La valorisation des déchets industriels est de nos jour un défit international ayant des intérêts économiques et environnementaux. Dans ce cadre, l’entreprise Solvay travail sur la gestion de ses déchets et plus particulièrement ceux produits de la fabrication du carbonate de sodium « soude ». Ils sont actuellement stockés dans des bassins de décantation. Cependant, des contraintes règlementaires sont récemment apparues limitant ainsi la construction de nouveaux bassins. La valorisation de ces déchets est par conséquent impérative pour l’entreprise. Plusieurs voies de valorisation sont envisageables, notamment le recours à des nouveaux procédés qui permettraient d’en produire de nouveaux matériaux.En effet, un nouveau matériau issu des déchets industriels appelé « Gel d’Apatite » fait l’objet de ce travail de thèse. L’objectif est de caractériser le Gel d’Apatite et de proposer et d’étudier une voie permettant sa valorisation. Ce matériau est constitué principalement d’hydroxyapatite et de l’eau. Il se distingue par un comportement thixotropique et par sa capacité de rétention des métaux lourds. Cette dernière propriété a permis d’envisager sa valorisation dans la dépollution et la protection des nappes phréatiques. La voie étudiée dans ce travail de recherche est la valorisation du Gel d’Apatite dans les Barrières Perméables Réactives « BPR(s)»; technique passive de traitement des eaux souterraines in-situ.La finalité de ces travaux de recherche serait de dresser un cahier de charge du Gel d’Apatite et de définir un mélange conforme au mode de valorisation étudié / The valorization of industrial wastes is nowadays a worldwide challenge that offers several environmental and social interests. In some fields this valorization allows the preservation of natural resources and the releasing of spaces devoted to the wastes storage. Further, it allows developing of new innovative materials and low-cost products. Consequently industries industries have followed these guidelines. A collaborative investigation has been established with Solvay and Ecole Centrale de Lille in order to work on this topic.A new material: hydroxyapatite gel, is thus developed from non-toxic wastes in an industrial research laboratory. This material is composed by hydroxyapatite and water. It is characterized by its capacity to retain heavy metal by ion exchange. This particular characteristic led to consider its valorization in the water pollution control as the permeable reactive barrier (PRB) in particular. In deed, the permeable reactive barrier is a passive technique of in situ groundwater treatment.The results from this study were useful for a better planning of Permeable Reactive Barriers (PRB). The latter requires a high permeability to ensure groundwater flow and a high retention capacity for heavy metals

Le cisplatine est l’un des trois agents anticancéreux les plus utilisés en chimiothérapie contre les tumeurs solides. Cependant, les doses utilisées sont limitées par des effets secondaires importants et l’existence des résistances innées ou acquises vis-à-vis de cette drogue. Ce travail vise à augmenter l’index thérapeutique du cisplatine (réduire ses effets secondaires et augmenter son activité anti-tumorale). Pour cela des nanoparticules hautement chargées en cisplatine en couche par couche à base de nucléolipides ont été préparées. Les études physico-chimiques (TEM, DLS, XPS, microscopie à fluorescence, ICP-optique) ont révélé que les nanoparticules à double couche étaient plus stables en milieu biologique par rapport aux formulations en mono-couche. Les études biologiques réalisées sur deux lignées tumorales ovariennes (IGROV1 et SKOV3) ont montré que cette formulation améliore l’activité cytotoxique du cisplatine et inhibe le développement des résistances. L’étude du mécanisme d’action (internalisation, apoptose, génotoxicité, réplication de l’ADN) a confirmé que les nanoparticules à double couche augmentent le taux de cisplatine internalisé qui, une fois libéré dans les cellules, arrête la réplication de l’ADN et induit la mort cellulaire par apoptose. Aucune toxicité intrinsèque aux nano-objets n’est observée. Les études in vivo de ces nanoparticules à double couche après injection en intraveineuse de 5, 7 et 9 mg/Kg ont révélé que cette formulation augmente la dose maximale tolérée et présente une activité anti-tumorale vis-à-vis des lignées cellulaires PROb et GV1A1. Cette stratégie d’élaboration des nanoparticules en couche par couche de nucléolipides nous a permis d’insérer des PEG avec ou sans acide folique pour le ciblage et d’introduire une deuxième drogue lipophile, le paclitaxel. Les tests in vitro (cytotoxicité, internalisation) ont montré l’intérêt de ces modifications. / Cisplatin is one of the three most commonly used anticancer drugs in chemotherapy against solid tumors. However, the doses used are limited by significant side effects and the existence of resistance. The aim of this work is to increase the therapeutic index of cisplatin. For this purpose, highly charged nucleolipids nanoparticles “layer-by-layer” of cisplatin were prepared. The physico-chemical studies (TEM, DLS, XPS, ICP, Fluorescence microscopy) revealed that the bilayer nanoparticles were more stable in biological environment compared with mono-layer formulations. Biological studies carried in two ovarian carcinoma cells lines (IGROV1 and SKOV3) showed that this formulation enhances the cytotoxic activity of cisplatin and inhibits the development of resistance. The study of the mechanism of action (internalization, apoptosis, genotoxicity, DNA replication) demonstrated the nanoparticles with double layer increases the rate of cisplatin internalized then released into the cells, stops the replication of DNA and induces cell death by apoptosis. No intrinsic toxicity of nano-objects is observed. In vivo studies of these nanoparticles double layer after intravenous injection of 5, 7 and 9 mg/Kg in the rats showed this formulation increases the maximum tolerated dose and has an antitumor activity against PROb en GV1A1 cells lines. This strategy of developing layer-by-layer nucleolipids nanoparticles allows to insert PEG with or without folic acid for targeting and introducing second drug, a lipophilic paclitaxel. In vitro study (cytotoxicity, internalization) have shown the benefits of both modification.

No description available.

La combustion de la biomasse est l’une des sources majoritaires de particules atmosphériques en périodes hivernales dans les vallées alpines, et particulièrement en vallée de l’Arve où des dépassements des seuils européens sont très régulièrement observés. Ceci a conduit à la mise en place d’un large programme de remplacement des dispositifs de chauffage au bois les moins performants dans le cadre d’une des actions du Plan de Protection de l’Atmosphère, le Fond Air Bois. Le projet DECOMBIO (DÉconvolution de la contribution de la COMbustion de la BIOmasse aux PM10 dans la vallée de l’Arve) a ainsi été mis en place en octobre 2013 afin de mesurer l’impact de cette politique de rénovation des appareils de chauffage au bois sur la qualité de l’air. C’est dans ce programme que s’inscrivent ces travaux de thèse dont l’objectif principal est de valider les méthodologies mises en place en routine pour permettre une déconvolution rapide de la combustion de la biomasse et mettre en relation les éventuels changements observés avec les avancées des remplacements de dispositifs de chauffage au bois domestiques.Pour mener à bien ce travail, trois sites, représentant les différentes situations de la vallée de l’Arve, ont été instrumentés (Marnaz, Passy et Chamonix) afin de suivre en continu, et tout au long du projet DECOMBIO, l’évolution des concentrations atmosphériques du Black Carbon (BC) et des traceurs moléculaires permettant de distinguer la contribution de la combustion de la biomasse des autres types de combustion. Un important jeu de données a été acquis entre novembre 2013 et octobre 2014 grâce à des prélèvements réguliers sur filtre permettant une caractérisation très fine de la composition chimique des particules atmosphériques. L’utilisation de l’approche statistique « Positive Matrix Factorization » (PMF) a permis de mieux appréhender les différentes sources entrant en jeu dans les émissions de particules au sein de cette vallée avec notamment un intérêt particulier pour les émissions de la combustion de la biomasse. Le développement de cette méthodologie d’attribution et de quantification des sources de particules basé sur l’utilisation de traceurs organiques spécifiques, de contraintes particulières appliquées à ce modèle et de données de déconvolution de la matière carbonée constitue une avancée importante dans la définition des facteurs sources issus de ce modèle.Les méthodologies développées au cours de ce travail, permettant une amélioration des connaissances et des contributions des sources, constituent donc des outils directement utilisables par les Associations Agréées de Surveillance de la Qualité de l’Air (AASQA), notamment pour l’évaluation quantitative des mesures prises pour améliorer la qualité de l’air dans le cadre de Plans de Protection de l’Atmosphère, entre autres celui de la vallée de l’Arve. / Biomass burning is one of the major sources of atmospheric particles during wintertime in Alpine valleys, and more especially in the Arve valley where exceedances of the European regulated limit value are regularly observed. This situation led to the establishment of an important program of replacement of old wood stoves with new ones as part of an action of an Atmospheric Protection Plan (APP), the “Fonds Air Bois”. The research program DECOMBIO (“DÉconvolution de la contribution de la COMbustion de la BIOmasse aux PM10 dans la vallée de l’Arve”) has been set up in October 2013 to estimate the impact of this wood stoves renewal policy on air quality. This thesis works be incorporated within this program and have for main objective to validate methodologies used in routine to enable a fast deconvolution of the biomass burning source and to compare any observed changes with progress of wood stove changeout.To complete this work, three sites, representing the different situations of the Arve valley, were instrumented (Marnaz, Passy and Chamonix) to monitor the continuing evolution of atmospheric concentrations of Black Carbon (BC) and molecular markers enabling to distinguish between the biomass burning contribution and that of other types of combustion. A large dataset was acquired between November 2013 and October 2014 thanks to regular filter samples enabling a vast chemical characterization of PM10. The use of statistical analysis “Positive Matrix Factorization” (PMF) has led to an enhanced appreciation of particle emission sources within this valley with a focus on biomass burning emissions. The development of this methodology of identification and source apportionment based on the use of specific organic markers, specific constraints and data from carbonaceous matter deconvolution is an important progress in definition of factors from this model.The developed methodologies during this work, enabling an improvement of knowledges and source apportionment, are tools directly usable by French Accredited Associations for Air Quality Monitoring, especially for the quantitative assessment of actions introduced to improve air quality as part of Atmospheric Protection Plans, for example the one in the Arve valley.

Dans le Sud-Est de la France, le département des Alpes-Maritimes, singulier du fait de son relief contrasté, est soumis au jeu des brises et inversions thermiques nocturnes. L’agglomération littorale contribue aux émissions de particules qui sont un des polluants les plus nocifs pour la santé humaine. La pollution de l’air n’est évidemment pas répartie de manière homogène dans le temps et dans l’espace. Les topoclimats sont un protagoniste de la pollution de l’air au sein de cet espace littoral montagneux. La problématique centrale de cette thèse consiste donc à comprendre pourquoi et comment les topoclimats influencent la variabilité spatio-temporelle des concentrations de particules dans le sud-ouest du département, tout en considérant qu’ils ne sont pas seuls à expliquer les concentrations. Afin de répondre à cette question, plusieurs objectifs privilégiant les mesures de terrain, et la modélisation ont été fixés :- exploiter des données de concentrations de particules et de variables météorologiques acquises à l’aide de plusieurs appareils de mesures, de manière fixe et itinérante, en plusieurs endroits et à différentes échelles spatio-temporelles ;- caractériser les écoulements d’air à faible altitude à l’aide de ballons équilibrés (dits CLB) et les mettre en relation avec les niveaux de PM10 mesurés ; - caractériser chimiquement les PM10 pour évaluer la contribution des principales sources d’émissions ;- tester la capacité d’un logiciel de dispersion atmosphérique à simuler en relief contrasté les effets des topoclimats sur la variabilité spatio-temporelle des PM10.L’influence des topoclimats sur la pollution de l’air particulaire a été établie. / In the Southeastern of France, the department of the Alpes-Maritimes is singular by contrasting terrain and is submitted to breezes and temperature inversions. The coastal urbanization contributes to the particulate matters emissions that are part of the most harmful substances to human health. Air pollution is not spread heavenly in time and space, of course. Topoclimates are one of the protagonists of air contamination within this mountainous coastal area. The focus of this thesis work is to understand why and how topoclimates have impact on the spatio-temporal variability of particle concentrations in the Southwest of the department, while considering that they are not alone to explain the concentrations. The researcher identified several objectives to answer this question and he gave priority to ground measures and modeling: - To explore data about the particulate matters and meteorological characteristics that were collected through the use of several measuring tools, in a fixed and travelling way, in different places and on various spatio-temporal scales;- To identify and characterize air flows at low altitude with CLB (Constant Level Balloon) and cross compare them with the measured levels PM10; - To chemically analyse PM10 to assess the contribution of the main sources of emission;- To test the capacity of an atmospheric dispersion software to simulate the impact of topoclimates on the spatio-temporal variety of PM10 on mountainous and uneven landscapes.The influence of topoclimates on the air pollution has been scientifically established.

O mel é um alimento de uso milenar, açucarado de fácil digestão, que constitui uma importante fonte de energia, contribuindo para o equilíbrio do processo biológico do corpo humano, sendo elaborado a partir da desidratação e transformação do néctar das flores nativas pelas abelhas produtoras. Para que o mel seja comercializado para o consumo humano, ele precisa atender aos requisitos mínimos de identidade e qualidade exigidos pela Legislação Brasileira. No Brasil a criação de abelhas é dividida em duas práticas distintas, a Apicultura tradicional, que utiliza as abelhas Apis mellifera e a Meliponicultura que utiliza as abelhas sem ferrão como a Jataí (Tetragonisca angustula). Os méis de abelhas sem ferrão tem maior valor comercial comparado ao mel tradicional, entretanto são comercializados sem uma legislação própria. Na literatura existem poucos trabalhos que tratam da composição destes tipos de méis que são popularmente conhecidos por suas propriedades benéficas à saúde. Em vista do exposto acima, o objetivo deste presente trabalho foi o de comparar a composição e a qualidade de méis de Apis mellifera com os de abelhas sem ferrão da espécie Tetragonisca angustula, popularmente conhecida como Jataí. Para tanto as amostras de méis foram obtidas de colméias de Apis mellifera e de Tetragonisca angustula de uma mesma região botânica, o que foi possível constatar que os méis de abelha Jataí apresentaram maior diversidade botânica em relação aos méis de Apis. Neste trabalho foram utilizados os métodos de avaliação estabelecidos pela Legislação Brasileira para qualidade de mel de Apis mellifera e os valores sugeridos para méis de mellponíneos do Brasil pe10s pesquisadores VILLAS - BOAS e MALASPINA (2005). A maioria das amostras de Apis apresentaram-se dentro da legislação vigente, enquanto méis Jataí apresentaram os parâmetros: umidade (23,40 -25,60%), acidez (21,65 - 63,85 mE/Kg) e açúcares redutores (44,78 - 67,54%) e sacarose aparente (0,43 - 1,60%) fora dos padrões estabelecido pela legislação vigente para os méis de Apis mellifera. No entanto, encontram-se dentro dos valores sugeridos para méís de meliponíneos brasileiros, pelos pesquisadores acima mencionados. Além das análises físico-químicas tradicionais e a análise polínica também foi determinada a composição nutricional, sendo que o mel de Apis apresentou maior de valor energético (43,58- 66,32 Kcal) em relação aos méis de Jataí (36,83 - 60,52 Kcal) (p<0,05). Também foram determinados os açúcares por CLAE, condutividade elétrica (uS/cm-1) e a análise de cor (mmPfund). As amostras de Apis mellifera apresentaram maior o teor glicose (%), frutose (%) e condutividade elétrica (uS/cm-1) em relação aos méis de Jataí Em relação as análises de cor notou-se maior predominância da coloração âmbar-claro, mas amostras analisadas. / Honey is considered as a food that provides energy, being elaborated from the dehydration and transformation of the nectar of the flowers by the bees. For the human consumption, honey needs to attend the minimum requirements of identity and quality demanded by the regulation. In Brazil beekeepers can be divided in two practical distinct ones: the traditional ones, which use Apis mellifera bees and the Meliponiculture which uses stingless bees such as Jataí bee (Tetragonisca angustula). There are no identity and quality parameters or regulation for this type of honey. Honey from of stingless bees are more expensive compared with the traditional honey, however their are commercialized without a proper regulation. In literature few works were found regarding the composition of these types of honey which are popularly known by its beneficiaI properties to human health. The objective of the present work is to compare the composition and quality of honey from Apis mellifera and from stingless bees (Tetragonisca angustula), popularly known as Jataí bee. Samples of honey were obtained from Apis mellifera and Tetragonisca angustula bees in the same botanical region. In this work the methods used were based on the Brazilian Regulation for quality control of honey from Apis mellifera and the values suggested for honeys of meliponíneos of Brazil for researchers VILLAS-BOAS and MALASPINA (2005). The majority of the samples of Apis had presented in accordance with the regulation while the Jataí honeys had presented: humidity (23,40 - 25.60%), acidity (21,65 - 63,85 mE/Kg) and reducing sugars (44,78 - 67.54%) are out of the standards for honeys of Apis mellifera. However, they are in accordance with the values suggested for honeys of Brazilian meliponíneos. The physicochemical, polinic and nutritional analysis were determined, and the honey of Apis bee presented greater amount of energy value (43,58 - 66,32 Kcal) in relation to the honeys of Jataí bee (36,83 - 60,52 Kcal) (p<O,05). The sugars for HPLC, electric conductivity (uS/cm-1) and analysis of color (mmPfund) were determined. Samples of Apis mellifera had presented greater values for glucose (%), frutose (%) and electric conductivity (uS/cm-1) in relation to the honeys from Jataí (p<0,05). Regarding the color analyses, it was predominance of the coloration clear -amber.

<p>Opisane&nbsp; su&nbsp; sinteze&nbsp; novih&nbsp; liganada&nbsp; bis(ftalazin-1hidrazon)-2,6-diacetilpiridna&nbsp; (Hz₂DAP&middot;2HCl),&nbsp; bis(3-hlorpiridazin-6-hidrazon)-2,6-diacetilpiridina (Hp₂DAP),&nbsp; 3-hlorpiridazin-6-hidrazon&nbsp; di(2-piridil) ketona&nbsp; (HpDPK),&nbsp; ftalazin-1-hidrazon&nbsp; di(2-piridil)<br />ketona&nbsp; (HzDPK)&nbsp; i&nbsp; ftalazin-1-hidrazon&nbsp; piridin-2-karbaldehida&nbsp; (HzPY).&nbsp; Zajedničko&nbsp; svojstvo&nbsp; dobijenih liganada&nbsp; je&nbsp; &scaron;to&nbsp; sadrže&nbsp; piridinski&nbsp; i&nbsp; diazinski&nbsp; prsten&nbsp; i sadrže&nbsp; samo&nbsp; donorne&nbsp; atome&nbsp; azota.&nbsp; Tokom&nbsp; nastajanja kompleksa dolazi do deprotonacije liganada. Svi ligandi su&nbsp; okarakterisani&nbsp; elementalnom&nbsp; analizom, termoanalitičkim&nbsp; metodama&nbsp; i&nbsp; metodom&nbsp; IR spektroskopije,&nbsp; dok&nbsp; neki&nbsp; i&nbsp; metodom&nbsp; NMR spektroskopije&nbsp; kao&nbsp; i&nbsp; rendgenskom&nbsp; strukturnom analizom.Za&nbsp; sintezu&nbsp; koordinacionih&nbsp; jedinjenja&nbsp; primenjeni&nbsp; soli Co(II),&nbsp; Ni(II),&nbsp; Cu(II)&nbsp; i&nbsp; Zn(II).&nbsp; Dobijeni&nbsp; kompleksi su okarakterisani&nbsp; elementalnom&nbsp; analizom, konduktomerijskim&nbsp; i&nbsp; magnetnim&nbsp; merenjima,&nbsp; IR spektroskopijom i termoanalitičkim metodama. Barem jedan&nbsp; kompleks&nbsp; iz&nbsp; svake&nbsp; serije&nbsp; je&nbsp; okarakterisan&nbsp; i rendgenskom strukturnom analizom. Urađena&nbsp; su&nbsp; i&nbsp; ispitivanja&nbsp; antimikrobne&nbsp; aktivnosti odabranih&nbsp; jedinjenja&nbsp; prema&nbsp; predstavnicima&nbsp; grampozitivnih i gram-negativnih bakterija i kulturu kvasca. Pored&nbsp; toga,&nbsp; urađena&nbsp; su&nbsp; i&nbsp; ispitivanja&nbsp; citotoksične,antiproliferativne&nbsp; i&nbsp; inhibitorne&nbsp; aktivnosti&nbsp; jedinjenja prema&nbsp; roditeljskim&nbsp; i&nbsp; multirezistentnim&nbsp; T-limfomnim ćelijama&nbsp; kancera.&nbsp; Utvrđeno&nbsp; je&nbsp; da&nbsp; neka&nbsp; jedinjenja pokazuju&nbsp; izrazito&nbsp; mikrobicidno,&nbsp; citotoksično, antiproliferativno i inhibitorno dejstvo.</p> / <p>The synthesis of new ligands dihydrochloride salt of 2,6-diacetylpyridne&nbsp;&nbsp; bis(phthalazine-1hydrazone) (Hz₂DAP&bull;2HCl),&nbsp; 2,6-diacetylpiridine&nbsp; bis(3- chloropyridazine-6-hydrazone)&nbsp; (Hp₂DAP),&nbsp; di(2-pyridyl)ketone&nbsp; 3-chloropyridazine- 6-hydrazone (HpDPK),&nbsp; di(2-pyridyl)ketone&nbsp; phthalazine-1-hydrazone&nbsp; (HzDPK)&nbsp; and&nbsp; &nbsp; pyridine-2-carbaldehide phthalazine-1-hydrazone&nbsp; (HzPY)&nbsp; have&nbsp; been described. All the ligands contain pyridine and diazine core and all of them have only nitrogen donor atoms. During the complex formation the deprotonation of ligands takes&nbsp; places.&nbsp; All&nbsp; of&nbsp; the&nbsp; ligands&nbsp; have&nbsp; been characterized&nbsp; by&nbsp; elemental&nbsp; analysis,thermoanalytical&nbsp; methods&nbsp; and&nbsp; IR&nbsp; spectroscopy.&nbsp; In some&nbsp; cases&nbsp; also&nbsp; by&nbsp; NMR&nbsp; spectroscopy&nbsp; and&nbsp; X-ray structural analysis.Co(II), Ni(II), Cu(II) and Zn(II) salts were&nbsp; used for the synthesis&nbsp; of&nbsp; the&nbsp; coordinational&nbsp; compounds.&nbsp; The obtained complexes were characterized by elemental analysis,&nbsp; molar&nbsp; conductivity&nbsp; and&nbsp; magnetic measurements,&nbsp; IR&nbsp; spectroscopy&nbsp; and thermoanalytical&nbsp; methods.&nbsp; At&nbsp; least&nbsp; one complex&nbsp; of each&nbsp; series&nbsp; were&nbsp; characterized&nbsp; by&nbsp; X-ray&nbsp; structural analysis.The antimicrobial activity of some of the compounds toward&nbsp; Gram-positive/Gram- negative&nbsp; bacteria furthermore,&nbsp; the&nbsp; cytotoxic,&nbsp; antiproliferative&nbsp; and inhibitory&nbsp; activity&nbsp; toward&nbsp; sensitive&nbsp; parental&nbsp; andmultiresistant&nbsp; T-lymphoma&nbsp; cancer&nbsp; cells&nbsp; have&nbsp; also been carried out. It&nbsp; can&nbsp; be&nbsp; concluded&nbsp; that&nbsp; some&nbsp; of&nbsp; the&nbsp; compounds exhibit&nbsp; outstanding&nbsp; antimicrobial,&nbsp; cytotoxic, antiproliferative, and inhibitory activity.</p>

Les assemblages lithiques dominent la plupart des sites archéologiques du Nunavik et constituent ainsi une véritable mine d’informations. Le nombre limité de travaux sur les matériaux de la côte est de la baie d’Hudson, nous a amené à nous pencher sur une source présente dans ce secteur. Notre objectif était alors de caractériser la matière première provenant de cette formation géologique, le chert Nastapoka. Pour ce faire, nous avons choisi la technique de fluorescence aux rayons X. Les résultats ont permis de constater, en plus des observations macroscopiques, la nature très variable de ce chert présentant une signature chimique complexe. Pour compléter le portrait, nous avons évalué l’utilisation du chert Nastapoka par les Paléoesquimaux par une comparaison d’analyses technologiques déjà effectuées sur les sites GhGk-4, GhGk-63 et IcGm-5. Cet examen a révélé que l’évolution des stratégies d’exploitation des matériaux lithiques dans cette région appui le continuum culturel Prédorsétien-Dorsétien observé ailleurs. / The dominant cultural material on Nunavik’s archaeological sites is lithics. As a result they constitute an important source of information on prehistoric lifeways. The lack of lithic raw materials resarchs carried out on the east coast of Hudson Bay gave us the opportunity to focus on a source in this area. The objective of this thesis research was to characterize one component of the geological formation: Nastapoka chert. In order to do this, X-ray fluorescence was chosen. The results demonstrate that it is difficult to construct a unique geochemical pattern for the source because of its variability. To complete the portrait, we take into account the technological use of Nastapoka chert by the Paleoeskimo groups by comparing three site’s studies (GhGk-4, GhGk-63 and IcGm-5). This analysis of the exploitation of this material reveals a developement from Predorset to Dorset that supports the idea of cultural continuum between the two periods.

<p>&nbsp;&nbsp; U ovoj doktorskoj disertaciji opisane su sinteze novih kompleksa prelaznih metala sa piridoksiliden-&nbsp; (PLAG), odnosno saliciliden-aminogvanidinom (SALAG). Dobijeni<br />kompleksi su okarakterisani elementalnom analizom, IR spektrima, konduktometrijskim i magnetnim merenjima, a većina i rendgenskom<br />strukturnom analizom. Osim toga, dobijene su i nove forme ovih &Scaron;ifovih baza, i to u vidu monokristala, čime su omogućena ispitivanja njihovih&nbsp; molekulskih i kristalnih struktura, kao i uporedna analiza sa koordinovanim ligandima.<br />&nbsp; &nbsp; Sa PLAG je sintetisano 7 novi&nbsp; kompleksa Cu(II), a pored toga po prvi put su<br />izolovani mono i bis(ligand) kompleksi Fe(III) i Co(III), mono(ligand) kompleksi&nbsp; V(V), kao&nbsp; i jedan kompleks Zn(II) u kojem ovaj potencijalno tridentatni&nbsp;<em> ONN&nbsp;</em> ligand,&nbsp; u<br />monoprotonovanoj formi,&nbsp; ima ulogu kontra-jona. Sa stanovi&scaron;ta geometrije zajedničko za izolovane komplekse Cu(II) i V(V) je da imaju kvadratno-piramidalnu strukturu, sa izuzetkom jednog kvadratno-planarnog kompleksa Cu(II), dok je u kompleksima Fe(III) i Co(III) nađeno očekivano oktaedarsko okruženje centralnog<br />jona. Pored ovih, sintetisano je i pet novih kompleksa sa SALAG, od kojih su dva<br />kompleksa Cu(II) i kompleks V(V) okarakterisani rendgenskom strukturnom<br />analizom, dok je mikrokristalnim bis(ligand) kompleksima Co(III) i Ni(III) na osnovu<br />fizičko-hemijskih karakteristika predložena odgovarajuća struktura.<br />&nbsp;&nbsp; Zajedničko za obe opisane &Scaron;ifove baze je da se koordinuju na&nbsp;<em> ONN&nbsp; </em>tridentatni način, i to preko atoma kiseonika deprotonovane fenolne grupe i atoma azota azometinske i imino grupe AG fragmeta. Posebno je nagla&scaron;eno da su&nbsp; sa<br />PLAG izolovana dva dimerna kompleksa Cu(II) u kojima je po prvi put nađena tetradentatna koordinacija ovog&nbsp; liganda, u koju je dodatno uključen atom kiseonika hidroksimetil-grupe PL-ostatka. Za razliku od SALAG, koji je u izolovanim kompleksima koordinovan isključivo kao monoanjon, nastao deprotonacijom fenolne<br />OH-grupe, za PLAG je osim ove, potvđena koordinacija u neutralnoj, zwitter-jonskoj, ali i dvostruko deprotonovanoj formi. Zwitter-jonska forma liganda nastaje migracijom atoma vodonika sa fenolnog hidroksila na piridinski atom azota PL-ostatka, dok deprotonacijom piridinskog ili hidrazinskog atoma azota, odnosno oba pomenuta atoma nastaju monoanjon i dianjon helatnog liganda, respektivno.<br />&nbsp;&nbsp; Na kraju, urađena su&nbsp; i ispitivanja antimikrobne aktivnosti odabranih jedinjenja<br />prema predstavnicima grampozitivnih i gramnegativnih bakterija, kao i dve kulture<br />kvasca. Tom prilikom nije utvrđena nikakva inhibitorna aktivnost&nbsp;&nbsp; prema primenjenim<br />bakterijskim sojevima, dok su u slučaju kvasaca izvesno mikrobicidno dejstvo pokazali samo kompleksi Cu(II).</p> / <p>This PhD thesis describes the syntheses of some new transition metal complexes with&nbsp; pyridoxilidene-&nbsp; (PLAG) and salicylideneaminoguanidine (SALAG). Obtained&nbsp; complexes are characterized by&nbsp;&nbsp; elemental analysis, IR&nbsp; spectroscopy,&nbsp; conductometric and magnetic measurements. Besides, the structural analysis of majority of the obtained complexes was performed. Some new forms of these Schiff&nbsp; bases are synthesized in form of single crystals, which made their X-ray analysis as well as comparison with coordinated forms possible.</p><p>With PLAG, 7 new Cu(II) complexes were obtained and for the first time mono and bis(ligand) complexes of Fe(III) and Co(III) as well&nbsp; mono(ligand)&nbsp; complexes&nbsp; of V(V) were isolated. Furthermore,&nbsp; the structure of Zn(II) complex in which PLAG in its monocationic form has a role of counter ion is presented. With the exception of one Cu(II) complex, all reported Cu(II) and V(V) complexes have a square-pyramidal geometry, whilst&nbsp; Fe(III)&nbsp; and Co(III)&nbsp; are situated in octahedral surroundings. Also, five new complexes of Cu(II), Co(III), Ni(II) and V(V) with SALAG were synthesized. In both&nbsp; Cu(II) complexes and V(V) complex the expected coordination mode and geometry were confirmed by X-ray analysis, while octahedral structure of bis(ligand) complexes with Co(III) and Ni(II) was proposed based on results of physico-chemical&nbsp; characterization.</p><p>Both PLAG and SALAG coordinate the metal ion in tridentate&nbsp; ONN&nbsp; manner, through the oxygen atom of deprotonated phenolic group and nitrogen atoms&nbsp; of azomethine and imino groups of AG moiety. It is also emphasized that in two dimeric Cu(II) complexes with PLAG tetradentate coordination mode was found, in which the oxygen atom of hydroxymethyl group of PL residue was additionally involved. Unlike SALAG, which is coordinated as monoanion in all of the examined complexes, PLAG can have one of three degrees of deprotonation. Zwitter-ion of PLAG is formed by migration of H-atom from phenolic oxygen to pyridine nitrogen, while the deprotonation of pyridine or/and hydrazine nitrogen, makes it mono-and dianion, respectively.</p><p>Also, microbiological tests on the selected compounds were preformed. Namely, antimicrobial activity of these compounds against some gram-positive and gram-negative bacteria, as well as some yeast cultures was examined and none of the samples showed antimicrobial activity against bacteria, whilst only Cu(II) complexes showed certain inhibitory effect against yeasts.</p>

Les assemblages lithiques dominent la plupart des sites archéologiques du Nunavik et constituent ainsi une véritable mine d’informations. Le nombre limité de travaux sur les matériaux de la côte est de la baie d’Hudson, nous a amené à nous pencher sur une source présente dans ce secteur. Notre objectif était alors de caractériser la matière première provenant de cette formation géologique, le chert Nastapoka. Pour ce faire, nous avons choisi la technique de fluorescence aux rayons X. Les résultats ont permis de constater, en plus des observations macroscopiques, la nature très variable de ce chert présentant une signature chimique complexe. Pour compléter le portrait, nous avons évalué l’utilisation du chert Nastapoka par les Paléoesquimaux par une comparaison d’analyses technologiques déjà effectuées sur les sites GhGk-4, GhGk-63 et IcGm-5. Cet examen a révélé que l’évolution des stratégies d’exploitation des matériaux lithiques dans cette région appui le continuum culturel Prédorsétien-Dorsétien observé ailleurs. / The dominant cultural material on Nunavik’s archaeological sites is lithics. As a result they constitute an important source of information on prehistoric lifeways. The lack of lithic raw materials resarchs carried out on the east coast of Hudson Bay gave us the opportunity to focus on a source in this area. The objective of this thesis research was to characterize one component of the geological formation: Nastapoka chert. In order to do this, X-ray fluorescence was chosen. The results demonstrate that it is difficult to construct a unique geochemical pattern for the source because of its variability. To complete the portrait, we take into account the technological use of Nastapoka chert by the Paleoeskimo groups by comparing three site’s studies (GhGk-4, GhGk-63 and IcGm-5). This analysis of the exploitation of this material reveals a developement from Predorset to Dorset that supports the idea of cultural continuum between the two periods.