An analytical methodology for the determination of triazines in environmental samples incorporating a molecularly imprinted solid-phase extraction (MISPE) process using a propazine-imprinted polymer was developed. Two different polymers were prepared using acetonitrile or toluene as porogen, and their optimum loading, washing, and elution conditions were established. Although both polymers were able to recognize several chlorotriazines (propazine, atrazine, simazine, desethylatrazine, and desisopropylatrazine), the polymer prepared in toluene showed the best performance and was also capable of recognizing a methylthiotriazine (prometryn). A binding study carried out in this polymer demonstrated that it possesses heterogeneous binding sites with different binding abilities. From this study, it was also concluded that desethylatrazine and desisopropylatrazine displace the other triazines at high concentrations, including the template molecule. The accuracy and selectivity of the MISPE process developed was verified using a certified reference material for drinking water containing atrazine and simazine among other commonly used pesticides. Finally, the MISPE procedure was successfully applied to the cleanup of drinking and groundwater, soil, and corn sample extracts, and the triazines were determined by micellar electrokinetic chromatography.
In this paper, the Langmuir-Freundlich isotherm is used to model the interaction of several triazines (desethylatrazine, desisopropylatrazine, simazine, atrazine, propazine and prometryn) with a propazine-imprinted polymer and to explain the observed cross-reactivity. Different rebinding experiments (each herbicide alone or all together in a mixture) were carried out and the experimental binding isotherms were fitted to the Langmuir-Freundlich isotherm. The fitting coefficients obtained (total number of binding sites, mean binding affinity and heterogeneity index) allowed the description of the kind of binding sites present in the imprinted polymer under study. It was concluded that the recognition mechanism was mainly governed by the molecular size although slight differences in the molecular structure may also play an important role. The obtained results suggest that the use of this new methodology can open new pathways for understanding how molecular recognition in imprinted polymers takes place.
Selenium is an essential element in the human diet. Interestingly, there has been an increased consumption of dietary supplements containing this element in the form of either inorganic or organic compounds. The effect of using selenium as a dietary supplement in yogurt has been evaluated. For this purpose, different concentrations of inorganic Se (ranging from 0.2 to 5000 microg g(-1)) have been added to milk before the fermentation process. Biotransformation of inorganic Se into organic species has been carefully evaluated by ion-exchange, reversed-phase, or size-exclusion chromatography, coupled to inductively coupled plasma mass spectrometry (ICP-MS). Yogurt fermentation in the presence of up to 2 microg g(-1) of Se(IV) produces a complete incorporation of this element into proteins as has been demonstrated applying a dialysis procedure. Analysis by SEC-ICP-MS showed that most of them have a molecular mass in the range of 30-70 kDa. Species determination after enzymatic hydrolysis has allowed the identification of Se-cystine using two different chromatographic systems. The biotransformation process that takes place during yogurt fermentation is very attractive because yogurt can act as a source of selenium supplementation.
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