No abstract

Supercritical extracts of marigold (ME) were produced and characterized. The bioaccessibility of terpenes, especially that of pentacyclic triterpenes (PT), the particle-size distribution, and antioxidant activity after the in vitro codigestion of ME with olive oil (OO) were determined. ME produced without cosolvent was richer in taraxasterol, lupeol, α-amyrin, and β-amyrin than extracts with cosolvent. All terpenes showed high bioaccessibility without OO (>75%). Significant correlations were found between the molecular properties of compounds (logP and number of rotatable bonds) and their bioaccessibility. Codigestion with OO enhanced the bioaccessibility (around 100% for PT), which could be related to a higher abundance of low-size particles of the digestion medium. The antioxidant activity of the digested ME increased around 50%, regardless of OO. PT-rich extracts from marigold display high bioaccessibility and improved antioxidant activity after in vitro digestion, although complete bioaccessibility of PT can be reached by codigestion with oil, without affecting antioxidant activity.

Nowadays, the subject of the quality assurance of the analytical results is acquiring more and more importance. This work presents a basic theoretical and empirical approximation to the expanded uncertainty associated to the TXRF measurements. Two theoretical models has been proposed and compared systematically with the empirical expanded uncertainty obtained. The main consequences derived of this work are the following; theoretical model B explains with a high degree of agreement the empirical expanded uncertainties associated to the TXRF measurements, while theoretical model A explains partially the instrumental repeatability of the TXRF system. On the other hand, an unexpected U-behavior has been found for the empirical uncertainty in TXRF measurements whose explanation can be due to the sum of several sources of uncertainty not considered like variations of the Compton background or the nonlinearity of the Si(Li) detector quantum efficiency. Additionally, it has been shown that the roughness and small geometrical variations of the sample depositions are the more important uncertainty sources in the experimental TXRF measurements.

The methodology developed for evaluating, by total reflection X-ray fluorescence, the main elements in used three-way catalysts for cars after more than 59 000 km is described. The analytical method does not require chemical manipulation of the samples, is quick (30 min for sample preparation and 10 min for analysis), precise (between 1% and 10% of variation coefficient), and simple. The two catalytic monoliths contained in the cartridge of a car with more than 59,000 km have been analyzed. The mass relationships between the detected elements and Si, a component of the cordierite ceramic substrate, have been used to follow the axial and radial profiles of the elements. Information concerning the loss of active elements and the retention of contaminating elements as a consequence of the working conditions was attained by comparison between the results obtained for the used catalyst (59 000 km) with those of a fresh catalyst (0 km). The interface effect between the first and the second catalytic bricks was also studied.