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61.
62.
The coupled-column (LC-LC) system, consisting of a first column packed with internal surface reversed phase (ISRP) (50 x 4.6mm ID) and a Chrompack C18 (100 x 4.6 mm ID) as second column, allowed the simultaneous determination of five benzoylurea insecticides in dichloromethane (CH2Cl2) extracts of vegetable samples without any clean-up step. This system was combined with a photochemically induced fluorescence (PIF) post-column derivatization in order to provide strongly fluorescent photoproducts from the non-fluorescent benzoylureas. Limits of detection ranged from 0.21 to 0.98 microg L(-1) of pesticide (equivalent to 0.14-0.65 microg kg(-1) in vegetable samples) and limits of determination ranged from 4.0 to 10.0 microg L(-1) (equivalent to 2.7-6.7 microg kg(-1)). Linearity of the method was established between 2 and 1800 microg L(-1), depending upon the compound. Validation of the total method was performed by randomly analyzing recoveries of four vegetable samples (aubergine, cucumber, green bean, and tomato) spiked at two levels of concentration (10.0 and 33.3 microg kg(-1)). The combination of the LC-LC system with PIF detection provides a sensitive, selective, and rapid method for the determination of pesticides in vegetable samples at levels lower than the maximum residue levels (MRLs) established for these compounds by Spanish legislation. 相似文献
63.
The synthesis of new hybrid ferrocene and pi-extended tetrathiafulvalene (TTF) donor(1)-pi-donor(2) molecular assemblies 16a-c has been carried out by a Wittig-Horner reaction of the respective phosphonate esters 15a-c with 2-(2-ferrocenylvinyl)-9, 10-anthraquinone (18) prepared by olefination of ferrocenecarboxaldehyde (14) and the anthraquinone phosphonium salt 17. Electrochemical studies show that the D(1)-pi-D(2) (D = donor) molecular assemblies 16a-c essentially retain the redox characteristics of both ferrocene and the pi-extended TTF components and the effects of solvent, temperature, scan rate, and working electrode are significant. Most importantly, pronounced intramolecular electronic interactions between the two donor moieties were observed by cyclic voltammetry and Osteryoung square wave voltammetry in both the ground and charged states. Semiempirical calculations support the electrochemical observations. 相似文献
64.
Sono-induced cold vapor generation (SI-CVG) has been used for the first time in combination with a graphite furnace atomizer for determination of Hg in natural waters by electrothermal-atomic absorption spectrometry after in situ trapping onto a noble metal-pretreated platform (Pd, Pt or Rh) inserted into a graphite tube. The system allows ‘in-atomizer trapping’ of Hg without the use of conventional reduction reactions based on sodium borohydride or tin chloride in acid medium for cold vapor generation. The sono-induced reaction is accomplished by applying ultrasound irradiation to the sample solution containing Hg(II) in the presence of an organic compound such as formic acid. As this organic acid is partly degraded upon ultrasound irradiation to yield CO, CO2, H2 and H2O, the amount of lab wastes is minimized and a green methodology is achieved. 相似文献
65.
Coleman RS Perez RJ Burk CH Navarro A 《Journal of the American Chemical Society》2002,124(44):13008-13017
Evaluation of the sequence selectivity, noncovalent association, and orientation of the DNA cross-linking agent azinomycin B on its duplex DNA receptor is described. A strong correlation between sequence nucleophilicity and cross-linking yield was observed, and steric effects due to the thymine C5-methyl group were identified. Detailed studies on the role of the azinomycin naphthoate using viscometry, fluorescence contact energy transfer, and DNA unwinding assays point to a nonintercalative binding mode for this group. A kinetic assay for agent regioselectivity was used to determine the orientation of binding and covalent cross-link formation. 相似文献
66.
Acetonitrile and [D3]acetonitrile in the vicinal region of a planar AgX fiber contain linear dipole–dipole linked oligomers as shown by 1) comparison of infrared band intensity ratios in the gaseous and condensed phases and 2) remarkable plots of absorbance (C? N stretch) versus time during evaporation from an AgX planar fiber element. The plots (CH3CN 2252 cm?1, CD3CN 2262 cm?1) reveal the presence of octamers, hexamers, tetramers, and dimers along with some heptamer, trimer, and monomer structures. A novel isotope effect arises from the somewhat smaller size of the CD3CN resulting in an increase in the CN band intensity. The organized oligomers may be termed pseudocrystals and are the main components responsible for absorption intensity in the infrared spectrum of acetonitrile, on the AgX planar fiber or in an IR cell. 相似文献
67.
Liu JA Petzold CJ Ramirez-Arizmendi LE Perez J Kenttämaa H 《Journal of the American Chemical Society》2005,127(37):12758-12759
Laser-induced acoustic desorption combined with mass spectrometry has been used to demonstrate that phenyl radicals can attack dinucleoside phosphates at both the sugar and base moieties, that purine bases are more susceptible to the attack than pyrimidine bases, and that the more electrophilic the radical, the more efficient the damage to dinucleoside phosphates. 相似文献
68.
The Through Oven Transfer Adsorption Desorption (TOTAD) interface is used to directly introduce large volumes of water (1 mL or more) into a capillary gas chromatograph. The TOTAD interface is a greatly modified programmed temperature vaporizer injector incorporating changes that affect the pneumatics, sample introduction, solvent elimination, and operation mode. The system can easily be automated. The technique is applied to the analysis of pesticide residue in standard solutions and real water samples from the Ebro River (northeastern Spain). The speed of sample introduction was 1 mL/min, and the solvent elimination was almost complete. A nitrogen phosphorous detector is used, and the relative standard deviation varied from 5.7% to 11.7% for the absolute peak areas. The sensitivity achieved by introducing 1 mL of the sample is sufficient for most pesticide-residue analyses in water. The limits of detection ranged from 0.5 to 8.1 ng/L. 相似文献
69.
Vass S Grimm H Bányai I Meier G Gilányi T 《The journal of physical chemistry. B》2005,109(24):11870-11874
Slowly diffusing water molecules were found by quasi-elastic neutron scattering (QENS) in a sodium dodecyl sulfate (SDS) micellar solution, and both their diffusion coefficient (4.33 x 10(-6) cm2 x s(-1)) and mole fraction (0.057) were determined. After successfully checking the mean slowing down of solvent molecules by the gradient compensated stimulated spin-echo (GCSTE) pulse sequence NMR method, a similar effect was observed with this technique in the solvent phase of dodecyl trimethylammonium bromide (DTAB) and differing chain length (X = 12, 20, 30, and 40) ethoxylated nonyl phenol (9NX) micellar systems. Following the literature, the experimental results are qualitatively explained by assuming that, apart from ionic hydration, H-bonds may form between the solvent molecules and the O or N atoms present in the hydrophilic (head)groups of the micelle-forming monomers. 相似文献
70.
Varga I Mészáros R Szakács Z Gilányi T 《Langmuir : the ACS journal of surfaces and colloids》2005,21(14):6154-6156
A simple one-step synthesis is described for the functionalization of poly(vinyl chloride) used for the preparation of anionic surfactant-selective membrane electrodes. The method is based on the nucleophilic substitution of a fraction of the chlorine atoms bound to the poly(vinyl chloride) backbone by trimethylamine. The prepared slightly charged polymer gave rise to high-quality surfactant-selective electrode membranes, which had a Nernstian response, short response time, and appropriate stability. 相似文献