Contribution à la connaissance du métabolisme secondaire des Thymelaeaceae et investigation phytochimique de l'une d'elles: "Gnidia involucrata" Steud. ex A. Rich

Dans le but de mieux connaître le métabolisme secondaire de la famille des Thymelaeaceae et de découvrir de nouveaux composés naturels à intérêt thérapeutique, 30 extraits provenant de 8 espèces africaines ont été soumis à un criblage chimique et biologique. Les cibles biologiques suivantes ont servi à l?évaluation de l?activité des extraits étudiés : la moisissure phytopathogène Cladosporium cucumerinum, la levure commensale Candida albicans, la bactérie opportuniste Bacillus subtilis, la larve du moustique vecteur de la fièvre jaune Aedes aegypti et l?hôte intermédiaire mollusque de la schistosomiase urinaire Biomphalaria glabrata. Les propriétés antiradicalaires et inhibitrices de l?acétylcholinestérase de ces extraits ont également été dépistées. Des analyses sur CCM avec révélation chimique, ainsi que des expériences LC/DAD-UV, ont permis demettre en évidence la présence de tanins, de flavonoïdes et de xanthones dans les extraits polaires. Sur la base des résultats de ces analyses préliminaires, l?investigation phytochimique des extraits méthanoliques des racines et des parties aériennes de Gnidia involucrata a été entreprise. Cette démarche a permis l?isolement de 8 composés naturels et leur caractérisation complète au moyen de méthodes spectroscopiques (UV, MS, CD, 1H- et 13C-NMR). Les activités de ces produits purs ont été évaluées et il est apparu qu?ils possédaient presque tous des propriétés antiradicalaires intéressantes, supérieures à celles du BHT, un antioxydant de synthèse (E 321) utilisé dans l?industrie alimentaire. Deux benzophénones simples, respectivement O- et C-glucosylées, ont été isolées des parties aériennes de G. involucrata au côté de la mangiférine, une C-glycosylxanthone ubiquitaire. Ces découvertes sont remarquables à plusieurs titres : (1) les benzophénones simples (nonprénylées) sont très rares dans la nature ; (2) c?est la première fois qu?une Oglycosylbenzophénone a été décrite ; (3) aucune xanthone n?avait été mise en évidence auparavant dans la famille et (4) les benzophénones semblent ne pas être que des produits intermédiaires dans la biosynthèse des xanthones. Trois 3,8??-biflavanones du type GB ont été isolées des racines et des parties aériennes de la même plante, dont deux stéréoisomères se trouvant en mélange. Une analyse LC/CD a permis d?attribuer les configurations absolues des quatre carbones asymétriques de chaque molécule. Cette classe de métabolites secondaires est réputée pour ses propriétés analgésiques et sa présence chez les Thymelaeaceae est prometteuse. Des techniques couplées de pointe ont été utilisées dans ce travail et ont montré leur apport inestimable dans le domaine de la recherche phytochimique. Une analyse LC/ MSn a ainsi permis de mettre en évidence on-line trois C-glycosylflavones ? l?isoorientine, l?isovitexine et la vitexine ? dans les extraits méthanoliques bruts de G. involucrata. De plus, les parties aériennes de cette même plante ont servi de matériel pour le développement d?une nouvelle méthode d?analyse d?extraits bruts : la LC/1H-NMR time-slice. Cette approche consiste à « découper » le temps d?analyse par des interruptions régulières du flux LC, durant lesquelles les données NMR nécessaires sont acquises. Le problème de la faible sensibilité relative de la LC/NMR a été partiellement résolu par ce biais et a permis d?envisager l?utilisation de la NMR au sein de systèmes de couplages multiples en série avec d?autres méthodes spectrales (UV, MS, IR, CD,?).<br/><br/>With the aim of acquiring a better knowledge of the secondary metabolism of the family Thymelaeaceae and of the discovering of new natural therapeutics, 30 extracts from 8 African plant species were submitted to chemical and biological screening. The following biological targets were used to estimate the activity of the extracts under study: the phytopathogenic fungus Cladosporium cucumerinum, the commensal yeast Candida albicans, the opportunistic bacteria Bacillus subtilis, larvae of the yellow fever-transmitting mosquito Aedes aegypti and the intermediate snail host of urinary schistosomiasis Biomphalaria glabrata. The antiradical and acetylcholinesterase-inhibiting properties of these extracts were also investigated. TLC analyses followed by chemical detection, together with LC/DAD-UV experiments, showed the presence of tannins, flavonoids and xanthones in the polar extracts. On the basis of these results, a phytochemical investigation of the methanol extracts of the roots and the aerial parts of Gnidia involucrata was undertaken. This procedure led to the isolation of 8 natural products, which were then characterised by spectroscopic means (UV, MS, CD, 1H- and 13C-NMR). The activities of the pure compounds were then further evaluated: almost all of them exhibited very interesting antiradical properties, superior to those of BHT, a synthetic antioxidant (E 321) used in the food industry. Two simple benzophenones, one O- and one C-glycosylated, were isolated from the aerial parts of G. involucrata, together with mangiferin, a ubiquitous C-glycosylxanthone. These findings are of multiple importance: (1) simple (non-prenylated) benzophenones are very rare in nature; (2) it is the first time that an O-glycosylbenzophenone has been described; (3) no xanthones have been previously reported in the family and (4) benzophenones do not seem to be exclusive intermediates in the biosynthesis of xanthones. Three 3,8??-biflavanones of the GB type were isolated from the roots and the aerial parts of the same plant, among them two stereoisomers in mixture. A LC/CD analysis allowed the assignment of the absolute configurations of all four stereocenters in both molecules. This class of secondary metabolite is well known for its analgesic properties and its presence in the Thymelaeaceae is very promising. Advanced hyphenated techniques were used in this work and showed their inestimable contribution to the field of phytochemical research. A LC/MSn analysis, for example, allowed the on-line characterisation of three C-glycosylflavones ? isoorientin, isovitexin and vitexin ? in the crude methanol extracts of G. involucrata. Furthermore, the aerial parts of this plant were used as material for the development of a new analytical method for crude plant extracts: time-slice LC/1H-NMR. This approach consisted in "slicing" the analytical procedure by interrupting the LC flow at given intervals, during which the necessary NMR data were acquired. The relative lack of sensitivity of LC/NMR was partially surmounted by this means, allowing one to envisage the use of NMR in a multiple hyphenated system, together with other spectroscopic methods (UV, MS, IR, CD,?)

Investigation of interaction between native and impurity defects in ZnSe

Zinc selenide is a prospective material for optoelectronics. The fabrication of ZnSe­based light-emitting diodes is hindered by complexity of p-type doping of the component materials. The interaction between native and impurity defects, the tendency of doping impurity to form associative centres with native defects and the tendency to self-compensation are the main factors impeding effective control of the value and type of conductivity. The thesis is devoted to the study of the processes of interaction between native and impurity defects in zinc selenide. It is established that the Au impurity has the most prominent amphoteric properties in ZnSe among Cu, Ag and Au impurities, as it forms a great number of both Au; donors and Auz„ acceptors. Electrical measurements show that Ag and Au ions introduced into vacant sites of the Zn sublattice form simple single-charged Agz„+ and Auzn+ states with d1° electron configuration, while Cu ions can form both single-charged Cuz„ (d1) and double-charged Cuzr`+ (d`o) centres. Amphoteric properties of Ag and Au transition metals stimulated by time are found for the first time from both electrical and luminescent measurements. A model that explains the changes in electrical and luminescent parameters by displacement of Ag ions into interstitial sites due to lattice deformation forces is proposed. Formation of an Ag;-donor impurity band in ZnSe samples doped with Ag and stored at room temperature is also studied. Thus, the properties of the doped samples are modified due to large lattice relaxation during aging. This fact should be taken into account in optoelectronic applications of doped ZnSe and related compounds.

Investigation of defect formation and electronic transport in microcrystalline silicon deposited by hot-wire CVD

We have investigated doped and undoped layers of microcrystalline silicon prepared by hot-wire chemical vapour deposition optically, electrically and by means of transmission electron microscopy. Besides needle-like crystals grown perpendicular to the substrate's surface, all of the layers contained a noncrystalline phase with a volume fraction between 4% and 25%. A high oxygen content of several per cent in the porous phase was detected by electron energy loss spectrometry. Deep-level transient spectroscopy of the crystals suggests that the concentration of electrically active defects is less than 1% of the undoped background concentration of typically 10^17 cm -3. Frequency-dependent measurements of the conductance and capacitance perpendicular to the substrate surface showed that a hopping process takes place within the noncrystalline phase parallel to the conduction in the crystals. The parasitic contribution to the electrical circuit arising from the porous phase is believed to be an important loss mechanism in the output of a pin-structured photovoltaic solar cell deposited by hot-wire CVD.

Investigation of business models of free zones and possible implications in South East Finland

Tutkielma tarkastelee vapaa alue konseptia osana yritysten kansainvälistä toimitusketjua. Tarkoituksena on löytää keinoja, millä tavoin vapaa alueen houkuttelevuutta voidaan lisätä yritysten näkökulmasta ja millaista liiketoimintaa yritysten on vapaa alueella mahdollista harjoittaa. Tutkielmassa etsitään tekijöitä, jotka vaikuttavat vapaa alueen menestykseen ja jotka voisivat olla sovellettavissa Kaakkois-Suomen ja Venäjän raja-alueelle ottaen huomioon vallitsevat olosuhteet ja lainsäädäntö rajoittavina tekijöinä. Menestystekijöitä ja liiketoimintamalleja haetaan tutkimalla ja analysoimalla lyhyesti muutamia olemassa olevia ja toimivia vapaa alueita. EU tullilain harmonisointi ja kansainvälisen kaupan vapautuminen vähentää vapaa alueen perinteistä merkitystä tullivapaana alueena. Sen sijaan vapaa alueet toimivat yhä enenevissä määrin logistisina keskuksina kansainvälisessä kaupassa ja tarjoavat palveluita, joiden avulla yritykset voivat parantaa logistista kilpailukykyään. Verkostoituminen, satelliitti-ratkaisut ja yhteistoiminta ovat keinoja, millä Kaakkois-Suomen alueen eri logistiikkapalvelujen tarjoajat voivat parantaa suorituskykyään ja joustavuutta kansainvälisessä toimitusketjussa.

Concentrations of resveratrol and derivatives in foods and estimation of dietary intake in a Spanish population: European Prospective Investigation into Cancer and Nutrition (EPIC)-Spain cohort

Resveratrol has been shown to have beneficial effects on diseases related to oxidant and/or inflammatory processes and extends the lifespan of simple organisms including rodents. The objective of the present study was to estimate the dietary intake of resveratrol and piceid (R&P) present in foods, and to identify the principal dietary sources of these compounds in the Spanish adult population. For this purpose, a food composition database (FCDB) of R&P in Spanish foods was compiled. The study included 40 685 subjects aged 35-64 years from northern and southern regions of Spain who were included in the European Prospective Investigation into Cancer and Nutrition (EPIC)-Spain cohort. Usual food intake was assessed by personal interviews using a computerised version of a validated diet history method. An FCDB with 160 items was compiled. The estimated median and mean of R&P intake were 100 and 933 mg/d respectively. Approximately, 32% of the population did not consume RΠ The most abundant of the four stilbenes studied was trans-piceid (53·6 %), followed by trans-resveratrol (20·9 %), cis-piceid (19·3 %) and cis-resveratrol (6·2 %). The most important source of R&P was wines (98·4 %) and grape and grape juices (1·6 %), whereas peanuts, pistachios and berries contributed to less than 0·01 %. For this reason the pattern of intake of R&P was similar to the wine pattern. This is the first time that R&P intake has been estimated in a Mediterranean country.