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831.
Fábio A. Silva Cilene C. F. Padilha Gustavo Rocha de Castro Paulo dos Santos Roldan Ana R. de Araujo Nogueira Paula M. Moraes Pedro M. Padilha 《Central European Journal of Chemistry》2011,9(1):119-125
This paper proposes a method to determine selenium in samples of fish muscle and liver tissue using ultrasound assisted extraction
process, and analysed by graphite furnace atomic absorption spectrometry (GFAAS). The selenium content was extracted by 0.10
M HCl at the optimal extraction conditions which were established as follows: sample mass of 100 mg; granulometry of the sample
<60 μm; sonication time of five 40 s cycles; and sonication power of 136 W. The selenium determinations were performed by
GFAAS, at a drying temperature of 120°C/250°C, pyrolysis temperature of 1300°C, atomization temperature of 2300°C, and cleaning
temperature of 2800°C. Palladium nitrate was used as a chemical modifier coinjected with the samples, and tungsten as a permanent
modifier. The concentration of selenium determined in the pool of fish muscle and liver tissue were 280.4±4.2 e 592.3±6.7
μg kg−1, respectively. The accuracy and precision of the proposed extraction method were evaluated using certified standard Bovine
Muscle — NIST 8414. The results obtained by the ultrasonic extraction method were equivalent to those obtained by the method
of acid mineralization of samples in a microwave oven 相似文献
832.
The solvability of a class of singular integral equations with reflection in weighted Lebesgue spaces is analyzed, and the
corresponding solutions are obtained. The main techniques are based on the consideration of certain complementary projections
and operator identities. Therefore, the equations under study are associated with systems of pure singular integral equations.
These systems will be then analyzed by means of a corresponding Riemann boundary value problem. As a consequence of such a
procedure, the solutions of the initial equations are constructed from the solutions of Riemann boundary value problems. In
the final part of the paper, the method is also applied to singular integral equations with the so-called commutative and
anti-commutative weighted Carleman shifts. 相似文献
833.
Alba MD Castro MA Clarke SM Medina S Messe L Millán C 《Solid state nuclear magnetic resonance》2011,40(4):138-143
The mixing of molecules adsorbed from solution to different interfaces has both industrial and academic relevance and the mixing behaviour at the interface is a key to understanding for example, that the surface tension of a mixture of two surfactants is lower than either of the two pure materials and many other effects. In this paper, we report, for the first time, the application of Solid State NMR to the study of alkane/alcohol mixtures, in a range of relative size ratio between 0 and 0.35, adsorbed onto graphite at high, multilayer coverage. Moreover, this paper evaluated, for the first time, the utility of the combined used of 1H and 2H NMR for: (i) determining the surface composition and (ii) making a theoretical approach to the sorption isotherm. A variety of preferential adsorption behaviour is reported. Preferential adsorption of the longer molecule (decane vs. heptanol) from a mixture has been observed. However, if both components are of similar length, the alcohol is preferentially adsorbed (heptanol vs. octane and octanol vs. octane). Finally, a linear relation between the relative size ratio and the amount of alcohol at monolayer coverage is observed. 相似文献
834.
Isabel M.S. Lampreia Carlos A. Nieto de Castro 《The Journal of chemical thermodynamics》2011,43(4):537-545
A new method for accurately converting vibrating tube periods of oscillation in density values is presented. This method is based on the fundamental requirement of the non-dependence on pressure of the vibration period of the cell under vacuum. An analytical method permits to correctly evaluate the evacuated vibrating tube periods of the Anton Paar cells namely the high pressure cells, 512 and 512P, as a function of temperature. It is further shown that the previously experimental method for the determination of this parameter is not suitable for obtaining reliable density values. A new simple calibration procedure is described and tested over wide ranges of temperature, T = (283.15 to 323.15) K and pressure, P = (0.1 to 60) MPa. New recommended density values for n-alkanes (C6, C7, C8, and C10) and tetrachloromethane, calculated by the proposed method, are given and compared with literature values in terms of mutual uncertainties. 相似文献
835.
León-González Z Ferreiro-Vera C Priego-Capote F de Castro MD 《Journal of chromatography. A》2011,1218(20):3013-3021
The in vivo metabolism of the xenobiotic agent 2-ethylhexyl 4-(N,N-dimethylamino)benzoate (EDP), a UV filter commonly used in sunscreen cosmetic products, was studied by targeting metabolomics analysis in human urine. The metabolomic study involved the use of urine from male and female volunteers before and after application of an EDP-containing sunscreen cosmetic. The metabolism of EDP in urine was studied by using the triple quadrupole detector in a combination of Precursor Ion Scanning and Neutral Loss Scanning modes, with and without enzymatic hydrolysis. Detected metabolites were subsequently confirmed as glucuronide conjugates of 4-(N,N-dimethylamino)benzoic acid and 4-(N-methylamino)benzoic acid by liquid chromatography-time-of-flight/mass spectrometry (LC-TOF/MS) in the accurate mass mode. In this way, the existence of phase II metabolism in the detoxification of EDP by effects of the lipophilic character of this sunscreen agent was confirmed. Hence, to study the in vivo metabolism of EDP, a fully automated method using a solid-phase extraction (SPE) workstation connected on-line to a liquid chromatograph and a triple quadrupole mass analyzer (LC-MS/MS) was developed. The ensuing hyphenated method is very simple and requires minimal human intervention. Following thorough optimization of the SPE and LC-MS/MS conditions, the analytical procedure was validated and standard addition calibration used for the quantitative correction of matrix effects. The proposed method was applied to determine the phase I metabolites of EDP in urine samples and afforded limits of detection from 0.1 to 1.1 ng and accuracy of 91-107% with relative standard deviations in the range 1.5-8.7% (sample volume: 100 μL). Based on the results of in vivo percutaneous absorption of a single application of the sunscreen, about 0.5% of the amount of the applied EDP is excreted in urine. 相似文献
836.
Density functional and coupled cluster calculations on neutral monodehydro[12]annulenes (C(12)H(10)) reveal a global minimum that should be kinetically stable. At the CCSD(T)/cc-pVDZ//BHLYP/6-31G* level, the unsymmetrical CTCTC conformer 1a lies at least 3 kcal/mol below all other isomers studied. The two isomers closest in energy to 1a are Mo?bius structure 5a (CCTCC) and all-cis 6a. Isomer 1a can undergo conformational automerization with E(a) = 3.9 kcal/mol, implying that this process would be rapid on the NMR time scale, and computed (1)H NMR parameters (GIAO-B3LYP/6-311+G**//RHF/6-31G*) are presented. Cumulenic dehydro[12]annulene isomers, with 1,2,3-butatriene subunits, were found to be reactive intermediates in the interconversion of different configurations of the alkyne forms. Pathways for configuration change of 1a, and for subsequent rearrangement to biphenyl, were investigated. The 28 kcal/mol overall barrier for the lowest energy pathway connecting 1a to biphenyl suggests that 1a is kinetically stable with respect to valence isomerization. 相似文献
837.
Klara Slezakova Dionísia Castro Arlindo Begonha Maria da Conceição Alvim-Ferraz Maria do Carmo Pereira 《Microchemical Journal》2011,99(1):51-59
Air pollution represents a serious risk not only to environment and human health, but also to historical heritage. In this study, air pollution of the Oporto Metropolitan Area and its main impacts were characterized. The results showed that levels of CO, PM10 and SO2 have been continuously decreasing in the respective metropolitan area while levels of NOx and NO2 have not changed significantly. Traffic emissions were the main source of the determined polycyclic aromatic hydrocarbons (PAHs; 16 PAHs considered by U.S. EPA as priority pollutants, dibenzo[a,l]pyrene and benzo[j]fluoranthene) in air of the respective metropolitan area. The mean concentration of 18 PAHs in air was 69.9 ± 39.7 ng m−3 with 3-4 rings PAHs accounting for 75% of the total ΣPAHs. The health risk analysis of PAHs in air showed that the estimated values of lifetime lung cancer risks considerably exceeded the health-based guideline level. Analytical results also confirm that historical monuments in urban areas act as passive repositories for air pollutants present in the surrounding atmosphere. FTIR and EDX analyses showed that gypsum was the most important constituent of black crusts of the characterized historical monument Monastery of Serra do Pilar classified as “UNESCO World Cultural Heritage”. In black crusts, 4-6 rings compounds accounted approximately for 85% of ΣPAHs. The diagnostic ratios confirmed that traffic emissions were the major source of PAHs in black crusts; PAH composition profiles were very similar for crusts and PM10 and PM2.5. 相似文献
838.
Queiroz LH Lacerda V dos Santos RB Greco SJ Cunha Neto A de Castro EV 《Magnetic resonance in chemistry : MRC》2011,49(3):140-146
This work aims at using theoretical calculations of shielding tensors (σ) through different methods [gauge-independent atomic orbital (GIAO), continuous set of gauge transformations (CSGT) and individual gauges for atoms in molecules (IGAIM)] and spin-spin coupling constants J using GIAO method to compare these methods and to corroborate the data obtained with the assignment of all of (1)H and (13)C NMR signals and the relative stereochemistry of the 1,6-epoxycarvone and the α-epoxypinene. All the (1)H and (13)C NMR signals were assigned unequivocally. The stereochemistry for the epoxides is trans and the B3LYP theory level with CSGT and IGAIM methods is the best choice to evaluate theoretical chemical shifts for compounds studied. 相似文献
839.
Wang S Itoh T Fujimori T Monteiro de Castro M Silvestre-Albero A Rodríguez-Reinoso F Ohba T Kanoh H Endo M Kaneko K 《Langmuir : the ACS journal of surfaces and colloids》2012,28(19):7564-7571
Transitional metals (M) were dispersed on single-wall carbon nanohorns (M/SWCNHs, M = Fe, Co, Ni, Cu) by simple thermal treatment of the deposited metal nitrate without H(2) reduction. Nanometallic Ni particles on SWCNH were evidenced by high-resolution transmission electron microscopic observation and X-ray photoelectron spectroscopy. The nano-Ni dispersed on SWCNH showed the highest CH(4) decomposition activity; the activity of used transitional metals decreases in the order Ni ? Co > Fe ? Cu. On the other hand, the reaction rate over Ni/SWCNH was much larger than that over Ni/Al(2)O(3), and the former provided CO(x)-free H(2) and cup-stacked carbon nanotubes, while Ni/Al(2)O(3) produced CO(x) in addition to H(2). SWCNH was superior to Al(2)O(3) as the catalyst support of Ni for the CH(4) decomposition reaction. 相似文献
840.
Castro JL Lopez-Ramirez MR Arenas JF Soto J Otero JC 《Langmuir : the ACS journal of surfaces and colloids》2012,28(24):8926-8932
The surface-enhanced raman scattering (SERS) of benzoic acid/benzamide and salicylic acid/salicylamide on silver colloids show important wavenumber shifts with respect to the Raman spectrum of the band assigned to mode 1;ν(ring) when adsorbed on the metal surface (ca. +50 cm(-1)). In the case of the acids, this shift is originated by the deprotonation of the carboxylic group in agreement with the well-known fact that aromatic acids are adsorbed on silver as carboxylates. However, the main conclusion of this work is that a similar behavior is found for the respective amides that do not behave as acids in water solution. The here studied aromatic amides are adsorbed as azanions on silver nanoparticles even at pH 7 and link to the metal through the nitrogen and oxygen atoms of the ionized carboxamide group. This is a very surprising result given that amides are not significantly ionized even at pH 13-14. The deprotonation of these amides is not determined exclusively by the pH, but it is mainly caused by the strong affinity of the anionic species to the metal. Therefore, the SERS must be cautiously used as a universal pH sensor if the adsorption occurs through the ionizable group. In order to support this conclusion, theoretical DFT force field calculations have been carried out, confirming that deprotonated benzamide and salicylamide interact with the metallic surface. 相似文献