L’avènement des nanotechnologies engendre une exposition accrue de l’homme aux nanomatériaux, représentant un risque d’un genre nouveau. A cet égard un grand nombre de recherches porte sur l’étude de leur toxicité. Néanmoins, les questions de dégradation et transformation des nanoparticules dans l’organisme sont encore peu abordées. Des études effectuées au laboratoire ont montré qu’après injection de nanoparticules d’oxyde de fer in vivo, celles-ci sont confinées dans les lysosomes où elles sont dégradées. Une partie de mes travaux de thèse se sont concentrés sur une voie possible de métabolisation des produits de dégradation issus de nanoparticules d’oxydes de fer par l’intermédiaire d’une protéine intervenant dans le métabolisme du fer, la ferritine. Nous avons élaboré plusieurs stratégies afin de détecter et de suivre le transfert de métaux vers la ferritine. Ces travaux ont permis de mettre en évidence un processus de prise en charge des produits de dégradation des nanoparticules d’oxyde de fer à l’échelle moléculaire. Une seconde partie de mes travaux ont été consacré au suivi des produits issus de la dégradation des nanoparticules d’oxyde de fer à l’échelle de l’organisme. La haute concentration endogène en fer rendant impossible ce suivi, une stratégie consistant à marquer les nanoparticules de fer avec un isotope du fer, le 57Fe, a permis de suivre les dynamiques de circulation des produits de dégradation in vivo sur une période de six mois. Nous avons également effectué un double marquage des nanoparticules, du cœur inorganique ainsi que de leur enrobage afin de caractériser leur intégrité in vivo / With the advent of nanotechnology, the exposure of humans to nanomaterials increased, representing a risk of a new kind. Although the potential toxicity of such nanomaterials is extensively studied, their long term fate, biotransformation and degradation in the organism are still poorly understood. It was demonstrated earlier in the laboratory, that after intravenous injection, iron oxide nanoparticles undergo local intracellular degradation within lysosomes. In this context, we are interested in the fate of by products from iron oxide nanoparticles. Part of my thesis has focused on a possible pathway for metabolizing these degradation products through a protein involved in iron metabolism, the ferritin. We first studied, in solution, the degradation processes of iron oxide nanoparticles in the presence of these proteins as well as the iron transfer processes from nanoparticles to ferritin. The difficulty is the high concentration of endogenous iron which makes impossible to demonstrate these in vivo transfers. Thus, we have developed a strategy, using doped iron oxide nanoparticles with a scarce element in the organism, to track these phenomena in vivo. This work highlighted a possible mechanism of biological recycling, remediation and detoxification of nanoparticles mediated by endogenous proteins at the molecular scale. A second part of my work was devoted to develop a multi-scale method to study the life cycle of metal oxide nanoparticles and their by products in organism. The main challenge is to differentiate iron stemming from the nanoparticles from the endogenous iron. This specific tracking problem is routinely encountered in geochemical studies and solved by labelling the target material with minor stable isotopes. Therefore, iron oxide nanoparticles enriched in the minor stable isotope 57Fe were synthetized and injected intravenously in mice to follow dynamic circulations of iron oxide nanoparticles and their byproducts. We have also labelled the coating to track the nanoparticles integrity in mice over a period of six month

El objetivo general de esta investigación es analizar la importancia de la iconoplástica y del diseño de información para generar una mejor percepción al diseño del etiquetado frontal en los productos industrializados. Por este motivo, la hipótesis planteada para esta investigación es la propuesta de intervención del estudio iconoplástico y el diseño de información en el sistema de etiquetado frontal generan una mejor percepción en los jóvenes adultos. Esta investigación es cualitativa porque se realizaron encuestas a 50 consumidores para conocer sus molestias visuales sobre el etiquetado frontal. Además, se entrevistó a abogados e ingenieros agroindustriales para saber si el etiquetado frontal de advertencias puede ser modificado. Por último, se entrevistó a diseñadores para corroborar los errores técnicos que presenta este sistema de etiquetado en cuanto a diseño gráfico. Para esta investigación la solución consiste en la modificación del etiquetado frontal de productos industrializados. Para ello, se utiliza una retícula para ordenar la información de manera profesional, se cambió la forma de octágono porque da más espacio a la composición. Como resultados se obtuvo que los consumidores consideran una buena propuesta ya que los símbolos se organizan de mejor manera dentro de un espacio reducido. Las conclusiones de este proyecto es que el estudio iconoplástico y el diseño de la información ayudan a resolver la gráfica del etiquetado frontal puesto que la información se organiza mejor. Además, este proyecto fue testeado por un público piloto y se concluyó que generaría impacto en cualquier grupo porque la está mejor organizada. / The main objective for this research is to analyze the importance of iconoplastic and design information to create a better perception on front-of-pack labelling of industrialized products. For this reason, the hypothesis is that the intervention approach of the iconoplastic study and design information on front-of-pack labelling creates a better perception in young adults. This research is qualitative because surveys were made to 50 consumers that confirms their visual disturbance about the front-of-pack labelling design. Also, lawyers and Agro-industrial engineers were interviewed to prove that this labelling could be modified in the future. Finally, designers were also interviewed to corroborate some graphic design technical issues. The research’s solution consists on modifying the front-of-pack labelling of industrialized products. For this, a grid was used for organizing all the information to create uniformity between the symbols, the form was changed from octagon to hexagon, the typography was changed to Franklin Gothic Condensed because it leaves more blank space for the composition. As a result, it was obtained that consumers consider this is a good solution because the symbols are organized in a better way. The conclusions that were found at the end of this project are that the iconoplastic study and the design information help to resolve graphic problems that preset the front-of-pack labelling because the information is organized on grids. Also, this project was only tested on a small group of people, but they consider this solution could generate impact in any public because the information is better organized. / Trabajo de investigación

<p>Our common future involves many important challenges. People and nature need to improve the relationship in order to reach an ecologically sustainable development. In a society where consumption of products steadily increases, the consumer awareness about social and environmental issues connected to the products becomes an importent factor. More and more companies choose to work more actively with these issues and more and more products get labelled by some of the eco labelling organisations. From the cradle to the gate means that a study has been done on a part of a products life cycle. In this master thesis a pair of cotton trousers has been followed from the cotton field and through the manufacturing chain in order to sees how much resource that are connected to the cultivation and to the production. Methological approach has been Life Cycle Inventory (LCI) according to ISO 14040. The empirical material is collected in South India, in an area known for its intense cotton manufacturing. </p><p>Studies like this can be a good way of showing the environmental impacts of a certain product. LCI can for example work as a criterion for eco labelling, but the methodology could also support the overall environmental work in companies.</p>

<p>Methods for the ¹¹C-labeling of carbonyl compounds applicable in the preparation of radiotracers for Positron Emission Tomography (PET) are described. To this end [¹¹C]carbon monoxide at low concentration was used in transition metal- mediated reactions.</p><p>Stille couplings were employed in the synthesis of [<i>carbonyl-</i>¹¹C]ketones from methyl and aryl halides with [¹¹C]carbon monoxide. The synthesized [<i>carbonyl-</i>¹¹C]ketones were obtained from the corresponding organostannanes with analytical radiochemical yields up to 98%.</p><p>A number of synthetic routes were designed using [¹¹C]carbon monoxide and rhodium complexes. Nitrene intermediates were generated from azides and reacted via a rhodium-mediated carbonylation reaction as a general synthetic route to [<i>carbonyl-</i>¹¹C]isocyanates, versatile precursors. [<i>carbonyl-</i>¹¹C]Isocyanate reacted via nucleophilic attack of an amine to form <i>N,N’</i>-diphenyl[¹¹C]urea in 82% analytical radiochemical yield, ethyl phenyl[¹¹C]carbamate was synthesized by the same route, using ethanol as the nucleophile, in 70% radiochemical yield. [¹¹C]Isocyanate was also able to react in a [2+3] cycloaddition with ethylene oxide to form 3-phenyl[<i>carbonyl-</i>¹¹C]oxazolidin-2-one in over 80% analytical radiochemical yield. This method was applied to the synthesis of a potential efflux system tracer [¹¹C]hydroxyurea in 38% isolated radiochemical yield and the derivative 1-hydroxy-3-phenyl[¹¹C]urea in 35% isolated radiochemical yield. Carbene intermediates, generated from diazo compounds, were reacted with [¹¹C]carbon monoxide in the rhodium-mediated synthesis of [<i>carbonyl-</i>¹¹C]ketenes. [<i>carbonyl-</i>¹¹C]Ketene intermediates were utilised in the synthesis of diethyl[<i>carbonyl</i>-¹¹C]malonate, from ethyl diazoacetate and ethanol. The product was obtained with a 20% isolated radiochemical yield. Alkylation of diethyl[<i>carbonyl</i>-¹¹C]malonate, with ethyliodide and tetrabutylammonium fluoride, was successfully accomplished and diethyl diethyl[<i>carbonyl</i>-¹¹C]malonate was synthesized in 50% analytical radiochemical yield. Several (<i>carbonyl-</i>¹³C)compounds were also synthesized using the described methods as a way of characterizing the position of the label using ¹³C-NMR.</p>

<p>Compounds labelled with ¹¹C (<i>β</i>⁺, t_1/2 = 20.4 min) are used in positron emission tomography (PET), which is a quantitative non-invasive molecular imaging technique. It utilizes computerized reconstruction methods to produce time-resolved images of the radioactivity distribution in living subjects. </p><p>The feasibility of preparing [¹¹C]methyl iodide from [¹¹C]methane and iodine via a single pass through a non-thermal plasma reactor was explored. [¹¹C]Methyl iodide with a specific radioactivity of 412 ± 32 GBq/µmol was obtained in 13 ± 3% decay-corrected radiochemical yield within 6 min via catalytic hydrogenation of [¹¹C]carbon dioxide (24 GBq) and subsequent iodination, induced by electron impact. </p><p>Labelled ethyl-, propyl- and butyl iodide was synthesized, within 15 min, via palladium-mediated carbonylation using [¹¹C]carbon monoxide. The carbonylation products, labelled carboxylic acids, esters and aldehydes, were reduced to their corresponding alcohols and converted to alkyl iodides. [1-¹¹C]Ethyl iodide was obtained via palladium-mediated carbonylation of methyl iodide with a decay-corrected radiochemical yield of 55 ± 5%. [1-¹¹C]Propyl iodide and [1-¹¹C]butyl iodide were synthesized via the hydroformylation of ethene and propene with decay-corrected radiochemical yields of 58 ± 4% and 34 ± 2%, respectively. [1-¹¹C]Ethyl iodide was obtained with a specific radioactivity of 84 GBq/mmol from 10 GBq of [¹¹C]carbon monoxide. [1-¹¹C]Propyl iodide was synthesized with a specific radioactivity of 270 GBq/mmol from 12 GBq and [1-¹¹C]butyl iodide with 146 GBq/mmol from 8 GBq. </p><p>Palladium-mediated hydroxycarbonylation of acetylene was used in the synthesis of [1-¹¹C]acrylic acid. The labelled carboxylic acid was converted to its acid chloride and subsequently treated with amine to yield <i>N-</i>[<i>carbonyl</i>-¹¹C]benzylacrylamide. In an alternative method, [<i>carbonyl</i>-¹¹C]acrylamides were synthesized in decay-corrected radiochemical yields up to 81% via palladium-mediated carbonylative cross-coupling of vinyl halides and amines. Starting from 10 ± 0.5 GBq of [¹¹C]carbon monoxide, <i>N-</i>[<i>carbonyl</i>-¹¹C]benzylacrylamide was obtained in 4 min with a specific radioactivity of 330 ± 4 GBq/µmol. </p>

Methods for the 11C-labeling of carbonyl compounds applicable in the preparation of radiotracers for Positron Emission Tomography (PET) are described. To this end [11C]carbon monoxide at low concentration was used in transition metal- mediated reactions. Stille couplings were employed in the synthesis of [carbonyl-11C]ketones from methyl and aryl halides with [11C]carbon monoxide. The synthesized [carbonyl-11C]ketones were obtained from the corresponding organostannanes with analytical radiochemical yields up to 98%. A number of synthetic routes were designed using [11C]carbon monoxide and rhodium complexes. Nitrene intermediates were generated from azides and reacted via a rhodium-mediated carbonylation reaction as a general synthetic route to [carbonyl-11C]isocyanates, versatile precursors. [carbonyl-11C]Isocyanate reacted via nucleophilic attack of an amine to form N,N’-diphenyl[11C]urea in 82% analytical radiochemical yield, ethyl phenyl[11C]carbamate was synthesized by the same route, using ethanol as the nucleophile, in 70% radiochemical yield. [11C]Isocyanate was also able to react in a [2+3] cycloaddition with ethylene oxide to form 3-phenyl[carbonyl-11C]oxazolidin-2-one in over 80% analytical radiochemical yield. This method was applied to the synthesis of a potential efflux system tracer [11C]hydroxyurea in 38% isolated radiochemical yield and the derivative 1-hydroxy-3-phenyl[11C]urea in 35% isolated radiochemical yield. Carbene intermediates, generated from diazo compounds, were reacted with [11C]carbon monoxide in the rhodium-mediated synthesis of [carbonyl-11C]ketenes. [carbonyl-11C]Ketene intermediates were utilised in the synthesis of diethyl[carbonyl-11C]malonate, from ethyl diazoacetate and ethanol. The product was obtained with a 20% isolated radiochemical yield. Alkylation of diethyl[carbonyl-11C]malonate, with ethyliodide and tetrabutylammonium fluoride, was successfully accomplished and diethyl diethyl[carbonyl-11C]malonate was synthesized in 50% analytical radiochemical yield. Several (carbonyl-13C)compounds were also synthesized using the described methods as a way of characterizing the position of the label using 13C-NMR.

Compounds labelled with 11C (β+, t1/2 = 20.4 min) are used in positron emission tomography (PET), which is a quantitative non-invasive molecular imaging technique. It utilizes computerized reconstruction methods to produce time-resolved images of the radioactivity distribution in living subjects. The feasibility of preparing [11C]methyl iodide from [11C]methane and iodine via a single pass through a non-thermal plasma reactor was explored. [11C]Methyl iodide with a specific radioactivity of 412 ± 32 GBq/µmol was obtained in 13 ± 3% decay-corrected radiochemical yield within 6 min via catalytic hydrogenation of [11C]carbon dioxide (24 GBq) and subsequent iodination, induced by electron impact. Labelled ethyl-, propyl- and butyl iodide was synthesized, within 15 min, via palladium-mediated carbonylation using [11C]carbon monoxide. The carbonylation products, labelled carboxylic acids, esters and aldehydes, were reduced to their corresponding alcohols and converted to alkyl iodides. [1-11C]Ethyl iodide was obtained via palladium-mediated carbonylation of methyl iodide with a decay-corrected radiochemical yield of 55 ± 5%. [1-11C]Propyl iodide and [1-11C]butyl iodide were synthesized via the hydroformylation of ethene and propene with decay-corrected radiochemical yields of 58 ± 4% and 34 ± 2%, respectively. [1-11C]Ethyl iodide was obtained with a specific radioactivity of 84 GBq/mmol from 10 GBq of [11C]carbon monoxide. [1-11C]Propyl iodide was synthesized with a specific radioactivity of 270 GBq/mmol from 12 GBq and [1-11C]butyl iodide with 146 GBq/mmol from 8 GBq. Palladium-mediated hydroxycarbonylation of acetylene was used in the synthesis of [1-11C]acrylic acid. The labelled carboxylic acid was converted to its acid chloride and subsequently treated with amine to yield N-[carbonyl-11C]benzylacrylamide. In an alternative method, [carbonyl-11C]acrylamides were synthesized in decay-corrected radiochemical yields up to 81% via palladium-mediated carbonylative cross-coupling of vinyl halides and amines. Starting from 10 ± 0.5 GBq of [11C]carbon monoxide, N-[carbonyl-11C]benzylacrylamide was obtained in 4 min with a specific radioactivity of 330 ± 4 GBq/µmol.

The thesis describes the application of the relaxation labelling algorithm to NLP disambiguation. Language is modelled through context constraint inspired on Constraint Grammars. The constraints enable the use of a real value statind "compatibility". The technique is applied to POS tagging, Shallow Parsing and Word Sense Disambigation. Experiments and results are reported. The proposed approach enables the use of multi-feature constraint models, the simultaneous resolution of several NL disambiguation tasks, and the collaboration of linguistic and statistical models. / La tesi descriu l'aplicació de l'algorisme d'etiquetat per relaxacio (relaxation labelling) a la desambiguació del llenguatge natural. La llengua es modela mitjançant restriccions de context inspirades en les Constraint Grammars. Les restriccions permeten l'ús d'un valor real que n'expressa la "compatibilitat". La tècnica s'aplica a la desambiguació morfosintàctica (POS tagging), a l'anàlisi sintàctica superficial (Shallow Parsing) i a la desambiguació semàntica (Word Sense Disambigation), i se'n presenten experiments i resultats. L'enfoc proposat permet la utilització de models de restriccions amb trets múltiples, la resolució simultània de diverses tasques de desambiguació del llenguatge natural, i la col·laboració de models linguístics i estadístics.

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