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Development of Soft Chemical Processes: Preparation of TiO(2) Films and Powders at Low TemperatureGutiérrez Tauste, David 25 April 2008 (has links)
El processament convencional de materials d'òxid de titani (TiO2) inherentment implica un consum energètic important i ha esdevingut una limitació tecnològica per a la fabricació de dispositius emprant substrats termolàbils així com per a la preparació de materials híbrids orgànic/TiO2. Aquesta tesi doctoral tracta del desenvolupament de processos químics per a la preparació de capes i pols de TiO2 d'acord amb principis de Química Verda, posant especial èmfasi en el processament a baixa temperatura. Plantejaments simples, benignes amb el medi ambient i de baix cost són els desitjats sota aquestes directrius. A més a més, els mètodes a baixa temperatura (idealment fins a un màxim proper a 100ºC) haurien de donar lloc a materials que exhibeixin propietats similars a aquells processats a alta temperatura o tractats solvotermalment. S'ha focalitzat especial interès en la recerca d'aplicacions pràctiques dels materials produïts en camps com la conversió d'energia solar i materials actuadors. / El procesamiento convencional de materiales de óxido de titanio (TiO2) inherentemente implica un consumo energético importante y ha resultado una limitación tecnológica para la fabricación de dispositivos utilizando substratos termolábiles así como para la preparación de materiales híbridos orgánico/TiO2. Esta tesis doctoral trata el desarrollo de procesos químicos suaves para la preparación de capas y polvos de TiO2 de acuerdo con principios de Química Verde, poniendo especial énfasis en el procesamiento a baja temperatura. Planteamientos simples, benignos con el medioambiente y de bajo conste son los deseados bajo estas directrices. Además, los métodos a baja temperatura (idealmente hasta un máximo próximo a 100ºC) deberían dar lugar a materiales que exhiban propiedades similares a aquellos procesados a alta temperatura o tratados solvotermalmente. Se ha centrado especial interés en la búsqueda de aplicaciones prácticas de los materiales producidos en campos como la conversión de energía solar y materiales actuadores. / Conventional high-temperature processing of titanium dioxide (TiO2) materials inherently implies important energy consumption and has became a technological limitation for fabricating devices employing thermolabile substrates as well as preparing hybrid organic/TiO2 materials. This PhD thesis deals with the development of chemical processes for preparing TiO2 films and powders fitting Green Chemistry principles, putting special emphasis on low-temperature processing. Simple, environmentally benign and low-cost approaches are desired upon these guidelines. Moreover, low-temperature methods (ideally up to a maximum closer to 100ºC) should give rise to materials exhibiting properties similar than those processed at high temperature or solvothermally treated. Special interest has been focused on finding practical applications of the as-prepared materials in fields such as solar energy conversion and actuating materials.
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Fotokatalitička stabilnost odabranih aktivnih komponenata kardiovaskularnih lekova: kinetika, mehanizam i toksičnost intermedijera / Photocatalytic stability of selected active components of cardiovascular drugs: kinetics, mechanism and toxicity of the intermediatesArmaković Sanja 01 July 2016 (has links)
<p>Ispitana je direktna i indirektna razgradnja odabranih β-blokatora (metoprolol- tartarata, MET i propranolol-hidrohlorida, PRO) kao i diuretika (hidrohlortiazida, HCTZ) i njegovog stabilnog intermedijera hidrolize 4-amino-6-hlor-1,3-benzendisulfonamida (ABSA). Praćena je i kinetika razgradnje direktnom i indirektnom fotolizom uz primenu UVA, UVC, sunčevog i simuliranog sunčevog zračenja (SSZ). Najpre je ispitana stabilnost MET pod dejstvom SSZ, UVA, UVC, UVA/H<sub>2</sub>O<sub>2 ,</sub> i UVA/ BrO<sub>3</sub><sup>-</sup>. Dalje je ispitana efikasnost razgradnje MET pod dejstvom O<sub>3</sub>i UVC/O<sub>3.</sub> Identifikovano je deset intermedijera tokom UVC, O<sub>3 </sub>i UVC/O<sub>3</sub> razgradnje, pri čemu samo jedan ima značajno višu toksičnost prema algama i bakterijama u odnosu na ostale. Efikasnost fotokatalitičke razgradnje MET je ispitana u TiO<sub>2</sub> suspenzijama sa komercijalnim katalizatorima (Wackherr i Degussa P25). Mehanizam fotokatalitičke razgradnje je detaljno ispitan, pri čemu je identifikovano četrnaest intermedijera. EC<sub>50</sub> vrednost MET i njegovih smeša nastalih pri fotokatalitičkoj razgradnji su određene na tri ćelijske linije sisara (H-4-II-E, HT-29 i MRC-5). Kako bi se povećala efikasnost rocesa fotokatalitičke razgradnje primenom komercijalnih katalizatora, ispitan je uticaj prisustva elektron-akceptora u suspenziji, pri čemu je upoređen uticaj O<sub>2</sub>/H<sub>2</sub>O<sub>2</sub>, i O<sub>2</sub>/ BrO<sub>3</sub><sup>-</sup> na mehanizam razgradnje. Na osnovu teorije funkcionala gustine stekao se uvid u promene unutar molekula MET u prisustvu reaktivnih radikala. Takođe, ispitana je efikasnost nedopiranih TiO<sub>2</sub> , kao i dopiranih La(III) nanoprahova sintetisanih sol−gel postupkom, u razgradnji MET. Uticaj temperature kalcinacije na fotokatalitičku efikasnost TiO 2 nanoprahova dopiranih pomoću La(III) ispitana je na supstratima MET i PRO, pri čemu je analiziran i uticaj strukture polaznog jedinjenja na informacija efikasnost fotokatalitičke razgradnje. Rezultati su upoređeni sa nedopiranim TiO<sub>2 </sub>nanoprahom i TiO<sub>2 </sub>Degussa P25 (pri pH-vrednosti 9). Pored toga, ispitana je kinetika i toksičnost PRO i njegovih intermedijera nastalih tokom razgradnje sa TiO<sub>2 </sub>Degussa P25. Ispitan je i uticaj strukture polaznog jedinjenja (MET, HCTZ i ABSA) na fotorazgradnju pod dejstvom UVA, sunčevog i simuliranog sunčevog zračenja, u odsustvu/prisustvu TiO<sub>2</sub> Degussa P25. Takođe, ispitan je i sinergistički efekat MET i ABSA na proces hidrolize, direktne fotolize i fotokatalize sa SSZ/TiO<sub>2 </sub>Degussa P25. Kako bi se stekao uvid u toksičnost proučavanih sistema, ispitan je njihov uticaj na rast odabranih ćelijskih linija sisara.</p> / <p>Direct and indirect degradation of selected β-blockers (metoprolol tartrate, MET and propranolol hydrochloride, PRO) and also diuretic (hydrochlorothiazide, HCTZ) in addition to its stable hydrolysis intermediate 4-amino-6-chloro- 1,3-benzenedisulfonamide (ABSA) were investigated. The kinetics of their degradation obtained by direct and indirect photolysis under UVA, UVC, sunlight and simulated sunlight irradiation (SSI) have been followed. Firstly, the stability of MET under influence of SSI, UVA, UVC, UVA/H<sub>2</sub>O<sub>2</sub> , and UVA/ BrO<sub>3</sub><sup>-</sup> has been investigated. Further, the efficiency of MET degradation under influence of O<sub>3</sub>, and UVC/O<sub>3</sub> has been explored. Ten intermediates have been identified during the UVC, O<sub>3</sub>, and UVC/O<sub>3</sub> treatments, while only one intermediate had significantly higher toxicity towards the algae and bacteria in respect to the others. Efficiency of photocatalytic degradation of MET was investigated in TiO<sub>2</sub> suspensions with commercial catalysts (Wackherr and Degussa P25). Mechanism of photocatalytic degradation was investigated in detail according to which fourteen intermediates were identified. EC 50 value of MET and its mixtures formed during the photocatalytic degradation has been determined at three mammalian cell lines (H-4-II-E, HT-29, and MRC-5). In order to improve the efficiency of photocatalytic degradation process applying commercial catalysts, the influence of presence of electron acceptors in suspension has been investigated and the influence of O<sub>2</sub>/H<sub>2</sub>O<sub>2 </sub>and O<sub>2</sub>/BrO<sub>3</sub><sup>-</sup> to the mechanism of degradation has been compared. Based on the density functional theory an insight to the changes within MET molecule in the presence of reactive radicals has been made. Also, the efficiency of bare TiO<sub>2</sub>, as well as doped La(III) nanopowders synthesized by sol-gel procedure, in the degradation of MET has been investigated. The influence of calcination temperature on hotocatalytic efficiency of TiO<sub>2 </sub>nanopowders doped with La(III) has been studied on the MET and PRO substrates, and the influence of structure of the starting compound on the efficiency of photocatalytic degradation had been analyzed. Results have been compared with bare TiO<sub>2 </sub>nanopowder and TiO<sub>2</sub> Degussa P25 (at pH value of 9). Besides, kinetics and toxicity of PRO and its intermediates formed during the degradation with TiO<sub>2</sub> Degussa P25 have been investigated. The influences of starting compound’s structure (MET, HCTZ, and ABSA) to photodegradation under UVA, sunlight and SSI, in the absence/presence of TiO<sub>2</sub> Degussa P25, have been investigated. Also, the synergistic effects of MET and ABSA to the process of hydrolysis, direct photolysis, and photocatalysis with SSI/TiO<sub>2</sub> Degussa P25 have been investigated. In order to get an insight into the toxicity of the studied systems, their influence on the growth of selected mammalian cell lines has been investigated as well.</p>
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