Estimation of comprehensive two-dimensional gas chromatographic response from one-dimensional gas chromatography data

Trabajo presentado a la XV Reunión Científica de la Sociedad Española de Cromatografía y Técnicas Afines (SECyTA) celebrada en Castellón de la Plana del 28 al 30 de octubre de 2015Optimization of a separation in comprehensive two-dimensional gas chromatography (GC×GC) requires the selection of an appropriate set column, and the optimisation of their respective dimensions, temperature programs and flow rates. Until not so long ago, a time consuming trial and error process was the only way to select the columns and chromatographic conditions for the two GC dimensions. During the last few years, several attempts have been proposed to estimate the chromatographic response in GC×GC [1-4]. Although most of these methods are helpful contributions, some of them focussed exclusively on the retention time estimation and do not consider the effect of peak width, also essential for a correct prediction of the chromatographic separation capability. Others are based on theoretical formulas not applicable to the extreme experimental conditions used in GC×GC, or are only valid for specific types of compounds or stationary phases: these models cannot be corrected for different separation problems. In this work, modelization of retention time and peak width has been carried out from experimental 1D GC data in order to estimate the response in GC×GC separation for different column sets operated under different flows and temperatures. Several theoretical and experimental models are proposed for estimation of 1D and 2D retention time and peak width; in experimental models, 1D GC data are required together with information on column characteristics and operation conditions. Models for hold-up time, retention factor and peak width were first validated in 1D GC from the fit between experimental and calculated data. Their validation in GC×GC was carried out by using n-alkanes and a mixture of disaccharides as their trimethylsilyl oxime derivatives. Comparison of experimental and estimated data showed good results for retention time in both first and second dimension. Peak widths presented, however, some errors, caused by the no consideration on estimation of the effect of the modulator or the rather unusual chromatographic conditions used. The developed programme is very versatile as it can be used for the calculation of the chromatographic response of compounds with different polarity and volatility, analysed under different pressures and temperature ramps, and with different sets of columns. [1] J.V. Seeley, E.M. Libby, K.A.H. Edwards, S.K. Seeley, J. Chromatogr. A 1216 (2009) 1650. [2] F.L. Dorman, P.D. Schettler, L.A. Vogt, J.W. Cochran, J. Chromatogr. A 1186 (2008) 196. [3] Y. Zhao, J. Zhang, B. Wang, S.H. Kim, A. Fang, B. Bogdanov, Z. Zhou, C. McClain, X. Zhang, J. Chromatogr. A 1218 (2011) 2577. [4] S. Zhu, S. He, D.R. Worton, A.H. Goldstein, J. Chromatogr. A 1233 (2012) 147. Acknowledgements: This work has been funded by Ministerio de Economía y Competitividad (project CTQ2012-32957), Comunidad Autónoma de Madrid (Spain) and European funding from FEDER program (AVANSECAL-CM S2013/ABI-3028) and Fundación Ramón Areces. ACS thanks Ministerio de Economía y Competitividad of Spain for a Ramón y Cajal contract.CTQ2012-32957Peer reviewe

Sample preparation for the determination of carbohydrates in food and beverages

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Changes in the enantiomeric distribution of selected volatile constituents of Mentha pulegium L. powders caused by hot water treatment

The variation, in general, of the composition of the aromatic fraction and, in particular, of the enantiomeric composition of certain chiral volatile compounds of commercial Mentha pulegium L. powders caused by boiling water was evaluated. A comparison between the volatile profile of the studied herbs demonstrated that most M. pulegium L. samples contained high proportions of Mentha piperita L., even when this information was not specified on the label. Likewise, substantial changes in the volatile fraction of the infusions with respect to the composition of the original plant used in their preparation were found. The enantiomeric composition of some chiral compounds of the dried plant material, particularly limonene, was modified by adding hot water, whereas others were kept invariable. The results shown in this work reflect the need for the control of the composition of commercial powders and brews of M. pulegium L. to ensure their correct application

Separation of disaccharides by comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry. Application to honey analysis.

A new method based on comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC-ToF MS) has been developed for the first time for the analysis of complex mixtures of disaccharides previously converted to their trimethylsilyl oximes (TMSO). Among the different experimental parameters considered for optimization, both the column set combination and the dimensions of the second-dimension column were found to be the most significant with regard to the complete resolution of structurally similar disaccharides. Application of the optimized method to honey analysis allowed the separation of most of the honey disaccharides previously described in the literature. Furthermore, 12 other unknown disaccharides have been separated by this method and characterized from their mass spectral data

Gas chromatographic-mass spectrometric characterisation of tri- and tetrasaccharides in honey

A GC-MS method has been used to characterize tri- and tetrasaccharides in honey after their derivatization into trimethylsilyloxime derivatives. Based on retention data and mass spectra, a total of 25 trisaccharides were characterized; 12 being unequivocally identified using standards and two of them detected for the first time in honey. Erlose and panose were the major trisaccharides in the 12 honeys under analysis, their concentrations ranging 30-1214 mg 100 g-1 of honey and 17-863 mg 100 g-1 of honey, respectively. The GC-MS method also allowed the analysis of tetrasaccharides. Besides nystose, another nine tetrasaccharides were characterized; six of them were sucrose derivatives. Tetrasaccharides were present in concentrations lower than 230 mg 100 g-1 of honey