<p>Ispitana je kinetika i mehanizam fotokatalitičke&nbsp;razgradnje herbicida kvinmeraka i klomazona u prisustvu&nbsp;UV/TiO₂&nbsp; Degussa P25, odnosno piklorama i&nbsp; klopiralida&nbsp;<br />primenom UV/TiO₂&nbsp; Wackherr pri različitim&nbsp;eksperimentalnim uslovima. Praćena je i kinetika&nbsp;razgradnje odabranih herbicida direktnom fotolizom uz&nbsp;primenu sunčevog, UV i vidljivog zračenja, kao i u&nbsp;odsustvu svetlosti. Pored toga, upoređena je efikasnost&nbsp;<br />UV/TiO₂&nbsp; Degussa P25, odnosno UV/TiO₂&nbsp; Wackherr sa&nbsp;vidljivim zračenjem, kao i direktnom fotolizom u&nbsp;prisustvu pomenutih izvora svetlosti.&nbsp; U cilju procene&nbsp;<br />citotoksičnosti klomazona i klopiralida, kao i sme&scaron;e&nbsp;klomazona i klopiralida i njihovih intermedijera nastalih&nbsp;tokom fotokatalitičke razgradnje ispitan je&nbsp; in vitro&nbsp; rast&nbsp;<br />ćelijskih linija&nbsp; MRC-5 i H-4-II-E.&nbsp; Nakon ispitivanja&nbsp;fotokatalitičke razgradnje odabranih herbicida u dvaput&nbsp;destilovanoj vodi, praćena je njihova razgradnja i u&nbsp;prirodnim vodama. Takođe, ispitan je uticaj dodatka&nbsp;hidrogenkarbonata i huminske kiseline na efikasnost&nbsp;razgradnje odabranih herbicida. Fotokatalitička razgradnja&nbsp;klomazona, piklorama i mekopropa je ispitivana i u&nbsp;prisustvu UV/TiO₂&nbsp; nanocevi. Aktivnost katalizatora TiO_2&nbsp;Wackherr&nbsp; i TiO₂&nbsp; nanocevi je upoređena sa TiO₂&nbsp; Degussa&nbsp;P25.</p> / <p>The kinetics and mechanism of photocatalytic degradation&nbsp;of the herbicides quinmerac and clomazone in the&nbsp;presence of UV/TiO₂&nbsp; Degussa P25, and of picloram and&nbsp;clopyralid using UV/TiO₂&nbsp; Wackherr under different&nbsp;experimental conditions were studied. The kinetics of&nbsp;degradation of selected herbicides by direct photolysis&nbsp;using sunlight, UV and visible radiation, and in the&nbsp;absence of light were followed. In addition, the&nbsp;efficiencies of UV/TiO₂&nbsp; Degussa P25 and UV/TiO_2&nbsp;Wackherr &nbsp;were compared with visible radiation and direct&nbsp;photolysis in the presence of the above mentioned light&nbsp;sources. In order to evaluate the cytotoxicity of clomazone&nbsp;<br />and clopyralid alone and in their mixture with&nbsp;intermediates formed during the photocatalytic&nbsp;degradation, in vitro growth of cell lines, MRC-5 and H-4-II-E was followed. After examining&nbsp; the photocatalytic&nbsp;degradation of selected herbicides in double distilled&nbsp;water, their decomposition in natural waters was also&nbsp;followed. Also, the influence of hydrogencarbonate and&nbsp;humic acid addition on the efficiency of degradation of&nbsp;selected herbicides was studied. Photocatalytic&nbsp;degradations of clomazone, picloram and mecoprop were&nbsp;investigated in the presence of UV/TiO_2&nbsp;nanotubes. Activities of the catalysts TiO₂&nbsp; Wackherr and TiO_2&nbsp;nanotubes were compared to TiO₂ Degussa P25.</p>

Rhizomania, caused by beet necrotic yellow vein virus (BNYVV), has been considered as an economically important disease around the world because of the extreme reduction in sugar beet yield and sugar content in affected plants. The spread of rhizomania all over the world, including the emergence of resistance- breaking virus isolates, have been become a major concern for the plant pathologists and plant breeders aiming at improving sugar beet resistance to   BNYVV as well as better understanding sugar beet-virus interactions during disease development. The main focus of this project is to elucidate the role of P25-interacting partner, the VIP1 transcription factor, in activation of transcription.  The isolation of the gene-of-interest (VIP1) was performed by RT-PCR on total RNA preparations extracted from root tissue of sugar beet (Beta vulgaris ssp. vulgaris).  The isolated gene of interest was cloned using gateway system into a binary expression vector and the obtained construct was then transformed into Agrobacterium tumefaciens for analysing transient expression in the experimental host (Nicotinana benthamiana).  Dual-luciferase promoter activity assay was performed on isolated leaf discs co-expressing P25 and VIP1 and compared to appropriate controls.  Six promoter constructs were tested. However, we observed an increase in luciferase activity (1.8-4.2-fold) upon co-expression of P25 and VIP1 only for two constructs tested, although the increase was not supported by Student’s t-test at 0.05 significance level. Nevertheless, the luciferase activity assay data for these two constructs were consistent with RNA-seq and RT-qPCR data obtained previously showing upregulation of the expression of these two specific sugar beet genes during BNYVV infection in sugar beets.     Thus, the results support our hypothesis that the interaction of the virus virulence factor P25 with VIP1 transcription factor is needed to activate transcription of certain genes in the nucleus for the virus benefit.

Spurred by change in government regulations and to leverage lower-cost technology and services, many land mobile radio (LMR) operators have begun transitioning from circuit-switched to packet-switched backbone networks to handle their future communication needs. Due to the unique demands of packet-switched backbone networks for LMR, it may not be wise to carry over the previously implemented security methods used with circuit-switch systems or to treat an LMR backbone as a regular packet-switched network. This thesis investigates security in packet-switched LMR backbone networks to identify security issues in packet-switched LMR networks and provide possible solutions for them. Security solutions that are examined include different types of virtual private networks (VPNs), various encryption and keying procedures for safe communication, and logic behind how and where to implement security functions within the network. Specific schemes examined include IP Security (IPSec), OpenVPN, Virtual Tunnel (VTun), and Zebedee. I also present a quantitative analysis of the effects that the solutions have on packet-switched networks, in terms of link utilization, and on voice traffic, in terms of delay and delay jitter. In addition, I evaluate, in general terms, the additional cost or complexity that is introduced by the different security solutions. Simulation with OPNET Modeler was used to evaluate how the various security schemes affect voice communication and network performance as a whole. Since OPNET Modeler does not provide models of security functions, the source code of the transceiver system models was modified to introduce additional overhead that is representative of the various security solutions. Through experimentation, simulation, and analysis of the security schemes considered, it was found that the most effective security scheme overall for a packet-switched LMR backbone network would either be IPSec or OpenVPN implemented at the base stations and end-hosts. Both security schemes provide strong encryption, flexibility, and are actively supported. However, if bandwidth is scarce and flexibility is less important, then a security solution with less overhead, such as VTun, should be considered. Thus, one has to balance performance with security to choose the most effective security solution for a particular application. / Master of Science

During this project, photocatalytic material, nano sized titanium dioxide, was introduced into poly (lactic acid) to produce functional surface capable of self-cleaning property. Samples containing 0%, 5%, 10%, 15% and 20% titanium dioxide were prepared and etched with proteinase K to expose the nano particles on the surface. It was shown that the nano titanium dioxide could dispersed in the polymer matrix pretty well, it was also found that the nano particles affected the thermal and mechanical properties of the polymer matrix differently , due to difference in concentrations of nano filler. The self-cleaning property was evaluated by decolouration of stains caused by coffee and red wine, also by detecting degradation of methylene blue via a UV-vis spectrophotometer. By measuring changes in absorbance of light at 664nm wavelength after a maximum of 24h UV irradiation, it was possible to measure the degradation property of the samples. / Program: Masterutbildning i textilteknik

This diploma thesis aims to optimalization the process of magnetron sputtering and creating of thin layers for use in advanced oxidation processes. During the work was created range of TiOx layers. For this process was used physical method of sputtering called PVD. The photocatalytic activity of the deposited films was tested by degradation of organic dyes Acid Orange 7. Furthermore, the layer was analyzed on surface morphology (SEM) and the layer thickness (profilometry). Study of created layers was focused on the link between the characteristics of each layer, deposition parameters and photocatalysis properties. Based on these results, the layers were applied in a system using AOP for the decomposition of organic substances. The first chapter is devoted to a summary of existing knowledge of photocatalysis and its principles. Another chapter is devoted to the theory and methods of applying thin layers and summary of knowledge of the low-pressure discharges. In the exprimental section there are described various components of the apparatus. Furthermore, the experimental part of the work focuses on the analysis of the optimization process of applying thin layers on titanium oxide. The last chapter of the thesis contains the results of the experiments on the basis of is designed another research progress of this issue.

La tristeza es la enfermedad viral más grave del cultivo de los cítricos y su agente causal es el virus de la tristeza de los cí­tricos (CTV). CTV induce uno o más de los siguientes sí­ndromes: I) decaimiento y muerte de los naranjos dulces (ND), pomelos y mandarinos injertados sobre el patrón naranjo amargo (NA), sí­ndrome conocido como "tristeza", II) enanismo, acanaladuras en la madera y fruta de pequeño calibre (stem pitting, SP), y III) enanismo y amarillamiento de plantas de semilla de limonero, pomelo y NA (seedling yellows, SY). La gama de huéspedes de CTV es muy restringida y hasta hace poco no se conocí­a ningún huésped herbáceo experimental. Actualmente, se sabe que la agroinfiltración de Nicotiana benthamiana, con clones de DNA complemantario (cDNA) del aislado T36 de CTV produce la infección sistémica de la planta, acompañada de sí­ntomas similares a los inducidos en cí­tricos, si bien la infección no queda limitada al floema. El aislado T36 induce SY y SP de lima Mejicana (LM), pero no en otros huéspedes como pomelo o ND. El estudio de los determinantes genéticos responsables de la inducción del sí­ndrome de SP requerí­a desarrollar un sistema genético basado en clones agroinfecciosos de un aislado inductor de estos sí­ntomas, como el aislado español T318A. Para ello, se partió de clones de cDNA de longitud completa de T318A previamente desarrollados en el laboratorio, capaces de replicarse en hojas de N. benthamiana pero incapaces de inducir infección sistémica y que presentaban varias mutaciones en su proteína de cápsida minoritaria p27. La corrección de dichas mutaciones y la construcción de nuevos clones de longitud completa de T318A marcados con el gen gfp, mostraron una correcta replicación en hojas agroinfiltradas de N. benthamiana, pero resultaron incapaces de inducir infección sistémica en este huésped experimental. La respuesta diferencial de N. benthamiana frente a distintas cepas de CTV permite estudiar los factores implicados en la interacción virus-huésped. Se analizó la interacción de las proteí­nas virales p20 y p25 de los aislados T36 y T318A con proteí­nas de N. benthamiana utilizando un abordaje consistente en: i) la expresión transitoria de p20/p25 marcadas con una etiqueta Strep-Tag en hojas de N. benthamiana, ii) purificación de los complejos proteí­na CTV-proteína huésped y análisis interactómico de los datos, y iii) estudio de la interacción directa entre p20/p25 y proteínas seleccionadas del huésped mediante análisis del doble hibrido en levadura y complementación bimolecular de fluorescencia (BIFC). Este abordaje proteómico mostró claras diferencias entre aislados que pueden explicar, en parte, el comportamiento diferencial de los aislados T36 y T318A en dicho huésped experimental. La inducción el síndrome de decaimiento por parte de CTV ha obligado a utilizar patrones tolerantes al decaimiento. Dichos patrones son menos adecuados. Las plantas de cí­tricos propagadas sobre NA e infectadas por CTV muestran necrosis en los tubos cribosos y disminución del floema funcional. Éstos desórdenes podrí­an ser consecuencia de la activación de los mecanismos de defensa como la reacción de hipersensibilidad desencadenada por la ruta del ácido salicí­lico o el silenciamiento génico mediado por RNA (post-transcriptional gene silencing, PTGS). Con el objetivo de avanzar en el mecanismo molecular de la resistencia del NA a la infección por CTV, se estudió el papel de diferentes genes de la planta implicados en las rutas mediante el uso de un vector viral basado en el genoma del virus del manchado foliar de los cítricos (citrus leaf blotch virus, CLBV). El silenciamiento génico de las rutas del AS o del PTGS en plantas NA y la inoculación de tres aislados de CTV patogénicamente diferentes mostró la implicación de ambas rutas en la defensa del NA frente a CTV. / Tristeza is the most important viral disease affecting citrus plants and Citrus tristeza virus (CTV) is the causal agent of this disease. CTV induces at least one of this syndromes: I) decline and death of sweet orange (SwO), grapefruits and mandarin trees grafted on sour orange (SO) rootstock, this syndromes is known as "tristeza", II) stunting, stem pitting (SP) and small fruits, and III) stunting and leaf chlorosis of lemon, grapefruit and SO seedlings (seedling yellows, SY). The host range of CTV is restricted and until recently no experimental herbaceous host was known. The agroinoculation Nicotiana benthamiana with clones of complementary DNA (cDNA) from the CTV isolate T36 cause the systemic infection of the plant and similar symptoms to those observed in citrus, although the infection is not limited to the phloem. T36 isolate induces SY and SP of Mexican lime (ML), but not in other hosts such as grapefruit and SwO. Therefore, to study the genetic determinants responsible of the SP syndrome induction was necessary to develop a genetic system based on agroinoculated clones from an isolate able to induce these symptoms, such as the Spanish isolate T318A. To do this, full length cDNA clones from T318A were obtained. They are able to replicate in N. benthamiana leaves but unable to induce systemic infection and showed several mutations in their protein of the minor coat, p27. The correction of these mutations and the construction of new clones of complete length from T318A labeled with the gfp gene, showed a proper replication in agroinoculated leaves of N. benthamiana, but they were still unable to induce systemic infection in this experimental host. The differential response of N. benthamiana to different CTV strains allows the study of the potential factors involved in the virus-host interaction. The aim of this work was study the interaction between the viral proteins p20 and p25 from the isolates T36 and T318A with N. benthamiana proteins with an analysis consisted in: I) the transitory expression of p20/p25 fused to Strep-Tag in N. benthamiana leaves, II) purification of the CTV protein-host protein complex and interatomic analysis of the data, and III) the study of the direct interaction between p20/p25 and selected plant proteins by the analysis of the double hybrid in yeast and bimolecular complementation of fluorescence (BIFC). The proteomic analysis showed strong differences between isolates that may partially explain the differential behavior of the T36 and T318A isolates in this experimental host. The induction of decline syndrome by CTV in citrus has leaded the use of tolerant rootstocks to decline. However, the use of such rootstocks is less suitable. Citrus plants propagated on SO rootstock and infected by CTV show phloem necrosis below the bud union that reduces the flow of carbohydrates to the roots. These symptoms may be a consequence of the activation of defense pathways in the plant, such as the hypersensitive reaction, hormone salicylic acid (SA) pathways or the RNA mediated post-transcriptional gene silencing (PTGS). Their relation is essential to know their implication in the decline. Therefore, the role of different genes involved in SA and PTGS has been studied by the silencing of plant genes using a viral vector (VIGS) based in the genome of the citrus leaf blotch virus (CLBV). The gene silencing of the SA and PTGS in SO and the inoculation of three different pathogenicity CTV isolates showed that both pathways are involved in the SO defense against CTV. The analysis of the proteins p20, p23 and p25 as possible suppressors of the AS indicating that the more virulent CTV isolates possess the more powerful suppressors. / La Tristesa és la malaltia viral més greu del cultiu dels cítrics. CTV induïx un o més de les sí­ndromes següents: I) decaïment i mort de taronger dolç§ (ND), pomelo i mandariner empeltats sobre el patró taronger amarg (NA), sí­ndrome conegut com "Tristesa", II) nanisme, estries en la fusta i fruita de xicotet calibre (SP) i III) nanisme i tonalitat groguenta de plantes de llavor de llimera, pomelo i taronger amarg (SY). El rang d'hostes de CTV és molt restringit i fins fa poc no es coneixia cap hoste herbaci experimental. Actualment es sap que la infecciò sistèmica en Nicotiana benthamiana amb clons de DNA complementari (cDNA) de l`aïllat de T36 provoca la infecció sistemàtica de la planta, acompanyada de síntomes similars als induïts en cí­trics, si be la infecció no queda llimitada al floema. L' aïllat T36 induïx SY i estries en la fusta de Llima Mexicana (LM), però no en altres hostes com a pomelo, ND o NA, l'estudi dels determinants genètics responsables de la inducció de la síndrome de SP requeria desenvolupar un sistema genètic basat en clons agroinfecciosos d'un aïllat inductor d'estos sí­mptomes, com l'aïllat espanyol T318A. Per a això, es va partir de clons de cDNA longitud completa de T318A prèviament desenvolupats al laboratori, capaços de replicar-se en fulls de N. benthamiana però incapaços d'induir infecció sistèmica i que presentaven varies mutacions en la seua proteïna de càpsida minoritatia p27. La correcció d`aquestes mutacions i la construcció de nous clons T318A de longitud completa marcats amb el gen gfp, van mostrar una correcta replicació en fulls agroinfiltradas de N. benthamiana però van resultar incapaços d'induir infecció sistèmica en aquest hoste experimental. La resposta diferencial dependent d'aïllat en N. benthamiana front CTV permet estudiar els possibles factors de la interacció virus- hoste. Es va dur a terme l'estudi de la funció de les proteínes virals p20 i p25 dels aïllats T36 i T318A amb proteïnes de N. benthamiana utilitzant un abordatge consistent en: i) l' expressió transitòria de les dues proteïnes p20/p25 marcades amb una etiqueta Strep-Tag en fulls de N. benthamiana, ii) purificació dels complexos proteïna CTV-proteïna hoste i anàlisi interactómic de les dades, i iii) estudi de la interacció directa per mitjà  de doble híbrid en llevat i complementació bimolecular de fluorescència (BIFC) de les proteïnes virals i determinades proteïnes de N. benthamiana. Aquest abordatge proteòmic va mostrar clares diferències entre aïllats que poden explicar el comportament diferencial dels aïllats T36 i T318A en aquest hoste experimental. La inducció de la sí­ndrome de decaïment per part de CTV en cí­trics ha obligat la utilització de patrons tolerants al decaïment. No obstant, aquestos patrons són agronòmicament menys adequats. Les plantes de cítrics propagades sobre NA i infectades por CTV mostren necrosi als tubs cribosos i disminució del floema funcional. Aquestos sí­mptomes poden ser conseqüència de l'activació de les rutes de defensa de la planta com la reacció d'hipersensibilitat, desencadenada per la ruta de l'àcid salicí­lic o el silenciamient gènic mediat per RNA (PTGS). Amb l'objectiu d'analitzar la implicació d¿aquestes rutes en la defensa, es va estudiar el paper de diferents gens implicats en la ruta de l'AS i del PTGS per mitjà  del silenciamient gènic induït per virus basat en el genoma del tacat foliar dels cítrics (CLBV). El silenciamient gènic de les rutes AS o PTGS en plantes NA i la inoculació de tres aïllats de CTV patogènicament diferents va mostrar la implicació de les dues rutes en la defensa del NA front CTV. L'analisis de les proteïnes p20, p23 i p25 com a possibles supressors de la ruta de l'AS va indicar que els aïllats més virulents de CTV posseïxen supressors més potents. / Gómez Muñoz, N. (2017). ESTUDIO DE LA INTERACCIÓN DIFERENCIAL ENTRE AISLADOS DEL VIRUS DE LA TRISTEZA DE LOS CÍTRICOS (CTV) Y SUS HUÉSPEDES [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/94624 / TESIS

Composite materials formed from two or more functionally different materials offer a versatile avenue to create a tailored material with well defined traits. Within this dissertation research, multi-functional composites were synthesized based on organic and inorganic materials. The functionally of these composites was experimentally tested and a semi-empirical model describing the sedimentation behavior of these particles was developed. This first objective involved the fabrication of microcomposites consisting of titanium dioxide (TiO2) nanoparticles confined within porous, microgels of a thermo-responsive polymer for use in the photocatalytic treatment of wastewater. TiO2 has been shown to be an excellent photocatalyst with potential applications in advanced oxidative processes such as wastewater remediation. Upon UV irradiation, short-lived electron-hole pairs are generated, which produce oxidative species that degrade simple organic contaminants. The rapid sedimentation of these microcomposites provided an easy gravimetric separation after remediation. Methyl orange was used as a model organic contaminant to investigate the kinetics of photodegradation under a range of concentrations and pH conditions. Although after prolonged periods of UV irradiation (~8-13 hrs), the titania-microgels also degrade, regeneration of the microcomposites was straightforward via the addition of polymer microgels with no loss in photocatalytic activity of the reformed microcomposites. The second objective within this dissertation involved the systematic development of abrasive microcomposite particles containing well dispersed nanoparticles of ceria in an organic/inorganic hybrid polymeric particle for use in chemical mechanical polishing/planarization (CMP). A challenge in IC fabrication involves the defect-free planarization of silicon oxide films for successful multi-layer deposition. Planarization studies conducted with the microcomposites prepared in this research, yield very smooth, planar surfaces with removal rates that rival those of inorganic oxides slurries typically used in industry. The density and size of these ceria-microgel particles could be controlled by varying the temperature or composition during synthesis, leading to softer or harder polishing when desired.

No description available.

<p>Kao &scaron;to je poznato, RS-2-(4-hlor-o-toliloksi)propionska kiselina (MCPP),&nbsp;(4-hlor-2-metilfenoksi)sirćetna kiselina (MCPA) i 3,6-dihlorpiridin-2-karboksilna kiselina &nbsp;(klopiralid) su herbicidi sa veoma &scaron;irokim spektrom dejstva, a pored toga su rastvorljivi u&nbsp;vodi, te&scaron;ko biorazgradljivi i prema literaturnim podacima su, nažalost, veoma često prisutni&nbsp;herbicidi u pijaćoj vodi. Proces heterogene fotokatalize uz primenu TiO₂i UV zračenja se&nbsp;pokazao kao veoma pogodan način za njihovo uklanjanje iz vode. Međutim, zbog velikog&nbsp;energetskog procepa od 3,2 eV (anataze-oblik), odnosno, 3,0 eV (rutil-oblik), veoma mali&nbsp;udeo bliskih UV zraka iz sunčeve svetlosti (oko 3&minus;4%) biva iskori&scaron;ćen u toku&nbsp;fotokatalitičkog procesa, &scaron;to ukazuje na to da je TiO_2&nbsp;praktično neaktivan u prisustvu&nbsp;sunčeve svetlosti. Na osnovu literaturnih podataka je zapaženo da postoji mogućnost&nbsp;fotorazgradnje pojedinih supstrata u prisustvu TiO_2&nbsp;primenom vidljive svetlosti. Na&nbsp;primeru MCPP je ispitana aktivnost TiO_2&nbsp;Degussa P25 kao fotokatalizatora u prisustvu&nbsp;vidljive svetlosti. Na osnovu refleksionih spektara je utvrđeno da MCPP adsorbovan na&nbsp;TiO_2&nbsp;Degussa P25 apsorbuje vidljivi deo spektra (&lambda; &ge;400 nm). Nastali prelazni kompleks&nbsp;je potvrđen FTIR merenjima. Efikasnost TiO2Degussa P25 primenom vidljive svetlosti je&nbsp;upoređena sa sunčevim i UV zračenjem, kao i direktnom fotolizom u prisustvu pomenutih&nbsp;izvora zračenja. Brzina fotokatalitičke razgradnje MCPP primenom vidljive svetlosti iznosi&nbsp;0,86 &mu;mol dm^&minus;3min^&minus;1, &scaron;to je oko 4 puta brže u poređenju sa direktnom fotolizom. Nadalje&nbsp;je ustanovljena optimalna masena koncentracija katalizatora od oko 8 mg cm^&minus;3, koja je&nbsp;znatno vi&scaron;a u poređenju sa primenom UV zračenja. Razlog je najverovatnije različit&nbsp;mehanizam fotorazgradnje koji se odvija primenom vidljivog i UV zračenja. Naime,&nbsp;prisustvo 2-metil-2-propanola (poznatog hvatača&nbsp;^&bull;OH-radikala) praktično ne utiče na&nbsp;brzinu fotokatalitičke razgradnje MCPP p rimenom vidljive svetlosti, &scaron;to ukazuje da se&nbsp;mehanizam razgradnje MCPP primenom &nbsp;vidljive svetlosti ne odvija posredstvom&nbsp;^&bull;OH-radikala, za razliku od onog uz primenu UV zračenja.</p><p>S obzirom da se katalizator TiO_2&nbsp;Degussa P25 uz primenu vidljive svetlosti nije&nbsp;<br />pokazao kao naročito efikasan kada je u pitanju razgradnja sva tri herbicida i imajući u&nbsp;vidu da se u poslednje vreme iz razloga praktične primene sve vi&scaron;e pribegava procesu dopovanja TiO_2&nbsp;različitim tipovima metala (alkalnih, zemnoalkalnih, prelaznih i dr.) i nemetala (halogenida, halkogenida i dr.), u okviru ove doktorske disertacije je ispitana aktivnost N-TiO₂(sintetisanih mokrim i suvim putem) i TiO_2&nbsp;(rutil) dopovanog sa različitim količinama Fe³⁺-jona (0,13&minus;1,48 at.%) pri razgradnji herbicida MCPP i MCPA primenom vidljive svetlosti. Pored toga je ispitana efikasnost TiO_2&nbsp;(anataze) takođe dopovanog sa različitim količinama Fe³⁺-jona (0,71&minus;1,80 at.%) na primeru MCPP.&nbsp;</p><p>Poredeći N-TiO_2&nbsp;(sintetisan mokrim putem) i N-TiO_2&nbsp;(sintetisani suvim putem), primećeno&nbsp;je da je u drugom slučaju efikasnost katalizatora veća oko 2 puta. Isto tako je zapažena u&nbsp;slučaju MCPP ne&scaron;to veća fotokatalitička aktivnost N-TiO_2&nbsp;(sintetisani suvim putem) u&nbsp;poređenju sa TiO_2&nbsp;(anataze). Kada je u pitanju MCPA aktivnost sva tri katalizatora je&nbsp;veoma slična. Pored toga je zapažena veća efikasnost N-TiO_2&nbsp;(sintetisan mokrim putem) u&nbsp;poređenju sa TiO_2&nbsp;Degussa P25 (oko 1,5 puta) i oko 5 puta u odnosu na direktnu fotolizu,&nbsp;dok su N-TiO_2&nbsp;(sintetisani suvim putem) oko 3 puta efikasniji u poređenju sa TiO_2&nbsp;Degussa P25 i oko 10 puta u &nbsp;poređenju sa direktnom fotolizom. Brzina solarne razgradnje&nbsp;je preko 100 puta manja nego primenom vidljivog i UV zračenja, &scaron;to je posledica različitih&nbsp;intenziteta pomenutih izvora ozračivanja i različitih uslova pri kojima je vr&scaron;ena razgradnja. &nbsp;Ustanovljena je optimalna masena koncentracija N-TiO_2&nbsp;(sintetisan mokrim putem) od&nbsp;4 mg cm^&minus;3.</p><p>Prilikom razgradnje MCPP i MCPA je nađeno da je brzina veća kada se kao&nbsp;katalizator &nbsp;koristi TiO_2&nbsp;(rutil) u poređenju sa Fe-TiO_2&nbsp;i da sa povećanjem količine Fe³⁺-jona fotokatalitička aktivnost uglavnom opada. Kada je kao fotokatalizator kori&scaron;ćen TiO_{2 &nbsp;}<br />(anataze) dopovan različitim količinama Fe³⁺-jona (od 0,71 do 1,80 at.%), razgradnja&nbsp;<br />MCPP je u svim slučajevima znatno sporija u odnosu na TiO_2&nbsp;(anataze).</p><p>S obzirom da su prema literaturnim podacima kinetika i mehanizam fotokatalitičke&nbsp;<br />razgradnje klopiralida nepoznati, ispitana je njegova stabilnost pri različitim&nbsp;eksperimentalnim uslovima. Tokom ispitivanja uticaja pH kako u prisustvu, tako i u&nbsp;odsustvu dnevne svetlosti u intervalu pH od 1,0&minus;9,0, nađeno je da ni u jednom slučaju ne&nbsp;dolazi do razgradnje supstrata u periodu od sedam meseci koliko je proces praćen. Takođe&nbsp;je ispitana kinetika fotokatalitičke razgradnje klopiralida primenom UV i vidljivog&nbsp;zračenja u prisustvu TiO_2&nbsp;Degussa P25, kao i direktna fotoliza primenom oba izvora&nbsp;zračenja. Nađeno je da je brzina fotokatalitičke razgradnje primenom UV zračenja veća&nbsp;oko 5 puta u odnosu na direktnu fotolizu. Za praćenje toka fotokatalitičke razgradnje&nbsp;klopiralida je izabrana pH-vrednost od 3,2. Nadalje je zapaženo da se u ispitivanom opsegu početnih koncentracija supstrata (0,5&ndash;3,0 mmol dm^&minus;3) kinetika fotokatalitičke razgradnje klopiralida može opisati pseudo-prvim redom. Pri ispitivanju uticaja masene koncentracije katalizatora (0,5&ndash;8 mg cm^&minus;3) na brzinu razgradnje klopiralida, ustanovljena je optimalna masena koncentracija primenjenog fotokatalizatora od oko 4 mg cm^&minus;3. Izračunata ukupna &nbsp;prividna energija aktivacije iznosi 7,74 kJ mol^&minus;1. Pored toga, prisustvo kiseonika ubrzava reakciju 2 puta, dok dodatak elektron-akceptora kao &scaron;to su (NH₄)₂S₂O₈, H₂O_2&nbsp;i KBrO_3&nbsp;pokazuje značajan i različit efekat na kinetiku fotokatalitičke razgradnje klopiralida. Pri ispitivanju uticaja etanola, kao hvatača slobodnih radikala, nađeno je da se heterogena fotokataliza odvija uglavnom preko ^&bull;OH-radikala.</p><p>Na osnovu LC&ndash;MS/MS (ESI+) merenja ustanovljeno je prisustvo nekoliko&nbsp;intermedijera: 3,6-dihlor-piridin-2-ol, 3,6-dihlor hidroksipiridin-2-karboksilna kiselina i&nbsp;3,3&#39;,6,6&#39;-tetrahlor-2,4&#39;-bipiridin-2&#39;-karboksilna kiselina. Na osnovu identifikovanih&nbsp;intermedijera, kao i kinetičkih rezultata, predložen je mogućput mehanizma fotokatalitičke&nbsp;razgradnje klopiralida.</p><p>Prilikom ispitivanja uticaja strukture molekula na brzinu razgradnje, konstatovano&nbsp;<br />je da u slučaju klopiralida praktično ne dolazi do fotokatalitičke razgradnje u prisustvu&nbsp;TiO_2&nbsp;(anataze) i N-TiO_2&nbsp;(sintetisani suvim putem) uz primenu vidljive svetlosti, kao i u&nbsp;slučaju TiO_2&nbsp;Degussa P25. Pored toga, primenom TiO_2&nbsp;(rutil) i Fe-TiO_2&nbsp;kao&nbsp;fotokatalizatora, sa povećanjem količine Fe³⁺-jona od 0,13 do 1,27 at.% raste brzina&nbsp;razgradnje klopiralida, ukazujući da strukturne osobine supstrata utiču na brzinu njihove&nbsp;razgradnje.</p> / <p>It is well known that RS-2-(4-chloro-o-tolyloxy)propionic acid (MCPP), (4-chloro-2- methyl-phenoxy)acetic acid (MCPA) and 3,6-dichloropyridine-2-carboxylic &nbsp;acid&nbsp;(clopyralid) are herbicides of wide activity spectrum. They are soluble in water, hardly&nbsp;biodegradable and, unfortunately, often present in drinking water.</p><p>Heterogeneous photocatalysis by application of TiO_2&nbsp;and UV radiation proved to&nbsp;be very suitable for their removal from water. However, due toits large energy gap, i.e.&nbsp;3.2 &nbsp;eV (anatase-form) and 3.0 eV (rutile-form), a very small fraction of sunlight in the near&nbsp;UV range (about 3&ndash;4%) is used during photocatalytic process, which is an indication of&nbsp;TiO_2&nbsp;inactivity in the presence of this light source. Some literature data report on the&nbsp;possibility of photodegradation of certain substrates by visible light in the presence of&nbsp;TiO₂. MCPP served as substrate for testing TiO_2&nbsp;Degussa P25 &nbsp;photocatalytic activity in the&nbsp;presence of visible light. On the basis of reflection spectra it was established that MCPP&nbsp;adsorbed on TiO_2&nbsp;Degussa P25 was absorbing visible spectrum radiation (&lambda; &ge;400 nm).&nbsp;The existence of thus formed &nbsp;charge-transfer complex was confirmed with FTIR analysis.&nbsp;The efficiency of &nbsp;TiO_2&nbsp;Degussa P25 with application of visible light was compared to&nbsp;sunlight and UV radiation, as well to directphotolysis in the presence of these light&nbsp;sources. The rate of MCPP photocatalytic degradation by means of visible light is&nbsp;0.86 &mu;mol dm^{&minus;3&nbsp;}min^&minus;1, which is about 4 times faster than direct photolysis. In addition, the&nbsp;optimal &nbsp;catalyst concentration of about 8 mg cm^&minus;3, much higher than using UV radiation,&nbsp;<br />was established. The reason is, probably, a different mechanism of &nbsp;hotodegradation &nbsp;in the&nbsp;presence of visible and UV irradiation. Namely, the presence of 2-methyl-2-propanol&nbsp;(well-known&nbsp;^&bull;OH radical scavenger) has practicallyno effect on the rate of &nbsp;MCPP&nbsp;photocatalytic degradation using visible light, which points that this degradation&nbsp;mechanism does not involve&nbsp;^&bull;OH radicals, in contrast to that established &nbsp;for UV radiation.</p><p>Since the catalyst TiO_2&nbsp;Degussa P25 with application of visible light was not very&nbsp;<br />efficient in degradation of all three herbicidesand in view that nowadays is very &nbsp;popular&nbsp;doping process of TiO₂ with different types of metals (alkali, alkaline-earth, transition, etc.)&nbsp;and non-metals (halogen, chalcogen, etc.), in the scope of this Ph.D. &nbsp;thesis activities of N-TiO_2&nbsp;(synthesized by wet and dry procedure) and TiO_2&nbsp;(rutile) doped with various amounts&nbsp;of Fe^3+&nbsp;(0.13&ndash;1.48 at.%) in degradation processes of &nbsp;herbicides MCPP and MCPA using&nbsp;visible light were studied. In addition, the efficiency of TiO_2&nbsp;(anatase) doped with various&nbsp;amounts of Fe^3+&nbsp;(0.71&ndash;1.80 at.%) was also tested for MCPP degradation. When comparing&nbsp;N-TiO_2&nbsp;(synthesized by wet procedure) and N-TiO₂ (dry procedure), it was observed that&nbsp;in the latter case the catalyst efficiency was about two times higher. In this case for MCPP&nbsp;was also observed somewhat higher photocatalytic activity of N-TiO₂ (synthesized by dry&nbsp;procedure) in comparison with TiO₂. When activities of all three catalysts towards MCPA&nbsp;are compared, the results are very alike. In addition, higher efficiency of N-TiO_{2 &nbsp;}(wet&nbsp;procedure) comparing to TiO_2&nbsp;Degussa P25 (about 1.5 times) and about 5 times in&nbsp;comparison to direct photolysis were recorded, while N-TiO₂ (dry procedure) was about 3&nbsp;times more efficient than TiO_2&nbsp;Degussa P25 and about 10 times in comparison with direct&nbsp;photolysis. The rate of solar degradation is about 100 times lower than by application of&nbsp;UV and visible radiation, as a consequence of various intensities of the mentioned light&nbsp;sources and different conditions of photodegradation. An optimal concentration of N-TiO₂&nbsp;(wet procedure) of 4 mg cm^&minus;3<br />&nbsp;was established.</p><p>During degradation of MCPP and MCPA it was observed that the rate is higher if&nbsp;TiO₂(rutile) was applied comparing to Fe-TiO_2&nbsp;and with increasing amount of Fe^3+&nbsp;photocatalytic activity mostly decreases. When TiO₂ (anatase) doped with various amounts&nbsp;of Fe^3+&nbsp;(0.71 to 1.80 at.%) was applied for MCPP degradation, the process was much&nbsp;slower than with undoped catalyst.</p><p>Since we have not found relevant literature data on kinetics and mechanism of&nbsp;photocatalytic degradation of clopyralid, its stability in different experimental conditions&nbsp;was tested. In investigating of influences of pH (1.0&ndash;9.0) both in presence and in absence&nbsp;of daylight, in no cases decomposition was observed during seven months experiments.&nbsp;Also, the kinetics of photocatalytic degradation of clopyralid using UV and visible&nbsp;irradiation in the presence of TiO_2&nbsp;Degussa P25 and in direct photolysis by application of&nbsp;both irradiation sources was studied. It was found that the &nbsp;rate of photocatalytic&nbsp;decomposition using UV radiation was 5 times higher comparing to direct photolysis. For&nbsp;clopyralid photocatalytic monitoring a pH value of &nbsp;3.2 was chosen. In addition, in the investigated concentration range (0.5&ndash;3.0 mmol &nbsp;dm^&minus;3) the photocatalytic degradation kinetics of clopyralid in the first stage of the reaction follows approximately a pseudo-first kinetic order. In investigation of influence of catalyst concentration (0.5&ndash;8 mg cm^&minus;3) on the rate of clopyralid degradation the highest reaction rate was observed at 4 mg cm^{&minus;3&nbsp;}of catalyst concentration The apparent activation energy of the reaction being 7.74 kJ mol^&minus;1. The absence of molecular oxygen resulted in a significant decrease (about 2 times) in the rate of clopyralid photodegradation. The effect of the presence of (NH₄)₂S₂O₈, H₂O_2&nbsp;and KBrO₃, acting as electron acceptors along with molecular oxygen affects clopyralid photocatalytic degradation considerably and indifferent ways. By studying the effect of ethanol as a hydroxyl radical scavenger it was shown that the heterogeneous catalysis takes place mainly via ^&bull;OH radicals.</p><p>LC&minus;MS/MS (ESI+) monitoring of the process showed that several pyridine-containing intermediates are formed: 3,6-dichloropyridin-2-ol, 3,6-dichloro&nbsp;hydroxypyridine-2-carboxylic acid and 3,3&#39;,6,6&#39;-tetrachloro-2,4&#39;-bipyridine-2-carboxylic&nbsp;acid. Based on the identified intermediates and overall kinetic results, a probable&nbsp;photocatalytic degradation mechanism was proposed.&nbsp;</p><p>Finally, in the case of clopyralid it was established that practically no degradation&nbsp;<br />occurs in the presence of TiO_2&nbsp;(anatase) and N-TiO₂ (dry procedure) with visible light &nbsp;and&nbsp;also with TiO_2&nbsp;Degussa P25. Besides of that, by using TiO_2&nbsp;(rutile) and Fe-TiO_2&nbsp;as&nbsp;photocatalysts it was noted that increasing the concentration of Fe^3+&nbsp;from 0.13 to 1.27 at.%&nbsp;comes to increasing photodegradation rate of clopyralid. Results indicate that differences&nbsp;in molecular structure of chosen compound, influence obtained photocatalytic activity to a&nbsp;great extent.</p>