Analysis of PCB by on-line coupled HPLC-HRGC

Summary On-line coupled HPLC-GC has been used for the fractionation and analysis of polychlorobiphenyls (PCB) according to their planarity. HPLC elution with porous graphitic carbon (PGC) as stationary phase, enables fractionation of PCB into classes according to the amount ofortho-substitution, which is related to congener toxicity. This is a preliminary step before GC analysis, which enables complete separation of PCB congeners according to vapour pressure. Conditions for HPLC-HRGC coupling were optimised, in particular the appropriate proper HPLC solvent was selected, because it determines eluent strength and selectivity and the transfer conditions. Different solvent were studied—n-hexane, dichloromethane, benzene, toluene, and their mixtures. Samples containing PCB standards and the commercial mixtures Aroclor 1242 and 1254 were analysed. Dichloromethane-n-hexane, 1:1, was selected as mobile phase for separation of poly-ortho from mono-ortho PCB; benzene-dichloromethane 30:70 resulted in the best separation of the most retained non-ortho-substituted PCB. Under these conditions the co-solvent trapping procedure, performed by adding 4% ethylbenzene as co-solvent, was used as transfer technique to overcome the drawback of losses of volatile congeners. Appropriate analysis conditions were successfully used to fractionate the technical PCB formulations Aroclor 1242 and 1254.     

Verminderung der Einwaage bei der Schwefelmikrobestimmung nach Schöniger

Zusammenfassung Es wurde die Möglichkeit untersucht, die Probemenge bei der Schwefelmikrobestimmung nachSchöniger, ohne das gewöhnliche Verfahren wesentlich zu modifizieren, durch Anwendung eines geänderten Kolbens zu vermindern.Innerhalb der üblichen Toleranzgrenzen liegende Ergebnisse (Standardabweichung ± 0,13%) wurden mit Einwaagen von 1,5 bis 2 mg erhalten.

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Summary The possibility was investigated of reducing the weight of sample in the micro determination of sulfur by theSchöniger procedure, but without essentially modifying the usual method, namely by using a modified flask. Samples weighing 1.5 to 2 mg gave results within the usual tolerance limits (standard deviation ± 0.13%).

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Résumé On a étudié la possibilité de diminuer la prise d'essai dans le mierodosage du soufre suivantSchöniger, sans altérer d'une manière importante le procédé habituel, en utilisant un ballon modifié. Les résultats qui se situent dans les limites de tolérance habituelles (écart-type=± 0,13%) correspondent à des prises, d'essai de 1,5 à 2 mg.

     

Rm Values, retention times and π values of a series of potentially mutagenic nitroimidazo[2,1-b]thiazoles

The R_m values and retention times of a series of nitroimidazo[2,1-b]thiazoles were obtained by means of thin-layer and high-performance liquid chromatography, respectively. Extrapolated R_m and log k′ values were correlated in a statistically significant way with π values calculated according to the literature.     

GC-MS in space research: decoding complex isothermal chromatograms recovered from space missions

An analytical procedure is described to study GC-MS isothermal chromatograms simulating those recovered from space missions: in fact GC plays a predominant role in space missions devoted to characterizing the chemical composition of extra-terrestrial atmospheres. SIM (selected ion monitoring) detection was used for monitoring selected chemical classes: a simplified chromatogram can be obtained giving information on the chemical composition of the complex mixture. Since only isothermal GC chromatograms are allowed by flight constraints, a time axis transformation is required to make them homogeneous: i.e., constant retention increments for CH2 additions in terms of a homologous series. The order in the linearized chromatogram can be simply singled out with a chemometric approach based on the study of the Autocovariance Function (ACVF) computed on the digitized chromatogram: the plot of the experimental autocorrelation function (EACF) shows well-shaped peaks if constant interdistances are repeated in different regions of the chromatogram. The method was applied to standard mixtures representative of planetary atmospheres--hydrocarbons, nitriles and oxygenated compounds with between 3 and 12 carbon atoms--analyzed in flight simulating conditions. The coupling of the selectivity of SIM detection with the interpretation power of the EACF procedure proves to be a powerful tool for interpreting data recovered from space missions: the chemical composition of the mixture can be identified by handling the raw SIM chromatograms.     

Comparison of the sequential simplex method and linear solvent strength theory in HPLC gradient elution optimization of multicomponent flavonoid mixtures

Summary Using a camomile flavonoid extract as the sample and four different reversed-phase partition systems, the ability of the Simplex procedure to produce optimum gradient separation of unknown multicomponent mixtures was checked against the linear solvent strength (LSS) gradient elution theory. On the same partition systems the mean solvent strenghts were measured by experimentally determined logk vs. mobile phase composition plots. These mean solvent strengths are compared to those inferred from the optimum gradients and the usefulness of LSS theory in multicomponent mixture gradient elution optimization is discussed.Dadicated to Prof. Dr. A Liberti on the occasion of his 70th birthday.     

Sequential potentiometric microdetermination of chloride and phosphate and its application to the determination of phosphorus and chlorine in organic compounds

Orthophosphate has been determined at the micro level in the presence of chloride by argentimetric potentiometric titration. Chloride is titrated first, at pH 3 in water-propan-2-ol (1:1 v/v), and phosphate in the same solution, buffered at pH 8.5-9.0. Under these conditions, the titration error from partial co-precipitation of silver oxide near the equivalence point is minimized. A procedure for performing the titration with an automatic apparatus is described. The method has been applied to the determination of phosphorus and chlorine in the same organic compound after mineralization by the Sch?niger method.     

Latex Fractionation by Sedimentation and Colloidal Crystallization: The Case of Poly(styrene-co-acrylamide)

Poly(styrene-co-acrylamide) (PS-AAM) latex was prepared, fractionated by sedimentation under gravity, and characterized by PCS, infrared spectra, secondary and backscattered electron imaging in the scanning electron microscope, and electron spectroscopy imaging in an analytical transmission electron microscope. Three latex fractions were obtained. The lower fraction was opalescent and its particles were the more uniform, concerning size, chemical composition, and topochemical features. This lower fraction was still further fractionated by zonal centrifugation in a density gradient, yielding two fractions with similar macrocrystal-forming abilities but different sizes and chemical compositions. These results confirm those previously obtained for the PS-HEMA latex. Copyright 2000 Academic Press.