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261.
Souza DZ Boehl PO Comiran E Mariotti KC Pechansky F Duarte PC De Boni R Froehlich PE Limberger RP 《Analytica chimica acta》2011,696(1-2):67-76
A method for the simultaneous identification and quantification of amphetamine (AMP), methamphetamine (MET), fenproporex (FEN), diethylpropion (DIE) and methylphenidate (MPH) in oral fluid collected with Quantisal? device has been developed and validated. Thereunto, in-matrix propylchloroformate derivatization followed by direct immersion solid-phase microextraction and gas chromatography-mass spectrometry were employed. Deuterium labeled AMP was used as internal standard for all the stimulants and analysis was performed using the selected ion monitoring mode. The detector response was linear for the studied drugs in the concentration range of 2-256 ng mL(-1) (neat oral fluid), except for FEN, whereas the linear range was 4-256 ng mL(-1). The detection limits were 0.5 ng mL(-1) (MET), 1 ng mL(-1) (MPH) and 2 ng mL(-1) (DIE, AMP, FEN), respectively. Accuracy of quality control samples remained within 98.2-111.9% of the target concentrations, while precision has not exceeded 15% of the relative standard deviation. Recoveries with Quantisal? device ranged from 77.2% to 112.1%. Also, the goodness-of-fit concerning the ordinary least squares model in the statistical inference of data has been tested through residual plotting and ANOVA. The validated method can be easily automated and then used for screening and confirmation of amphetamine-type stimulants in drivers' oral fluid. 相似文献
262.
Romano F Hudson A Doye JP Ouldridge TE Louis AA 《The Journal of chemical physics》2012,136(21):215102
We use a recently developed coarse-grained model for DNA to study kissing complexes formed by hybridization of complementary hairpin loops. The binding of the loops is topologically constrained because their linking number must remain constant. By studying systems with linking numbers -1, 0, or 1 we show that the average number of interstrand base pairs is larger when the topology is more favourable for the right-handed wrapping of strands around each other. The thermodynamic stability of the kissing complex also decreases when the linking number changes from -1 to 0 to 1. The structures of the kissing complexes typically involve two intermolecular helices that coaxially stack with the hairpin stems at a parallel four-way junction. 相似文献
263.
264.
Garbuio L Antonello S Guryanov I Li Y Ruzzi M Turro NJ Maran F 《Journal of the American Chemical Society》2012,134(25):10628-10637
We synthesized two series of compounds in which a nitroxide radical and a fullerene C(60) moiety were kept separated by a 3(10)-helical peptide bridge containing two intramolecular C═O···H-N hydrogen bonds. The direction of the resulting molecular dipole moment could be reversed by switching the position of fullerene and nitroxide with respect to the peptide nitrogen and carbon termini. The resulting fullerene-peptide-radical systems were compared to the behaviors of otherwise identical peptides but lacking either C(60) or the free radical moiety. Electrochemical analysis and chemical nitroxide reduction experiments show that the dipole moment of the helix significantly affects the redox properties of both electroactive groups. Besides providing evidence of a folded helical conformation for the peptide bridge, IR and NMR results highlight a strong effect of peptide orientation on the spectral patterns, pointing to a specific interaction of one of the helical orientations with the C(60) moiety. Time-resolved EPR spectra show not only that for both systems triplet quenching by nitroxide induces spin polarization of the radical spin sublevels, but also that the coupling interaction can be either weak or strong depending on the orientation of the peptide dipole. As opposed to the concept of dyads, the molecules investigated are thus better described as fullerene-peptide-radical systems to stress the active role of the bridge as an important ingredient capable of tuning the system's physicochemical properties. 相似文献
265.
Giancarlo V. Botteselle Welman C. Elias Luana Bettanin Rmulo F. S. Canto Drielly N. O. Salin Flavio A. R. Barbosa Sumbal Saba Hugo Gallardo Gianluca Ciancaleoni Josiel B. Domingos Jamal Rafique Antonio L. Braga 《Molecules (Basel, Switzerland)》2021,26(15)
Herein, we describe a simple and efficient route to access aniline-derived diselenides and evaluate their antioxidant/GPx-mimetic properties. The diselenides were obtained in good yields via ipso-substitution/reduction from the readily available 2-nitroaromatic halides (Cl, Br, I). These diselenides present GPx-mimetic properties, showing better antioxidant activity than the standard GPx-mimetic compounds, ebselen and diphenyl diselenide. DFT analysis demonstrated that the electronic properties of the substituents determine the charge delocalization and the partial charge on selenium, which correlate with the catalytic performances. The amino group concurs in the stabilization of the selenolate intermediate through a hydrogen bond with the selenium. 相似文献
266.
Silvanna L. A. Maranhão Luis C. Cides da Silva Alexandre F. Michels Flavio Horowitz Jivaldo R. Matos Márcia C. A. Fantini 《Brazilian Journal of Physics》2014,44(4):346-355
Well-ordered hexagonal mesoporous silica thin films, SBA-15 type, were synthesized with Pluronic P123 and tetraethyl orthosilicate in a diluted ethanol-hydrochloric acid solution. Films deposited on a broad range of distinct substrates by a sol-gel dip-coating method resulted in transparent and adherent samples. Transmission electron microscopy images revealed, predominantly, well-ordered regions of hexagonal arrays of cylindrical mesopores parallel to the substrate. X-ray reflectivity showed similar lattice parameters for all analyzed films, with a (h00) preferred orientation. The films presented diverse shrinkage susceptibilities, which were tested after different polymer removal procedures. Calcined films have 342 m2/g surface area, 0.130 cm3/g pore volume, and 6.8 nm pore diameter. The wetting characteristics of the substrates in water and alcoholic solutions were evaluated. The films showed different structural properties, mostly related to the mean surface roughness of the substrates and to the drying process. 相似文献
267.
The increasing interest in renewable energy, particularly in wind, has given rise to the necessity of accurate models for the generation of good synthetic wind speed data. Markov chains are often used for this purpose but better models are needed to reproduce the statistical properties of wind speed data. We downloaded a database, freely available from the web, in which are included wind speed data taken from L.S.I. -Lastem station (Italy) and sampled every 10 min. With the aim of reproducing the statistical properties of this data we propose the use of three semi-Markov models. We generate synthetic time series for wind speed by means of Monte Carlo simulations. The time lagged autocorrelation is then used to compare statistical properties of the proposed models with those of real data and also with a synthetic time series generated through a simple Markov chain. 相似文献
268.
We study the ergodic properties of generic continuous dynamical systems on compact manifolds. As a main result we prove that generic homeomorphisms have convergent Birkhoff averages under continuous observables at Lebesgue almost every point. In spite of this, when the underlying manifold has dimension greater than one, generic homeomorphisms have no physical measures—a somewhat strange result which stands in sharp contrast to current trends in generic differentiable dynamics. Similar results hold for generic continuous maps. To further explore the mysterious behaviour of C 0 generic dynamics, we also study the ergodic properties of continuous maps which are conjugated to expanding circle maps. In this context, generic maps have divergent Birkhoff averages along orbits starting from Lebesgue almost every point. 相似文献
269.
Evaluation of laser induced breakdown spectroscopy for cadmium determination in soils 总被引:2,自引:0,他引:2
Dario Santos Jr. Lidiane C. Nunes Lilian C. Trevizan Quienly Godoi Flavio O. Leme Jez Willian B. Braga Francisco Jos Krug 《Spectrochimica Acta Part B: Atomic Spectroscopy》2009,64(10):1073
Cadmium is known to be a toxic agent that accumulates in the living organisms and present high toxicity potential over lifetime. Efforts towards the development of methods for microanalysis of environmental samples, including the determination of this element by graphite furnace atomic absorption spectrometry (GFAAS), inductively coupled plasma optical emission spectrometry (ICP OES), and inductively coupled plasma-mass spectrometry (ICP-MS) techniques, have been increasing. Laser induced breakdown spectroscopy (LIBS) is an emerging technique dedicated to microanalysis and there is a lack of information dealing with the determination of cadmium. The aim of this work is to demonstrate the feasibility of LIBS for cadmium detection in soils. The experimental setup was designed using a laser Q-switched (Nd:YAG, 10 Hz, λ = 1064 nm) and the emission signals were collimated by lenses into an optical fiber coupled to a high-resolution intensified charge-coupled device (ICCD)-echelle spectrometer. Samples were cryogenically ground and thereafter pelletized before LIBS analysis. Best results were achieved by exploring a test portion (i.e. sampling spots) with larger surface area, which contributes to diminish the uncertainty due to element specific microheterogeneity. Calibration curves for cadmium determination were achieved using certified reference materials. The metrological figures of merit indicate that LIBS can be recommended for screening of cadmium contamination in soils. 相似文献
270.