Chemometric treatment of vanillin fingerprint chromatograms. Effect of different signal alignments on principal component analysis plots.

This study describes the chemometric treatment of vanillin fingerprint chromatograms to distinguish vanillin from different sources. Prior to principal component analysis, which is used to discriminate vanillin from different origins, the fingerprints are aligned. Three alignment algorithms are tested, correlation optimized warping (COW), target peak alignment (TPA) and semi-parametric time warping (STW). The performance of the three algorithms is evaluated and the effect of the different alignments on the PCA score plots is investigated. The alignment obtained with STW differs somewhat from that with COW and TPA. However, equivalent score plots were obtained regarding the different vanillin groups.

Robustness study of a reversed-phase liquid chromatographic method for the analysis of carboxylic acids in industrial reaction mixtures.

The robustness study of the reversed-phase liquid chromatographic method developed for the quantitative analysis of carboxylic acids is a real asset to prepare method transfer because it provides an indication of its reliability during routine use. Indeed, it was possible to predict the consequences of small variations in operating conditions on the responses. The design of experiments approach was applied to model the effects and interactions of a high number of factors varying simultaneously with a limited number of runs. First we identified the factors which potentially affect the chromatographic responses used for carboxylic acids quantitation: detection wavelength (lambda), column temperature (T), acetonitrile ratio in mobile phase (Me), duration of the plateau before the gradient (L) and gradient slope (S). Then we estimated the order of magnitude of realistic variations to assign factor levels. Finally a central composite design was carried out around the nominal conditions defined during method optimization. The statistical treatment of responses (retention factors, and concentrations) showed that the column temperature, the acetonitrile ratio in the mobile phase, the duration of the plateau before the gradient and the gradient slope were the most influent factors. The building of the robust domain from response-surfaces allowed us to give tolerance limits for the factors (216 nm< lambda <222 nm, 49.3 degrees C < T < 51.4 degrees C, 4.90% < Me < 5.18%, v/v, 4.5 min < L < 5.4 min, 9%< S <11%) for which the performances of the method were maintained.

Development and validation of a reversed-phase liquid chromatography method for the quantitative determination of carboxylic acids in industrial reaction mixtures.

Usually analysis of low molecular-mass carboxylic acids was performed by anion-exchange or ion-exclusion chromatographic methods. Reversed-phase liquid chromatography (RPLC) was evaluated in this work as an alternative method for the analysis of low molecular-mass aliphatic mono- and di-carboxylic acids (formic, acetic, propionic, butyric, valeric, caproic, succinic, glutaric and adipic) in aqueous media. The separation of the nine organic acids was optimised in 21 min on a high-density C18 column with an elution gradient made up of HClO4 aqueous solution 10(-3) mol L(-1) and acetonitrile. For the quantitation, external standard and standard addition methods were compared. Both methods gave similar results, so the most convenient method, external standard, was chosen for acids quantitation. Then the method had been validated and applied to the semi-quantitative analysis of formic and acetic acids and to the quantitative analysis of the others compounds in industrial reaction mixtures with concentrations ranging from 20 to 570 ppm.