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61.
Application of matrix solid-phase dispersion to the determination of a new generation of fungicides in fruits and vegetables 总被引:8,自引:0,他引:8
A method based on matrix solid-phase dispersion (MSPD) and gas chromatography to determine eight fungicides in fruits and vegetables is described. Fungicide residues were identified and quantified using nitrogen-phosphorus detection and electron-capture detection connected in parallel and confirmed by mass spectrometric detection. The method required 0.5 g of sample, C18 bonded silica as dispersant sorbent, silica as clean-up sorbent and ethyl acetate as eluting solvent. Recoveries from spiked orange, apple, tomato, artichoke, carrot and courgette samples ranged from 62 to 102% and relative standard deviations were less than 15% in the concentration range 0.05-10 mg kg(-1). Detection and quantitation limits ranged 3-30 microg kg(-1) and 10-100 microg kg(-1), respectively, with linear calibration curves up to 10 mg kg(-1). The analytical characteristics of MSPD compared very favourably with the results of a classical multiresidue method, which uses ethyl acetate and anhydrous sodium sulphate for the extraction. 相似文献
62.
Torres-Lapasió JR García-Alvarez-Coque MC Bosch E Rosés M 《Journal of chromatography. A》2005,1089(1-2):170-186
The problems associated to the modelling and optimisation of the chromatographic resolution of mixtures involving ionisable solutes at varying pH and acetonitrile content are discussed. Several retention models that separate the contributions of solute, column and stationary phase, were used. The retention was predicted with low errors in large pH domains (2-12), which was an essential requirement to face the optimisation of resolution. The selected mixture was particularly problematic under the viewpoint of resolution, owing to the excessively diverse acid-base behaviour of solutes. This variety led to sudden drops in retention at different pH for each solute, yielding numerous peak crossing, which made finding shared regions of high resolution especially difficult. Conventional resolution diagrams for these situations are scarcely informative, since both the overall and the worst elementary resolutions drop to zero if at least two compounds remain overlapped, even when all the others are baseline resolved. A new chromatographic objective function is proposed to address this drawback. This function, called "limiting peak count", is based on the limiting peak purity concept, and measures the success in the resolution focusing on the resolved solutes, in contrast to conventional resolution assessments that attend mainly to the least resolved solutes. Limiting peak count yields the same result as conventional assessments when full resolution is possible, but it is also able to discriminate the maximal resolving power in low-resolution situations. It offers a different perspective to that given by the complementary mobile phases approach, and the computation is far simpler. 相似文献
63.
Peter Bakó László Fenichel László Tôke 《Journal of inclusion phenomena and macrocyclic chemistry》1993,16(1):17-23
The complexing (in CHCl3) and extracting abilities of 18-crown-6 type compounds (1–15) were measured with Li, Na, K and NH4 cations. The substituents on the sugar part affected these properties significantly (K
a=103–107). Some substituents, like acetyloxy groups (3) decreased whereas others, like tosyloxy groups (10, 11) significantly increased the complexing ability and thus changed the selectivity. The compound with four tosyloxy groups (11) shows an excellent picrate salt extracting ability in a CH2Cl2-water system. 相似文献
64.
Summary Nickel(II) xanthates react with amines to form nickel(II) dithiocarbamates and thiourethanes, both products of nucleophilic substitution at the sp2 carbon atom. If the reaction is conducted under carbon monoxide the nickel and sulphur-containing byproduct of thiourethane formation is transformed partly into Ni(CO)4. 相似文献
65.
Diffusion-diffusion correlation and exchange as a signature for local order and dynamics 总被引:1,自引:0,他引:1
We demonstrate the use of new two-dimensional nuclear magnetic resonance experiments in the examination of local diffusional anisotropy under conditions of global isotropy. The methods, known as diffusion-diffusion correlation spectroscopy and diffusion exchange spectroscopy, employ successive pairs of magnetic field gradient pulses, with signal analysis using two-dimensional inverse Laplace transformation. Diffusional anisotropy is measured for water molecules in a polydomain lamellar phase lyotropic liquid crystal, 40 wt % nonionic surfactant C10E3 (C10H21O(CH2CH2O)6H) in H2O. 相似文献
66.
Methods for the on-line chromatographic preconcentration of Cr(III) and Cr(VI) have been developed. Cr(VI) has been preconcentrated on an RP C18 silica based column with tetrabutylammonium-bromide (TBABr) as ion-pairing agent. Specially for Cr(III) a new and effective preconcentration technique based on the sorption of Cr(III)-ions in a C18 column in presence of KH-phthalate has been developed. The efficiency of sample introduction into the atomic emission spectrometer could be improved by hydraulic high pressure nebulization. For the detection of chromium the acetylene/N(2)O flame has been used as a powerful emission spectrometric source. Applying these steps the detection limit (3sigma) could be improved to 25 pg/mL for Cr(III) and to 20 pg/mL for Cr(VI). The method has been applied for the chromium speciation in natural water samples. 相似文献
67.
Wagner-Czauderna Elżbieta Boroń-Cegiełkowska Agata Orłowska Elżbieta Kalinowski Marek K. 《Transition Metal Chemistry》2004,29(1):61-65
The visible absorption spectra of CoCl2 in binary mixtures of acetone, dmf, dma and dmso with H2O show the existence of configuration equilibria between tetrahedral (T) and octahedral (O) species. Linear correlations between the values of log K (K = [O]/[T]) and the mole fraction of H2O,
w, have been observed in all the systems under study; their slopes decrease linearly with an increase of the donor number, DN, of the organic component of the mixture. The formation of octahedral species is enthalpy favoured but entropy disfavoured. It was found that both H and S values change linearly with
w and the slopes of these relationships depend clearly on the DN values. 相似文献
68.
The cationization of poly(ethylene glycol)s, PEG 4000 and PEG 6000, under matrix-assisted laser desorption/ionization conditions was studied by using different concentration ratios of the sodium ion, as the reference ion, and another alkali metal ion (Li(+), K(+), Rb(+), Cs(+)). A linear correlation was found between the intensity ratio of the sodiated PEGs and PEGs cationized with alkali metal ions versus the initial concentration ratio of sodium and alkali metal ions. The slopes of these straight lines are proposed as a novel selectivity ratio for the ionization process. The intensity distribution of the cationized PEGs was also investigated. It was found that the cationized oligomers follow Poisson statistics. The M(n) and M(w) values were also evaluated. An explanation for the observed effects is given. 相似文献
69.
Optical yields obtained in the hydrogenation of acetophenone with cationic and in situ rhodium complex catalysts depend on the P/Rh ratio and on the ionic or non-ionic character of the active species. The enantioselectivity of the in situ catalyst containing (+)-DIOP is reversed by addition of achiral tri-n-alkyl-phosphines. On the basis of these observations and the amount of H2 consumed in preforming the catalysts, several different mechanisms are suggested: for example: cycles involving cationic rhodium complexes containing two (or three) phosphorus ligands and cycles involving non-ionic rhodium complexes with two phosphorus ligands in cis or trans positions. In the in situ catalyst with a Rh/(+)-DIOP/P-n-Bu3 1/1/1 ratio (+)-DIOP functions as a monodentate ligand. 相似文献
70.