell lines: PC-3 (prostate adenocarcinoma), SiHa (cervical carcinoma), A549 (lung carcinoma), and L929 (normal mouse fibroblasts). Extracts were also analyzed through liquid chromatography coupled with mass spectrometry (LC/MS) to record chemical fingerprints and determine the composition and metabolite variability between accessions. Using multiple covariate statistics, chemical and bioactivity datasets were integrated to recognize patterns and identify bioactive compounds among studied extracts. G. monspessulana seed-derived extracts exhibited dose-dependent antiproliferative activity on PC-3 and SiHa cell lines (>500 µg/mL < IC50 < 26.3 µg/mL). Seven compounds (1–7) were inferred as the compounds most likely responsible for the observed anti-proliferative activity and subsequently isolated and identified by spectroscopic techniques. A tricyclic quinolizidine (1) and a pyranoisoflavone (2) were found to be the most active compounds, exhibiting selectivity against PC-3 cell lines (IC50 < 18.6 µM). These compounds were used as precursors to obtain a quinolizidine-pyranoisoflavone adduct via Betti reaction, improving the activity against PC-3 and comparable to curcumin as the positive control. Results indicated that this composition–activity associative approach is advantageous to finding those bioactive principles efficiently within active extracts. This correlative association can be employed in further studies focused on the targeted isolation of anti-proliferative compounds from Genista plants and accessions. 相似文献
30.
Gredson Keiff Souza Andr Gallo Luiza Hauser Novicki Heitor Rodrigues Neto Eneida de Paula Anita Jocelyne Marsaioli Luis Fernando Cabea 《Molecules (Basel, Switzerland)》2022,27(13)
The drugs delivery system in the treatment of diseases has advantages such as reduced toxicity, increased availability of the drug, etc. Therefore, studies of the supramolecular interactions between local anesthetics (LAs) butamben (BTB) or ropivacaine (RVC) complexed with 2-hydroxypropyl-β-cyclodextrin (HP-βCD) and carried in Stealth liposomal (SL) are performed. 1H-NMR nuclear magnetic resonance (DOSY and STD) were used as the main tools. The displacements observed in the 1H-NMR presented the complexion between LAs and HP-βCD. The diffusion coefficients of free BTB and RVC were 7.70 × 10−10 m2 s−1 and 4.07 × 10−10 m2 s−1, and in the complex with HP-βCD were 1.90 × 10−10 m2 s−1 and 3.64 × 10−10 m2 s−1, respectively, which indicate a strong interaction between the BTB molecule and HP-βCD (98.3% molar fraction and Ka = 72.279 L/mol). With STD-NMR, the encapsulation of the BTB/HP-βCD and RVC/HP-βCD in SL vesicles was proven. Beyond the saturation transfer to the LAs, there is the magnetization transfer to the hydrogens of HP-βCD. BTB and RVC have already been studied in normal liposome systems; however, little is known of their behavior in SL. 相似文献