HPLC analysis of plant sterol oxidation products

Increased interest in the cholesterol-lowering effect of plant sterols has led to development of plant sterol-enriched foods. When products are enriched, the safety of the added components must be evaluated. In the case of plant sterols, oxidation is the reaction of main concern. In vitro studies have indicated that cholesterol oxides may have harmful effects. Due their structural similarity, plant sterol oxidation products may have similar health implications. This study concentrated on developing high-performance liquid chromatography (HPLC) methods that enable the investigation of formation of both primary and secondary oxidation products and thus can be used for oxidation mechanism studies of plant sterols. The applicability of the methods for following the oxidation reactions of plant sterols was evaluated by using oxidized stigmasterol and sterol mixture as model samples. An HPLC method with ultraviolet and fluorescence detection (HPLC-UV-FL) was developed. It allowed the specific detection of hydroperoxides with FL detection after post-column reagent addition. The formation of primary and secondary oxidation products and amount of unoxidized sterol could be followed by using UV detection. With the HPLC-UV-FL method, separation between oxides was essential and oxides of only one plant sterol could be quantified in one run. Quantification with UV can lead to inaccuracy of the results since the number of double bonds had effect on the UV absorbance. In the case of liquid chromatography-mass spectrometry (LC-MS), separation of oxides with different functionalities was important because some oxides of the same sterol have similar molecular weight and moreover epimers have similar fragmentation behaviour. On the other hand, coelution of different plant sterol oxides with the same functional group was acceptable since they differ in molecular weights. Results revealed that all studied plant sterols and cholesterol seem to have similar fragmentation behaviour, with only relative ion abundances being slightly different. The major advantage of MS detection coupled with LC separation is the capability to analyse totally or partly coeluting analytes if these have different molecular weights. The HPLC-UV-FL and LC-MS methods were demonstrated to be suitable for studying the photo-oxidation and thermo-oxidation reactions of plant sterols. The HPLC-UV-FL method was able to show different formation rates of hydroperoxides during photo-oxidation. The method also confirmed that plant sterols have similar photo-oxidation behaviour to cholesterol. When thermo-oxidation of plant sterols was investigated by HPLC-UV-FL and LC-MS, the results revealed that the formation and decomposition of individual hydroperoxides and secondary oxidation products could be studied. The methods used revealed that all of the plant sterols had similar thermo-oxidation behaviour when compared with each other, and the predominant reactions and oxidation rates were temperature dependent. Overall, these findings showed that with these LC methods the oxidation mechanisms of plant sterols can be examined in detail, including the formation and degradation of individual hydroperoxides and secondary oxidation products, with less sample pretreatment and without derivatization.

Analisi contrastiva delle modalità di traduzione in finnico dei Tempi verbali e delle perifrasi aspettuali dell'italiano

Analisi contrastiva delle modalità di traduzione in finnico dei Tempi verbali e delle perifrasi aspettuali dell italiano (Italian Philology) The topic of this research is a contrastive study of tenses and aspect in Italian and in Finnish. The study aims to develop a research method for analyzing translations and comparable texts (non-translation) written in a target language. Thus, the analysis is based on empirical data consisting of translations of novels from Italian to Finnish and vice versa. In addition to this, for the section devoted to solutions adopted in Finnish for translating the Italian tenses Perfetto Semplice and Perfetto Composto, 39 Finnish native speakers were asked to answer questions concerning the choice of Perfekti and Imperfekti in Finnish. The responses given by the Finnish informants were compared to the choices made by translators in the target language, and in this way it was possible both to benefit from the motivation provided by native speakers to explain the selection of a tense (Imperfekti/Perfekti) in a specific context compared with the Italian formal equivalents (Perfetto Composto/Perfetto Semplice), and to define the specific features of the Finnish verb tenses. The research aims to develop a qualitative method for the analysis of formal equivalents and translational changes ( shifts ). Although, as the choice of Italian and Finnish progressive forms is optional and related to speaker preferences, besides the qualitative analysis, I also considered it necessary to operate a quantitative one in order to find out whether the two items share the same degree of correspondence in frequency of use. In this study I explain translation choices in light of cognitive grammar, suggesting that particular translation relationships derive from so-called construal operations. I use the concepts of cognitive linguistics not only to analyze the convergences and divergences of the two aspectual systems, but also to redefine some general procedures related to the phenomenon of translation. For the practical analysis of the corpus were for the most part employed theoretical categories developed in a framework proposed by Pier Marco Bertinetto. Following this approach, the notions of aspect (the morphologic or morphosyntactic, subjective level) and actionality (the lexical aspect or objective level, traditionally Aktionsart) are carefully distinguished. This also allowed me to test the applicability of these distinctions to two languages typologically different from each other. The data allowed both the analysis of the semantic and pragmatic features that determine tense and aspect choices in these two languages, and to discover the correspondences between the two language systems and the strategies that translators are forced to resort to in particular situations. The research provides not only a detailed and analytically argued inventory about possible solutions for translating Italian tenses and aspectual devices in Finnish that could be of pedagogical relevance, but also new contributions about the specific uses of time-aspectual devices in the two languages in question.