Simultaneous determination of carbohydrates and simmondsins in jojoba seed meal (Simmondsia chinensis) by gas chromatography

Separate methods for the analyses of soluble carbohydrates in different plants and simmondsins in jojoba seed meal are described. A reliable gas chromatographic procedure for the simultaneous quantification of D-pinitol, myo-inositoL sucrose, 5-alpha-D-galactopyranosyl-D-pinitol. 2-alpha-D-galactopyranosyl-D-pinitol, simmondsin, 4-demethylsimmondsin, 5-demethylsimmondsin and 4,5-didemethylsimmondsin as trimethylsilyl derivatives in jojoba seed meal has been developed. The study of different extraction mixtures allowed for the quantitative recovery of the 9 analytes by a mixture of methanol-water (80:20, v/v) in the concentration range between 0.1 and 4%. Comparison of the separation parameters on three different capillary stationary phases with MS detection allowed for the choice of the optimal gas chromatographic conditions for baseline separation of the analytes.     

Determination of polydimethylsiloxane-seawater distribution coefficients for polychlorinated biphenyls and chlorinated pesticides by solid-phase microextraction and gas chromatography-mass spectrometry

Applications of solid-phase microextraction (SPME) in the measurement of very hydrophobic organic compounds (VHOCs) are limited, partly due to the difficulty of calibrating SPME fibers for VHOCs. This study used a static SPME strategy with a large sample volume (1.6 L) and a five-point calibration procedure to determine the distribution coefficients for a large suite of polychlorinated biphenyls (PCBs) and chlorinated pesticides between a polydimethylsiloxane (PDMS) phase (100 microm thickness) coated on a glass fiber and seawater. An extraction time of 12 days was deemed adequate for equilibrium calibration from kinetic experiments. Two groups of randomly selected fibers divided into three batches (up to nine fibers in each batch) were processed separately with two gas chromatography-mass spectrometry (GC-MS) systems. Matrix effects arising from losses of the analytes to glass container walls and stirring bars were corrected. Relative standard deviations within the same batch were generally smaller than those for the entire group. Furthermore, KfVf (Kf and Vf are the distribution coefficient of an analyte between the polymer-coated fiber and aqueous phase and the fiber volume, respectively) values determined with two GC-MS systems were statistically different. These results indicate the calibrated KfVf values were less affected by the random selection of SPME fibers than by other experimental conditions, and therefore average KfVf values may be used for the same type of commercially available SPME fibers. The relative accuracy of our calibration method was similar to that of a previous study [P. Mayer. W.H.J. Vaes, J.L.M. Hermens, Anal. Chem. 72 (2000) 459] employing different coating thickness and calibration procedure. The present study also obtained a bell-shaped relationship between log Kf and log Kow (octanol-water partition coefficient) for PCB congeners with the maximum log Kf corresponding to log Kow approximately 6.5. This bell-shaped relationship was attributed mainly to steric effects arising from the interplay between the PDMS thickness and molecular sizes of the target analytes.