This master’s thesis is divided into two parts; practical and theoretical. The theoretical part of this study describes the influence of high temperature on concrete structure and chemical, mechanical and physical changes, which take place during the exposure to high temperatures. The thesis also evaluates spalling of concrete and the methods to prevent it, as well as the function of polypropylene and cellulose fibers in the concrete. The practical part deals with design, production and testing of the cement-based concrete with the use of different fibers (polypropylene fibers and cellulose fibers). The properties and the means of applications in high temperatures are also included. The practical part also assesses the influence of high temperature on strength, porosity, visual changes of specimens, changes of surface and degradation of testing specimens due to heat loads according to normative heat curve (ISO 834) and also according to hydrocarbon curve. For clearer arrangement, the experimental tests are divided into two parts and the measured values are evaluated at the end of each part. The conclusion resumes all data obtained by testing and evaluates what is the most suitable formulation. The approach for further research is also discussed.

<p>Mikroplastika&nbsp; je&nbsp; sveprisutna&nbsp; u&nbsp; vodenom&nbsp; ekosistemu&nbsp; pri&nbsp; čemu&nbsp; se&nbsp; često<br />ističe značaj ispitivanja njihovog uticaja na pona&scaron;anje drugih jedinjenja u vodi.<br />Pod pojmom mikroplastika podrazumevaju se plastične čestice manje od 5 mm.<br />Imajući u vidu potrebu za unapređenjem znanja o &scaron;tetnom uticaju mikroplastike<br />u životnoj sredini u ovom radu sproveden je set eksperimenata u kom je ispitivan<br />mehanizam&nbsp; interakcija&nbsp; koje&nbsp; se&nbsp; uspostavljaju&nbsp; prilikom&nbsp; adsorpcije&nbsp; hlorovanih<br />fenola,&nbsp; derivata&nbsp; benzena&nbsp; i&nbsp; policikličnih&nbsp; aromatičnih&nbsp; ugljovodonika&nbsp; na mikroplastici&nbsp; u&nbsp; vodenom&nbsp; matriksu.&nbsp; Kako&nbsp; bi&nbsp; se&nbsp; &scaron;to&nbsp; detaljnije&nbsp; razumeo&nbsp; uticaj mikroplastike&nbsp; i&nbsp; osobina&nbsp; vodenog&nbsp; matriksa&nbsp; na&nbsp; pona&scaron;anje&nbsp; organskih&nbsp; polutanata, laboratorijska ispitivanja su sprovedena u sintetičkom i realnom vodenommatriksu.&nbsp; Takođe&nbsp; je&nbsp; sprovedena&nbsp; optimizacija&nbsp; izolovanja&nbsp; i&nbsp; karakterizacije mikroplastike iz kozmetičkih sredstava u cilju procene uticaja osobina primarne mikroplastike na uspostavljanje interakcija sa organskim polutantima. Na&nbsp; osnovu&nbsp; dobijenih&nbsp; rezultata&nbsp; istraživanja&nbsp; može&nbsp; se&nbsp; zaključiti&nbsp; da&nbsp; se optimalna metoda izolovanja mikroplastike iz kozmetičkih sredstava zasniva na dodatnom&nbsp; tretiranju&nbsp; osu&scaron;enog&nbsp; materijala&nbsp; 30%&nbsp; vodonik-peroksidom,&nbsp; nakon ekstrakcije&nbsp; sredstva&nbsp; u&nbsp; destilovanoj&nbsp; vodi,&nbsp; u&nbsp; cilju&nbsp; dobijanja&nbsp; čistijih&nbsp; uzoraka mikroplastike. Promena brzine me&scaron;anja ima znčajan uticaj na promenu stepena adsorpcije ispitivanih grupa organskih jedinjenja.&nbsp; Uticaj se ogleda u povećanju stepena adsorpcije sa porastom brzine me&scaron;anja, a maksimalni procenat adsorpcije postignut&nbsp; je&nbsp; pri&nbsp; brzini&nbsp; me&scaron;anja&nbsp; od&nbsp; 150&nbsp; o/min.&nbsp; Dodatno,&nbsp; disperzija&nbsp; pra&scaron;kastih materijala u vodi nema značajan uticaj na promenu stepena adsorpcije hlorovanih fenola,&nbsp; derivata&nbsp; benzena&nbsp; i&nbsp; policikličnih&nbsp; aromatičnih&nbsp; ugljovodonika&nbsp; na mikroplastici.Ravnotežno&nbsp; stanje&nbsp; između&nbsp; koncentracije&nbsp; hlorovanih&nbsp; fenola,&nbsp; derivata<br />benzena&nbsp; i&nbsp; policikličnih&nbsp; aromatičnih&nbsp; ugljovodonika&nbsp; u&nbsp; vodi&nbsp; i&nbsp; odabranih predstavnika&nbsp; mikroplastike&nbsp; (PEp,&nbsp; PE_PCPs_1,&nbsp; PE_PCPs_2,&nbsp; PEg,&nbsp; PET,&nbsp; PP&nbsp; i PLA) uspostavlja se nakon 24 i 48 h kontakta u zavisnosti od vrste jedinjenja. Na promenu&nbsp; adsorpcionog&nbsp; afiniteta&nbsp; hlorovanih&nbsp; fenola,&nbsp; derivata&nbsp; benzena&nbsp; i policikličnih aromatičnih ugljovodonika prema mikroplastici utiču kako fizičkohemijske&nbsp; osobine&nbsp; jedinjenja&nbsp; tako&nbsp; i&nbsp; karakteristike&nbsp; mikroplastike.&nbsp; Na&nbsp; osnovu kinetičkih&nbsp; eksperimenata, najveći adsorpcioni afinitet ka mikroplastici&nbsp; ispoljili su&nbsp; derivati&nbsp; benzena&nbsp; (qt=103-350&nbsp; &micro;g/g),&nbsp; dok&nbsp; je&nbsp; najmanji&nbsp; uočen&nbsp; kod&nbsp; hlorovanih fenola&nbsp; (qt=25-225&nbsp; &micro;g/g).&nbsp; Dobijeni&nbsp; rezultati&nbsp; adsorpcije&nbsp; derivata&nbsp; benzena&nbsp; na ispitivanim&nbsp; česticama&nbsp; mikroplastike&nbsp; takođe&nbsp; su&nbsp; ukazali&nbsp; na&nbsp; veći&nbsp; afinitet&nbsp; ovih jedinjenja&nbsp; ka&nbsp; mikroplastici,&nbsp; u&nbsp; poređenju&nbsp; sa&nbsp; jedinjenjima&nbsp; iz&nbsp; grupe&nbsp; policikličnih aromatičnih&nbsp; ugljovodonika&nbsp; i&nbsp; hlorovanih&nbsp; fenola&nbsp; sličnih&nbsp; logKow&nbsp; vrednosti. Dodatno,&nbsp; uticaj&nbsp; vodenog&nbsp; matriksa&nbsp; na&nbsp; adsorpciju&nbsp; hlorovanih&nbsp; fenola,&nbsp; derivata benzena&nbsp; i&nbsp; policikličnih&nbsp; aromatičnih&nbsp; ugljovodonika&nbsp; na&nbsp; mikroplastici&nbsp; zavisi&nbsp; od same grupe jedinjenja kao i od vrste mikroplastike pri čemu je najmanje izražen u&nbsp; slučaju&nbsp; ispitivanih&nbsp; policikličnih&nbsp; aromatičnih&nbsp; ugljovodonika,&nbsp; a&nbsp; najvi&scaron;e&nbsp; kod hlorovanih fenola.Visoke&nbsp; vrednosti&nbsp; koeficijenta&nbsp; determinacije&nbsp; kinetičkog&nbsp; modela&nbsp; pseudodrugog&nbsp; reda&nbsp; za&nbsp; adsorpciju&nbsp; hlorovanih&nbsp; fenola,&nbsp; derivata&nbsp; benzena&nbsp; i&nbsp; policikličnih aromatičnih ugljovodonika na čestice mikroplastike ukazjuju da je hemisorpcija mogući&nbsp; mehanizam.&nbsp; Pored&nbsp; visokih&nbsp; vrednosti&nbsp; koeficijenata&nbsp; determinacije&nbsp; u slučaju svih odabranih organskih jedninjenja dobijena konstanta brzine drugog reda&nbsp; bila&nbsp; je&nbsp; manja&nbsp; od&nbsp; po četne&nbsp; brzine&nbsp; adsorpcije&nbsp; &scaron;to&nbsp; ukazuje&nbsp; na&nbsp; znatno&nbsp; brže odvijanje&nbsp; adsorpcije&nbsp; pri&nbsp; kraćim&nbsp; vremenima&nbsp; kontakta&nbsp; (12-24&nbsp; h)&nbsp; nakon&nbsp; čega&nbsp; je<br />dolazilo do usporavanja procesa adsorpcije.Mehanizam adsorpcije hlorovanih fenola, derivata benzena i policikličnih aromatičnih ugljovodonika&nbsp; ispitivan&nbsp; je primenom Freundlich-ovog, Langmuirovog,&nbsp; Redlich-Peterson-ovog&nbsp; i&nbsp; Dubinine-Radusckevich-evog&nbsp; adsorpcionog modela. Vrednosti Freundlich-ovog eksponenta za adsorpciju hlorovanih fenola, derivata benzena i&nbsp; policikličnih aromatičnih ugljovodonika bile su manje od 1,<br />&scaron;to ukazuje na to da je slobodna energije adsorpcije na mikroplastci opadala sa povećanjem&nbsp; inicijalne&nbsp; koncetracije&nbsp; ispitivanih&nbsp; polutanata.&nbsp; Vrednosti maksimalnog adsorpcionog kapaciteta dobijene za&nbsp; adsorpcione procese PAH&nbsp; na česticama mikroplastike bile su u opsegu od 29,7-2596,5 &micro;g/g. Visoke vrednosti maksimalnih adsorpcionih kapaciteta dobijene su takođe za adsorpciju derivata benzena na ispitivanim vrstama mikroplastike&nbsp; 39,3-2010,1 &micro;g/g. S druge strane, uočeno&nbsp; je&nbsp; različito&nbsp; adsorpciono&nbsp; pon&scaron;anje&nbsp; hlorovanih&nbsp; fenola&nbsp; u&nbsp; zavisnosti&nbsp; od vodenog metriksa u kom su eksperimenti sprovedeni pri čemu su&nbsp; qmax&nbsp; vrednosti iznosile 20,00-205,6 &micro;g/g. Značajan uticaj&nbsp; pH vrednosti vodenog matriksa&nbsp; utvrđen je&nbsp; za adsorpciju hlorovanih&nbsp; fenola&nbsp; na&nbsp; mikroplastici,&nbsp; dok&nbsp; u&nbsp; slučaju&nbsp; derivata&nbsp; benzena&nbsp; i&nbsp; PAH promena pH vrednosti vodenog matriksa nije pokazala značajan uticaj. Rezultati dobijeni&nbsp; za&nbsp; adsorpciju&nbsp; hlorovanih&nbsp; fenola&nbsp; na&nbsp; mikroplastici&nbsp; ukazuju&nbsp; na&nbsp; nižu tendenciju&nbsp; ka&nbsp; formiranju&nbsp; interakcija&nbsp; hlorovanih&nbsp; fenola&nbsp; sa&nbsp; česticama mikroplastike pri pH 4 i pH 10, pri čemu se stepen adsorpcije kretao u opsegu od 8-35% i 15-35%, respektivno, u odnosu na pH 7 (55-65%). Najniži&nbsp; adsorpcioni&nbsp; afinitet&nbsp; uočava&nbsp; se&nbsp; pri&nbsp; adsorpciji&nbsp; ispitivanih&nbsp; grupa jedinjenja na PLA. Može se pretpostaviti da će se organski polutanti,&nbsp;&nbsp; ukoliko ova vrsta mikroplastike dospe u vodene sisteme, slabo vezivati na ovaj materijal pri čemu će značajno manje uticati na njihov trasport kroz životnu sredinu, u odnosu<br />na druge ispitivane vrste mikroplastike. Na&nbsp; osnovu&nbsp; dobijenih&nbsp; rezultata&nbsp; istraživanja&nbsp; može&nbsp; se&nbsp; zaključiti&nbsp; da&nbsp; na adsorpciju ispitivanih grupa organskih jedinjenja i mikroplastike značajan uticaj imaju&nbsp; fizičko-hemijske&nbsp; osobine&nbsp; ispitivanih&nbsp; jedinjenja&nbsp; kao&nbsp; &scaron;to&nbsp; su&nbsp; kiselinska konstanta, veličina molekula, hidrofobnost, stukturni raspored i dr. Pored toga, karakteristike vodenog matriksa, među kojima je najvažnija pH vrednost, imaju značajan&nbsp; uticaj&nbsp; na&nbsp; adsorpcioni&nbsp; afinitet&nbsp; jedinjenja&nbsp; ka&nbsp; mikroplastici.&nbsp; Dodatno,<br />struktura&nbsp; i&nbsp; poreklo&nbsp; polimera&nbsp; ima&nbsp; veliki&nbsp; uticaj&nbsp; na&nbsp; formiranje&nbsp; interakcija&nbsp; sa<br />ispitivanim grupama organskih polutanata. Dobijeni rezultati takođe ukazuju na<br />nemogućnost&nbsp; određivanje&nbsp; unifomnog&nbsp; mehanizma&nbsp; adsorpcije&nbsp; organskih<br />jedinjenja na česticama mikroplastike u vodi.</p> / <p>Microplastics&nbsp; are&nbsp; ubiquitous&nbsp; in&nbsp; aquatic&nbsp; ecosystems,&nbsp; so&nbsp; it&nbsp; is&nbsp; essential&nbsp; to study their&nbsp; impact on the behaviour of other compounds which are commonly present in water. The term microplastics refers to all plastic particles smaller than 5 mm. In order&nbsp; to address knowledge gaps relating to the potential harmful effects of microplastics in the environment, the experiments conducted during this thesis were designed to investigate the adsorption mechanism of chlorinated phenols, benzene derivatives, and polycyclic aromatic hydrocarbons on microplastics in water.&nbsp; To&nbsp; provide&nbsp; a&nbsp; more&nbsp; detailed&nbsp; understanding&nbsp; of&nbsp; the&nbsp; influence&nbsp; of&nbsp; different water&nbsp; matrices&nbsp; on&nbsp; adsorption&nbsp; properties&nbsp; of&nbsp; microplastics,&nbsp; experiments&nbsp; were conducted in both synthetic and real water matrices. In the course of this work, methods were optimised for the isolation and characterization of microplastifrom personal care products, in order to allow investigation&nbsp; of the influence of the&nbsp; properties&nbsp; of&nbsp; primary&nbsp; microplastics&nbsp; on&nbsp; their&nbsp; interactions&nbsp; with&nbsp; organic pollutants.Base on the obtained results, it can be concluded that the optimal method of isolating microplastics from personal care products is based&nbsp; on treating already dried&nbsp; material&nbsp; with&nbsp; 30%&nbsp; hydrogen&nbsp; peroxide,&nbsp; after&nbsp; extraction&nbsp; of&nbsp; the&nbsp; agent&nbsp; in distilled water, in order to obtain cleaner microplastic samples. The mixing rate was&nbsp; found&nbsp; to&nbsp; have&nbsp; a&nbsp; significant&nbsp; effect&nbsp; on&nbsp; the&nbsp; degree&nbsp; of&nbsp; adsorption&nbsp; of&nbsp; the investigated&nbsp; organic&nbsp; compounds.&nbsp; Increasing&nbsp; the&nbsp; mixing&nbsp; speed&nbsp; led&nbsp; to&nbsp; a&nbsp; higher<br />degree&nbsp; of&nbsp; adsorption,&nbsp; with&nbsp; the&nbsp; maximum&nbsp; adsorption&nbsp; percentage&nbsp; reached&nbsp; at&nbsp; a<br />mixing speed of 150 rpm. In addition, the dispersion of powdered materials in the&nbsp; water&nbsp; had&nbsp; no&nbsp; significant&nbsp; effect&nbsp; on the&nbsp; degree&nbsp; of&nbsp; adsorption&nbsp; of&nbsp; chlorinated phenols,&nbsp; benzene&nbsp; derivatives,&nbsp; and&nbsp; polycyclic&nbsp; aromatic&nbsp; hydrocarbons&nbsp; on microplastics.<br />The&nbsp; adsorption&nbsp; equilibrium&nbsp; between&nbsp; the&nbsp; concentration&nbsp; of&nbsp; chlorinated phenols,&nbsp; benzene derivatives and polycyclic aromatic hydrocarbons in water and selected types of microplastics (PEp, PE_PCPs_1, PE_PCPs_2, PEg, PET, PP, and&nbsp; PLA) was established after 24 and 48 h of contact time, depending on the selected&nbsp; group&nbsp; of&nbsp; organic&nbsp; pollutants.&nbsp; The&nbsp; adsorption&nbsp; affinity&nbsp; of&nbsp; chlorinated phenols,&nbsp; benzene&nbsp; derivatives,&nbsp; and&nbsp; polycyclic&nbsp; aromatic&nbsp; hydrocarbons&nbsp; towards microplastics&nbsp; was&nbsp; influenced&nbsp; by&nbsp; both&nbsp; the&nbsp; physicochemical&nbsp; properties&nbsp; of&nbsp; the compounds&nbsp; and&nbsp; the&nbsp; characteristics&nbsp; of&nbsp; the&nbsp; microplastics.&nbsp; Based&nbsp; on&nbsp; the&nbsp; kinetic experiments,&nbsp; the&nbsp; highest&nbsp; adsorption&nbsp; affinity&nbsp; for&nbsp; microplastics&nbsp; was&nbsp; shown&nbsp; by benzene derivatives (qt=103-350 &micro;g/g), while the lowest was&nbsp; observed during the adsorption of chlorinated phenols (qt=25-225 &micro;g/g). Benzene derivatives showed higher&nbsp; adsorption&nbsp; affinities&nbsp; for&nbsp; the&nbsp; selected&nbsp; microplastic&nbsp; particles&nbsp; than&nbsp; the polycyclic&nbsp; aromatic&nbsp; hydrocarbons&nbsp; and&nbsp; &nbsp; chlorinated&nbsp; phenols&nbsp; which&nbsp; had&nbsp; similar logKow&nbsp; values. The influence of the water matrix on adsorption of chlorinated phenols,&nbsp; benzene&nbsp; derivatives,&nbsp; and&nbsp; polycyclic&nbsp; aromatic&nbsp; hydrocarbons&nbsp; on microplastics&nbsp; depended&nbsp; on&nbsp; the&nbsp; specific&nbsp; functional&nbsp; groups&nbsp; of&nbsp; the&nbsp; investigated compounds as well as on the type of microplastics. Water matrix had little impact on&nbsp; the&nbsp; adsorption&nbsp; of&nbsp; polycyclic&nbsp; aromatic&nbsp; hydrocarbons&nbsp; on&nbsp; microplastics&nbsp; but greatly impacted the adsorption of chlorinated phenols. Fitting the pseudo-second order kinetic&nbsp; model to the&nbsp; adsorption data of chlorinated phenols, benzene derivatives, and polycyclic aromatic hydrocarbons on microplastic particles resulted in high correlation coefficients, indicating that chemisorption&nbsp; is&nbsp; the&nbsp; likely&nbsp; adsorption&nbsp; mechanism.&nbsp; In&nbsp; addition&nbsp; to&nbsp; the&nbsp; high correlation coefficients obtained for all the organic pollutants investigated, the pseudo-second order rate constants obtained were lower than the initiaadsorption rate, indicating significantly faster adsorption at shorter contact times (12-24 h), with adsorption slowing down as equilibrium was reached.The adsorption mechanism of chlorinated phenols, benzene derivatives,<br />and&nbsp; polycyclic&nbsp; aromatic&nbsp; hydrocarbons&nbsp; was&nbsp; investigated&nbsp; using Freundlich,Langmuir,&nbsp; Redlich-Peterson,&nbsp; Dubinine-Radusckevich,&nbsp; and&nbsp; Temkin&nbsp; adsorption models.&nbsp; The&nbsp; Freundlich&nbsp; exponent&nbsp; values&nbsp; for&nbsp; the&nbsp; adsorption&nbsp; of&nbsp; chlorinated phenols, benzene&nbsp; derivatives, and polycyclic&nbsp; aromatic&nbsp; hydrocarbons were&nbsp; less than 1 which indicates that the free energy of adsorption of these compounds on microplastics&nbsp; decreases&nbsp; as&nbsp; the&nbsp; initial&nbsp; concentration&nbsp; increases.&nbsp; The&nbsp; maximum adsorption capacities of PAHs on microplastic particles were in the range of 29.7-2596.5&nbsp; &micro;g/g.&nbsp; High&nbsp; maximum&nbsp; adsorption&nbsp; capacities&nbsp; were&nbsp; also obtained&nbsp; for the adsorption&nbsp; of&nbsp; benzene&nbsp; derivatives&nbsp; on&nbsp; the&nbsp; tested&nbsp; types&nbsp; of&nbsp; microplastics:&nbsp; 39.3-2010.1&nbsp; &micro;g/g.&nbsp; The&nbsp; chlorinated&nbsp; phenols&nbsp; behaved&nbsp; differently,&nbsp; and&nbsp; were&nbsp; more effected by the water matrix, with qmax values in&nbsp; the range 20.00-205.6 &micro;g/g. The pH of the water matrix was found to have a significant effect on the adsorption&nbsp; of&nbsp; chlorinated&nbsp; phenols&nbsp; on&nbsp; microplastics,&nbsp; whereas&nbsp; in&nbsp; the&nbsp; case&nbsp; of benzene&nbsp; derivatives&nbsp; and&nbsp; polycyclic&nbsp; aromatic&nbsp; hydrocarbons,&nbsp; the&nbsp; degree&nbsp; of<br />adsorption&nbsp; was&nbsp; largely&nbsp; independent&nbsp; of&nbsp; the&nbsp; water&nbsp; pH.&nbsp; For&nbsp; the&nbsp; adsorption&nbsp; of chlorinated&nbsp; phenols&nbsp; on&nbsp; microplastics,&nbsp; neutral&nbsp; pH&nbsp; conditions&nbsp; resulted&nbsp; in&nbsp; the greatest degrees of adsorption (55-65% at pH 7), while adsorption was inhibited under acidic (8-35% at pH 4) and basic (15-35% at pH 10) conditions. The microplastic type with the lowest observed adsorption affinities was PLA. It can be thus be assumed that in the event that this type of microplastic enters water systems, organic pollutants will only adsorb weakly to this material, such&nbsp; that&nbsp; it&nbsp; will&nbsp; have&nbsp; significantly&nbsp; less&nbsp; impact&nbsp; on&nbsp; the&nbsp; transport&nbsp; of&nbsp; the se compounds through the environment, than the other tested&nbsp; types of microplastics. The results obtained in this research demonstrate that the adsorption of the selected&nbsp; groups&nbsp; of&nbsp; organic&nbsp; pollutants&nbsp; on&nbsp; the&nbsp; microplastics&nbsp; investigated&nbsp; is significantly&nbsp; controlled&nbsp; by&nbsp; the&nbsp; physicochemical&nbsp; properties&nbsp; of&nbsp; the&nbsp; tested compounds, such as the dissociation constant, molecule&nbsp; size, hydrophobicity,<br />structural properties, etc. In addition, the characteristics of the water matrix play an important role in controlling adsorption of organic pollutants on microplastic, especially the water pH. In addition, the structure and aging of the polymers had a major influence&nbsp; on their interactions with the selected organic pollutants. The obtained&nbsp; results&nbsp; also&nbsp; demonstrate&nbsp; the&nbsp; difficulty&nbsp; in&nbsp; determining&nbsp; a&nbsp; uniform mechanism&nbsp; of&nbsp; adsorption&nbsp; between&nbsp; the&nbsp; various&nbsp; organic&nbsp; compounds&nbsp; and microplastic particles in water.</p>

La stéatose est la pathologie hépatique la plus répandue dans le monde, touchant environ 25 % de la population générale et jusqu’à 80 % des personnes en surpoids ou obèses. Cette maladie se traduisant par l’enrichissement des hépatocytes en triglycérides, est considérée comme bénigne. Cependant, environ 20 % des personnes atteintes de stéatose développent une stéatohépatite, pathologie caractérisée par une mort cellulaire et une inflammation et représentant un stade favorable au développement du carcinome hépatocellulaire. Les causes et mécanismes impliqués dans la progression de la stéatose vers la stéatohépatite sont encore à préciser. L’obésité, l’exposition aux contaminants environnementaux et la consommation d’alcool sont trois facteurs participant au développement des pathologies hépatiques. Pourtant, l’effet de l’interaction entre ces différents facteurs sur les pathologies hépatiques n’est pas connu. Dans ce contexte, cette thèse a eu pour objectif d’étudier l’impact d’une co-exposition au benzo[a]pyrène (B[a]P), un contaminant carcinogène environnemental, et à l’éthanol, utilisé à de faibles doses, sur les cellules hépatiques WIF-B9, présentant une stéatose préalable. Les résultats obtenus ont permis de démontrer qu’une telle exposition induit une progression de la stéatose hépatique vers un stade apparenté à une stéatohépatite, marquée par une augmentation de la mort cellulaire et de l’inflammation. Nous avons mis en évidence que la mort cellulaire résulterait de l’activation de p53 et d’une peroxydation lipidique. Une activation du récepteur aux hydrocarbures aromatiques et une production de monoxyde d’azote sont à l’origine de ces évènements via une modification du métabolisme de l’éthanol et du B[a]P conduisant à des dommages à l’ADN dépendants de la formation d’anion peroxynitrite. / Steatosis is the most common form of liver disease in the world, affecting around 25 % of the general population and up to 80 % of obese people. The disease is defined by the accumulation of triglycerides in hepatocytes and is generally considered as a benign condition. However, around 20 % of people with steatosis develop steatohepatitis, a disease characterized by cell death and inflammation, a condition that favors the development of hepatocellular carcinoma. The causes and mechanisms involved in the progression from steatosis to steatohepatitis are yet not fully understood. Obesity, exposure to environmental contaminants and alcohol consumption are three major factors contributing to the development of liver diseases. However, is still not yet clear what is the effect of the interaction between these different factors on liver diseases. In this context, the aim of this study was to evaluate the impact of a co-exposure to benzo[a]pyrene (B[a]P), an environmental carcinogenic contaminant, and ethanol, used at low doses, in WIF-B9 hepatic cell line, with a prior steatosis . The results demonstrate that this type of co-exposition induces a progression of hepatic steatosis to a steatohepatitis-like stage, marked by an increased cell death and an inflammation. We have shown that in this condition, cell death results from the activation of p53 and lipid peroxidation. Activation of the aromatic hydrocarbon receptor and production of nitric oxide are the origin of these events by a modification of both ethanol and B[a]P metabolism leading to peroxynitrite-dependent DNA damage.

A novel aryl hydrocarbon receptor nuclear translocator (ARNT)-interacting peptide (Ainpl) was characterized from human liver cDNA library using phage display. Ainpl suppresses hypoxia inducible factor-1a (HIF-1α) signaling pathway through an ARNTdependent manner. HIF-1α is known to be overexpressed in more than 90% of solid tumors, and the inhibition of HIF-1α is proved as an effective approach to suppress tumor growth. ARNT, as the obligatory heterodimeric partner of HIF-1α for downstream gene activation, was used as a bait to screen for Ainpl. Ainpl specifically interacts with the helix-loop-helix (HLH) subdomain of ARNT, but not with HIF-1α. GFP-Ainpl is localized in both cytoplasm and nucleus, and suppresses HIF-1α signaling by two mechanisms: (1) cytoplasmic GFP-Ainp 1 retains ARNT in the cell cytoplasm and (2) nuclear GFP-Ainpl inhibits HIF-1α/ARNT heterodimerization. The suppression of Ainpl on HIF-1α signaling was reversed by introducing ARNT into the cells using transient transfection. We further utilized HIV TAT protein transduction domain to deliver 6His-TAT-Ainpl into three different cancer cell lines (Hep3B, HeLa, MCF-7), and found that 6His-TAT-Ainpl co-localizes with ARNT in the cell nucleus. 6His-TATAinpl can be detected inside the cells after 30 min of transduction, and can reach the maximum level at 2 h. 6His-TAT-Ainp 1 remained detectable in the cells up to 96 h and had a half life of 24 h after transduction. In addition, 6His-TAT-Ainp 1 suppresses HIF-1α downstream genes at both message and protein levels in a dose-dependent manner. Taken together, molecules that target the HIF-1α and ARNT interface can be developed as viable drugs to suppress HIF-1α signaling.

Les procédés plasma-liquide sont considérablement étudiés en raison de leur potentiel élevé dans la production de divers nanomatériaux, parmi d’autres applications technologiques. En plus d'un rendement relativement élevé (mg/min) et d'une infrastructure simplifiée, les mécanismes de synthèse sont directs. Le fait que les produits restent confinés dans la solution, la manipulation de nanomatériaux ne présente un danger ni aux vivants ni à l’environnement. Dans ce mémoire de maitrise, les méthodes les plus courantes pour la synthèse de nanomatériaux, en particulier les systèmes plasma-liquide, sont discutées. La formation de différents régimes de plasma dans des liquides, dont chacun a des caractéristiques et des applications différentes, est présentée. Ensuite, le système multi-liquide et ses caractéristiques, telles que les caractéristiques électriques et la dynamique de l’émission des décharges dans différentes conditions, sont exposés. Pour la synthèse de nanoparticules, on traite les décharges Sparks (étincelles) avec une attention particulière. Au lieu de les produire entre deux électrodes immergées dans un liquide diélectrique, les décharges sont produites dans un hydrocarbure liquide entre une électrode et une solution conductrice. Cette dernière est produite via l’ajout de nitrate d’argent dans l’eau. Le plasma, via ses espèces réactives, réduit les ions Ag+ en Ag0 qui forment ensuite les nanoparticules. La décomposition de l’hydrocarbure produit aussi des espèces carbonées qui se recombinent sous forme d’une matrice hydrocarbonée. En se basant sur différentes méthodes de caractérisations (FTIR, MEB, MET, UV-vis, etc.), nous identifions deux zones de réactions : dans le plasma dans l’heptane et à l’interface plasma-solution. Les produits dans la première zone sont majoritairement des nanoparticules (< 10 nm) d’Ag enrobées dans une matrice de carbone hydrogénée. Cependant, les produits dans la solution sont des nanoparticules d’Ag (sans matrice) ayant une distribution de taille de quelques dizaines de nanomètres. / Plasma-liquid systems are significantly investigated due to their high potential in the production of various nanomaterials, among other technological applications. In addition to relatively high efficiency in production (mg/min) and simplified infrastructure, the mechanisms of synthesis are rather direct. Also, because the products are confined in solution, the handling of the nanomaterials do not present risks to the living or to the environment. In this master thesis, the most common methods for nanomaterial synthesis, in particular plasma-liquid systems, are discussed. Formation of different plasma regimes in liquids, which each of them has different features and application, are explained. Then, the multiple liquid system and their feature such as electrical characteristics and emission dynamic of the discharges at different conditions, are investigated. To produce nanoparticles, we present the Spark discharges with special attention. Instead of their production between two electrodes immersed in a liquid dielectric, the discharges are produced in a liquid hydrocarbon between one electrode and a conductive solution. This latter is prepared by adding silver nitrate to water. The plasma, through its reactive species, reduces the ions Ag+ to Ag0 that produces nanoparticles. The decomposition of the hydrocarbon produces carbonaceous species that recombine as hydrocarbon matrix. Based on the different characterisation techniques (FTIR, SEM. TEM. UV-vis, etc.), we identified two zones of reactions: in plasma in heptane and at the interface plasma-solution. The products in the former zone are majority 10 nm-particles of Ag embedded in a hydrocarbon matrix, while the products in solution are Ag nanoparticles (without matrix) with size of several tens of nanometers.

Le microbiome de la rhizosphère fait généralement référence aux communautés bactériennes, archées et fongiques ainsi qu'à leur matériel génétique entourant étroitement les systèmes racinaires des plantes. Le métagénome de ce microbiome a été appelé le deuxième génome de la plante puisqu’elle est capable de profiter de plusieurs fonctions dont elle manque. La communauté microbienne de la rhizosphère inclue entre autres des microorganismes ayant développé des interactions intimes et spécifiques de longue durée avec les racines des plantes. Il s'agit d'une communauté dynamique de microorganismes, à partir de laquelle une partie d’espèces a développé des interactions intimes et spécifiques de longue durée avec les racines des plantes. Les progrès récents dans l’étude des interactions plantes-microbes ont démontré leur impact considérable sur la croissance, la nutrition et la santé des plantes. Le microbiote de la rhizosphère est complexe avec une structure spatio-temporelle dynamique qui s'adapte rapidement en fonction des stress biotiques et abiotiques. Considérant l’importance du microbiome de la rhizosphère pour la santé des plantes, des informations précises sur leurs microbes associés sont d'une importance capitale pour déchiffrer les mécanismes d'adaptation des plantes aux stress médiés par le microbiome et comprendre comment les plantes recrutent des taxons microbiens clés pour mieux faire face aux conditions stressantes. Pour ce faire, nous avons mené trois études afin de faire la lumière sur les facteurs qui jouent un rôle dans le recrutement et la structure du microbiome de la rhizosphère de plantes dans les milieux stressés. Dans un premier lieu, nous avons testé si des inoculations répétées avec des protéobactéries influençaient la productivité des plantes et les communautés microbiennes associées à la rhizosphère de quatre espèces végétales poussant dans des sédiments contaminés par des hydrocarbures pétroliers. Une expérience de mésocosme a été réalisée en conception de blocs randomisés avec deux facteurs : 1) la présence ou l'absence de quatre espèces végétales collectées dans un bassin de sédimentation d'une ancienne usine pétrochimique, et 2) l'inoculation ou non avec un consortium bactérien composé de dix isolats de Protéobactéries. Les plantes ont été cultivées en serre pendant quatre mois. Le séquençage d'amplicon MiSeq, ciblant le gène de l'ARNr 16S bactérien l’ITS fongique, a été utilisé pour évaluer les structures de la communauté microbienne des sédiments provenant de mesocosmes plantés ou non plantés. Nos résultats ont montré qu’alors que l'inoculation provoquait un changement significatif dans les communautés microbiennes, la présence de la plante et de son identité spécifique avait une influence plus forte sur la structure du microbiome dans les sédiments contaminés par les hydrocarbures pétroliers. Ensuite, en utilisant le même dispositif expérimental, nous avons utilisé le séquençage d'amplicon MiSeq ciblant le gène de l'ARNr 18S pour évaluer les structures communautaires AMF dans les racines et la rhizosphère de plantes poussant dans des substrats contaminés et non contaminés. Nous avons également étudié la contribution de l'identité spécifique des plantes et du biotope (racines des plantes et sol rhizosphérique) dans la formation des assemblages AMF associés. Nos résultats ont montré que si l'inoculation provoquait un changement significatif dans les communautés AMF, la contamination du substrat avait une influence beaucoup plus forte sur leur structure, suivie par le biotope et l'identité végétale dans une moindre mesure. De plus, l'inoculation augmentait considérablement la production de biomasse végétale et était associée à une diminution de la dissipation des hydrocarbures pétroliers dans le sol contaminé. Le résultat de cette étude fournit des connaissances sur les facteurs influençant la diversité et la structure communautaire de l'AMF associée aux plantes en milieux stressés à la suite d’inoculations répétées d'un consortium bactérien. Finalement, nous avons testé l’effet d’une inoculation d’arbres avec des champignons mycorhiziens spécifiques sur leur survie et croissance, ainsi que l’extraction de métaux traces. Pour ce faire, une expérience sur le terrain a été menée dans laquelle nous avons cultivé le clone de Salix miyabeana "SX67" sur le site d'une décharge industrielle déclassée, et inoculé les arbustes avec le champignon arbusculaire mycorhizien Rhizophagus irregularis, le champignon ectomycorhizien Sphaerosporella brunnea, ou un mélange des deux. Après deux saisons de croissance, les saules inoculés avec le champignon S. brunnea ont produit une biomasse significativement plus élevée. Le Ba, le Cd et le Zn se sont avérés être accumulés dans les parties aériennes des plantes, où le Cd présentait les valeurs de facteur de bioconcentration les plus élevées dans tous les traitements. De plus, les parcelles où les saules ont reçu l'inoculation de S. brunnea ont montré une diminution significative des concentrations de Cu, Pb et Sn dans le sol. L'inoculation avec R. irregularis ainsi que la double inoculation n'ont pas influencé de manière significative la production de biomasse et les niveaux d’éléments traces du sol. Le résultat de cette étude apporte des connaissances sur la diversité et l’écophysiologie des microbes de la rhizosphère associés aux plantes de croissance spontanée à la suite d’inoculations répétées. De plus ils montrent le potentiel de l’utilisation de champignons mycorhiziens afin d’améliorer la santé et croissance des plantes dans des milieux pollués et toxiques. Ils soulignent aussi l'importance de la sélection des plantes afin de faciliter leur gestion efficace et accélérer les processus de remise en état des terres. / The rhizosphere microbiome generally refers to the bacterial, archaea, and fungal communities and their genetic material that closely surrounds the root systems of plants. The metagenome of this microbiome has been called the second genome of the plant because it is able to take advantage of several functions that it lacks. It is a vibrant community of microorganisms, from which part of the species has developed long-lasting, specific and intimate interactions with plant roots. Recent advances in the study of plant-microbe interactions have demonstrated their considerable impact on plant growth, nutrition and health. The rhizosphere microbiota is complex with a dynamic spatio-temporal structure which adapts rapidly to biotic and abiotic stresses. Considering the importance of the rhizosphere microbiome to plant health, accurate information about their associated microbes is of utmost importance in deciphering the mechanisms of plant adaptation to microbiome-mediated stress, and understanding how plants recruit key microbial taxa to better cope with stressful conditions. To do this, we conducted three studies to shed light on the factors that play a role in the recruitment and structure of the microbiome of the rhizosphere of plants in stressed environments. First, we tested whether repeated inoculations with Proteobacteria influenced the productivity of plants and the microbial communities associated with the rhizosphere of four plant species growing in sediments contaminated with petroleum hydrocarbons. A mesocosm experiment was carried out in design of randomized blocks with two factors: 1) the presence or absence of four plant species collected in a sedimentation basin of a former petrochemical plant, and 2) inoculation or not with a bacterial consortium made up of ten isolates of Proteobacteria. The plants were grown in the greenhouse for four months. MiSeq amplicon sequencing, targeting the bacterial 16S rRNA gene and the fungal ITS, was used to assess the microbial community structures of sediments from planted and unplanted microcosms. Our results showed that while inoculation caused a significant change in microbial communities, the presence of the plant and its specific identity had a stronger influence on the structure of the microbiome in sediments contaminated with petroleum hydrocarbons. Next, using the same experimental setup, we used MiSeq amplicon sequencing targeting the 18S rRNA gene to assess AMF community structures in the roots and rhizosphere of plants growing in contaminated and uncontaminated substrates. We also studied the contribution of the specific identity of plants and the biotope (plant roots and rhizospheric soil) in the formation of associated AMF assemblages. Our results showed that while inoculation caused a significant change in AMF communities, substrate contamination had a much stronger influence on their structure, followed by biotope and plant identity to a lesser extent. In addition, inoculation dramatically increased plant biomass production and was associated with decreased dissipation of petroleum hydrocarbons in contaminated soil. The result of this study provides knowledge on the factors influencing the diversity and community structure of AMF associated with plants in stressed environments following repeated inoculations of a bacterial consortium. Finally, we tested the effect of inoculating trees with specific mycorrhizal fungi on their survival and growth, as well as the extraction of trace metals. To do this, a field experiment was carried out in which we cultivated the Salix miyabeana "SX67" clone on the site of a decommissioned industrial landfill and inoculated the shrubs with the arbuscular mycorrhizal fungus Rhizophagus irregularis, the ectomycorrhizal fungus Sphaerosporella brunnea, or a mixture of both. After two growing seasons, willows inoculated with the fungus S. brunnea produced a significantly higher biomass. Ba, Cd and Zn were found to accumulate in the aerial parts of plants, where Cd had the highest bioconcentration factor values in all treatments. In addition, the plots where the willows were inoculated with S. brunnea showed a significant decrease in the concentrations of Cu, Pb and Sn in the soil. The inoculation with R. irregularis as well as the double inoculation did not significantly influence the biomass production and the soil trace elements levels The result of this study provides insight into the diversity and ecophysiology of rhizosphere microbes associated with spontaneously growing plants following repeated inoculations. In addition, they show the potential of using mycorrhizal fungi to improve plant health and growth in polluted and toxic environments. They also stress the importance of plant selection to facilitate their efficient management, in order to speed up land reclamation processes.

In this thesis, it has been studied the deamination of aromatic amines, through in situ formed diazonium salts as reaction intermediates, catalyzed by salicylic acid, a nontoxic, eco-friendly and economic catalyst. In the early part of the thesis (Chapter I) it has studied the deamination process using THF as solvent as hydrogen donor and anilines as radical source, to carry the hydrodeamination reaction, as well as the process in its deuterodeamination manner using deuterated solvent. Following with this study in Chapter II and Chapter III, it has been studied the addition of the aromatic radicals, generated with the methodology employed in the first chapter, to different types of double bond, to form α-arylketones (Chapter II) and γ-aryl lactones, throw a following intramolecular cyclization (Chapter III). Finally, in Chapter IV was studied the construction of arylphosphonates, starting from anilines as radical source, and triphenylphosphite, and in this case specially, mechanism was hard explored. In every work, the methodologies could be scaled-up above 1 g, reaction mechanisms were proposed and studied through control and mechanistical experiments, and follow reactions were carried out.

No description available.

The late Middle Jurassic (Callovian) Entrada Sandstone has been divided into two general facies associations consisting primarily of eolian sandstones in eastern Utah and "muddy" redbeds in central Utah. Sedimentary structures within the redbed portion are explained by the interfingering of inland sabkha, alluvial, and eolian depositional systems. A complete succession from the most basinward facies to the most terrestrial facies in the Entrada Sandstone consists of inland sabkha facies overlain by either alluvial or eolian facies. Where both alluvial and eolian facies interfinger, alluvial facies overlain by eolian facies is considered a normal succession. Sequence boundaries, often identified by more basinward facies overlying more landward facies, are observed in the Entrada Sandstone and are extrapolated for the first time across much of Utah, including both the eolian-dominated and redbed-dominated areas. Using these sequence boundaries as well as recent tephrochronologic studies, three time correlative surfaces have been identified in the Entrada. Based on the facies interpretations at each surface, five paleogeographic reconstructions and five isopach maps have been created, illustrating two major intervals of erg expansion and the location of the Jurassic retroarc foreland basin's potential forebulge. Eolian (erg-margin) sandstones pinch-out into muddy redbeds creating combination traps, as evidenced by dead oil (tar) and bleached eolian sandstone bodies within the Entrada. The Entrada Sandstone is a world-class analog for similar systems, such as the Gulf of Mexico's Norphlet Sandstone, where eolian facies grade into muddy redbed facies.

Introduction: L'étude des biomarqueurs a le potentiel de documenter sur les mécanismes sous-jacents de l'étiologie du cancer du poumon. Dans cette étude, nous avons étudié l’association entre la méthylation de l’ADN dans les gènes F2RL3 et AHRR et le cancer du poumon. Méthodes: Une étude cas-témoin avec échantillonnage cumulatif a été nichée dans la cohorte CARTaGENE. Les cas (N=187) se composent de tous les participants diagnostiqués avec un cancer du poumon incident entre le début de la cohorte (2009) et 2015 et qui avaient fourni un échantillon de sang; les témoins (N=378) ont été échantillonnés à la fin du suivi parmi les non-malades selon un appariement fréquentiel (2:1) pour l'âge, le sexe et le moment du prélèvement sanguin. Sequenom EpiTYPER® a été utilisé pour quantifier les niveaux de méthylation dans sept et 33 sites CpG de F2RL3 et AHRR, respectivement. Les rapports de méthylation de l'ADN sur tous les sites CpG individuels et en tant que mesure moyenne ont été paramétrés à la fois comme variables continues et catégorielles. Une régression logistique multivariable non conditionnelle a été utilisée pour estimer les rapports de cotes (OR) et les intervalles de confiance (IC) à 95 % de l’association entre la méthylation de F2RL3 et AHRR et le cancer du poumon tout en contrôlant les facteurs de confusion identifiés à l'aide de graphiques acycliques dirigés. Résultats: Une forte association inverse entre les niveaux moyens de méthylation de l'ADN et le cancer du poumon a été observée pour F2RL3 (OR par écart type (SD) de changement de méthylation = 0,65, IC à 95 %: 0,53-0,80) et AHRR (OR par SD de changement de méthylation = 0,66, IC à 95 %: 0,53 à 0,80). De même, les sites CpG individuels ont montré des ORs (par SD de changement de méthylation) allant de 0,61 à 0,70 pour six des sept sites CpG de F2RL3 et de 0,57 à 0,79 pour 17 des 33 sites CpG de AHRR. Les sites CpG restants de F2RL3 et AHRR n'ont montré aucune association avec le risque de cancer du poumon, à l'exception d'un site CpG dans AHRR (chr5:369774) qui avait un OR de 1,25 (IC à 95 %: 1,02-1,54). Conclusion : Ces résultats confirment le rôle des mécanismes épigénétiques dans l'étiologie du cancer du poumon. / Background: The study of biomarkers has the potential to inform on underlying mechanisms in lung cancer etiology. In this study, we investigated DNA methylation in the F2RL3 and AHRR genes, and lung cancer risk. Methods: A case-control study with cumulative sampling was nested in the CARTaGENE cohort. Cases (N=187) consisted of all participants diagnosed with incident lung cancer from baseline to 2015 and who had provided a blood sample; controls (N=378) were sampled at a ratio of 2:1 with frequency-matching by age, sex, and timing of blood sampling. Sequenom EpiTYPER® was used to quantify methylation levels in seven and 33 CpG sites of F2RL3 and AHRR, respectively. DNA methylation ratios across all individual CpG sites and as an average measure were parametrized both as continuous and categorical variables. Unconditional multivariable logistic regression was used to estimate odds ratios (ORs) and 95% confidence intervals (CI) for lung cancer associated with F2RL3 and AHRR methylation while controlling for confounders identified using directed acyclic graphs. Results: A strong inverse relationship between average DNA methylation levels and lung cancer was observed for both F2RL3 (OR per standard deviation (s.d.) in methylation change = 0.65, 95% CI: 0.53-0.80) and AHRR (OR per s.d. in methylation change = 0.66, 95% CI: 0.53-0.80). Similarly, ORs for individual CpG sites (per s.d. in methylation change) ranged from 0.61-0.70 for six out of the seven CpG sites of F2RL3 and from 0.57-0.79 for 17 out of 33 CpG sites of AHRR. The methylation levels of the remaining CpG sites within F2RL3 and AHRR were not associated with lung cancer risk, except for one CpG site within AHRR (chr5:369774) which had an OR of 1.25 (95% CI: 1.02-1.54). Conclusion: These findings support the role of epigenetic mechanisms in lung cancer etiology.