<p>U slučajevima neuspe&scaron;ne endodontske terapije, neophodno je ponovno lečenje kanala korena. Ortogradni endodontski retretman podrazumeva uklanjanje postojećeg materijala za punjenje iz kanala uz dodatno či&scaron;ćenje, dezinfekciju i ponovnu finalnu opturaciju kanala. Važan korak u toku retretmana je &scaron;to potpunije uklanjanje postojećeg kanalnog punjenja kako bi se pristupilo svim delovima kanalnog sistema. Cilj doktorske teze bio je da se ispita kvalitet čis&scaron;ćenja zidova kanala korena nakon endodontskog retretmana pomoću skening elektronske mikroskopije (SEM). Posmatran je uticaj vrste materijala za opturaciju, uticaj upotrebe rastvarača i uticaj ručnih i ma&scaron;inskih instrumenata na količinu zaostalog materijala na zidovima kanala. Takođe, ispitan je uticaj ovih faktora na apikalnu transportaciju materijala i na vreme potrebno za retretman, a utvrđena je i učestalost o&scaron;tećenja kori&scaron;ćenih instrumenata. Materijal i metode: Ukupan uzorak činilo je 125 ekstrahovanih, humanih jednokorenih zuba. Nakon preparacije kanala korena, 120 zuba je podeljeno u dve grupe i napunjeno pomoću dva različita materijala za opturaciju (gutaperkom i resilonom). U zavisnosti od tehnike uklanjanja ovih materijala, grupe su dalje podeljene u odnosu na kori&scaron;ćene instrumente (Hedstrom, ProTaper i Twisted File) i u odnosu na upotrebu rastvarača (sa i bez hloroforma). Preostalih 5 zuba, bez kanalnog punjenja, kori&scaron;ćeni su kao kontrolna grupa. Nakon zavr&scaron;enog retretmana, korenovi su uzdužnim cepanjem razdvojeni, a odabrane polovine posmatrane na SEM-u. Mikrofotografije svake trećine kanala načinjene su pri uveličanju od 500x. Količina preostalog materijala za punjenje ocenjivana je pomoću skale. Otvoreni dentinski kanalići prebrojavani su na mikrofotografijama načinjenim pri uveličanju od 1000x, u odnosu na uvek konstantnu povr&scaron;inu. Rezultati: Analiza rezultata ukazala je na postojanje statistički značajne razlike u kvalitetu či&scaron;ćenja zidova kanala u zavisnosti od uklanjanog materijala za opturaciju. Kvalitet či&scaron;ćenja zidova kanala bio je veći nakon uklanjanja gutaperke nego nakon uklanjanja resilona. Rotirajućim, ma&scaron;inskim instrumentima je efikasnije uklanjana gutaperka, a ručnim Hedstrom turpijama je bolje uklanjan resilon. Posmatrajući ceo uzorak, ProTaper instrumenti ostavljali su velike količine materijala na zidovima kanala nakon endodontskog retretmana. Međutim, uklanjanje materijala pomoću ovih instrumenata bilo je najbrže. Primena rastvarača značajno je doprinela bržem uklanjanju materijala, dok uticaj na kvalitet či&scaron;ćenja zidova kanala nije bio značajan. Posmatrajući kanal korena po trećinama, najveća količina materijala nalazila se u apikalnoj trećini, bez obzira na vrstu uklanjanog materijala i kori&scaron;ćenih instrumenata, i bez obzira na upotrebu rastvarača tokom retretmana. Učestalost o&scaron;tećenja instrumenata bila je značajno veća prilikom upotrebe Twisted File instrumenata. Apikalna transportacija materijala je bila veća tokom uklanjanja resilon materijala i kada su kori&scaron;ćene ručne Hedstrom turpije. Zaključak: Kvalitet či&scaron;ćenja zidova kanala nakon uklanjanja gutaperke je veći nego nakon uklanjanja resilona. Dizajn i vrsta instrumenata utiče na kvalitet či&scaron;ćenja zidova kanala korena. Upotreba rastvarača tokom retretmana ne utiče značajno na smanjenje količine materijala zaostalog na zidovima kanala. Ma&scaron;inski pokretani instrumenti i upotreba rastvarača značajno skraćuju vreme potrebno za endodontski retretman.</p> / <p>In cases when endodontic treatment fails, it is necessary to retreat the root canal. Orthograde endodontic retreatment requires the removal of the existing root filling material with additional cleaning, disinfection and refilling of the canal. An important step during retreatment is complete removal of existing filling materials, to regain access to all parts of the canal system. The aim of the doctoral thesis was to investigate the cleanliness of root canal walls after removal of two different obturation material. The retreatment efficacy was observed depending on the usage of solvent and different hand or rotary instruments. The amount of residual material on the canal walls was assessed using scanning electron microscopy (SEM). Also, apical transportation of the obturation material, working time and frequency of instrument damage during retreatment was recorded. Materials and Methods: The total sample consisted of 125 extracted, single-rooted human teeth. After root canal preparation, 120 teeth were divided in two groups and filled using two different obturation materials (gutta-percha and resilon). Depending on the technique of removing these materials, the groups were further divided, in relation to the used instruments (Hedstrom, ProTaper and Twisted File), as well as in relation to the use of solvent (with or without chloroform). The remaining 5 tooth without canal filling were used as a control group. After root canal desopturation, the longitudinaly splitted root halves were observed on SEM. Microphotography of each third were made at magnification of 500x. The amount of remaining filling material was evaluated by using a scale. Open dentinal tubules were counted on microphotographies made at a magnificiation of 1000x, on a surface that was always constant. Results: Analysis of the results indicated a significant difference in the cleanliness of the canal walls depending on the used obturation material. Cleanliness of the canal walls was higher after gutta-percha removal than after the removal of resilon.&nbsp; Rotary instruments were more effective in removing gutta-percha and Hedstrom hand files better removed resilon. ProTaper instruments left more residual material on canal walls, however endodontic retreatment with these instruments was the fastest. The application of solvent significantly contributed to faster material removal, while the impact on the increase of canal cleanliness was not significant. The largest amount of material remained in the apical third, regardless of the type of material removed and instruments used, and also regardless whether solvent was used for retreatment. The frequency of instrument deformation and fracture was significantly higher when Twisted File instruments were used. Apical transportation of material had a significantly higher occurrence during resilon removal and when manual Hedstrom files were used. Conclusion: Cleanliness of the canal walls was higher after the removal of gutta-percha than after the removal of resilon. The use of solvent is not significant on the increase of canal wall cleanliness, but significantly shortens the time needed for retreatment. There is a difference in the cleanliness of root canal walls depending on the used instruments. Engine-driven rotary instruments and the use of a solvent significantly shortens the time needed for endodontic retreatment.</p>

Le chlore est largement utilisé pour ses propriétés bactéricides dans les piscines. Dans les eaux de piscine, le chlore réagit avec les matières azotées et carbonées générées par l’activité humaine (sueur, salive, urine, peau) pour former divers composés toxiques tels que la monochloramine (NH2Cl), la dichloramine (NHCl2), le trichlorure d'azote (NCl3), le chloroforme (CHCl3), etc… qui se retrouvent dans l’atmosphère. La détection et la quantification de ces composés volatils à des teneurs ppb (partie par milliard) est un réel besoin afin de contrôler la qualité de l’air des piscines. Cependant il n’existe pas à ce jour des appareils à la fois sensibles et peu coûteux.L’objectif de ce travail de thèse est d’élaborer des capteurs chimiques colorimétriques, sensibles, sélectifs et peu coûteux de la monochloramine, du trichlorure d’azote et du chloroforme. Dans ce but, nous avons mis au point des capteurs chimiques réalisés à partir de matrices nanoporeuses de silicate dopée des réactifs. Ainsi le capteur de NCl3 dopé de NaI et d’amylose permet de mesurer de faibles teneurs de NCl3 (5 ppb à 180 ppb) dans les atmosphères humides (50-80% HR) des piscines. Grâce au changement rapide de couleur, de transparent à rose-violet, visible à l’œil nu, le capteur de NCl3 permet de surveiller la qualité de l’air dans les piscines. Le capteur sélectif de NH2Cl est basé sur la réaction de Berthelot. La matrice de silicate nanoporeuse dopée de nitroprussiate de sodium et de phénol en milieu alcalin, initialement transparente, devient bleue lors d’une exposition à NH2Cl gazeux. Ce capteur permet de détecter NH2Cl dans la gamme de 60 à 250 ppb dans une atmosphère très humide (≈ 80%). Utilisé pour la sonder la qualité des eaux de piscine, il permet de mesurer NH2Cl dans l’eau avec une limite de détection de 0,1 µmol•L-1. Une étude préliminaire de la détection de CHCl3 a également été entreprise pour déterminer les molécules-sonde aptes à réagir avec le chloroforme en formant des produits colorés. Les réactifs de la réaction de Fujiwara ont été sélectionnés. L’étude de la réactivité de la 2,2’-bipyridine en solution en présence d’une base forte a permis de mettre en évidence la formation simultanée de deux composés colorés, dont la formation dépend de la nature de l’environnement réactionnel. / In swimming-pools, chlorine is used as a disinfectant to minimize the risk to users from microbial contaminants. In water, chlorine reacts with nitrogen compounds generated by human activity like saliva, sweat, urine and skin, leading to the formation of toxic compounds, such as monochloramine (NH2Cl), dichloramine (NHCl2), nitrogen trichloride (NCl3), chloroform (CHCl3), etc… The detection and the quantification of these volatile compounds at ppb level (part per billion) is an important and significant challenge to be able to monitor the air quality in swimming pool. Or, there is currently no commercially available and low-cost system which can instantaneously measure at ppb concentrations.The aim of this research is to develop a cheap, sensitive and selective chemical and colorimetric sensors of monochloramine, nitrogen trichloride and chloroform. For this purpose, we developed chemical sensors based on the use of nanoporous silicate matrices doped with probe-molecules. The NCl3 sensor doped with NaI and amylose can detect NCl3 at ppb level (5 ppb – 180 ppb) in humid atmospheres (from 50% to 80% relative humidity) at ambient pool temperatures. Due to the fast change of color, visible with naked eyes, these sensors can be used to detect peaks of pollution and to monitor the air quality of indoor pools. The NH2Cl selective sensor is based on the Berthelot reaction. The nanoporous silicate matrices doped with sodium nitroprusside and phenol in an alkaline medium, turn from transparent to blue upon exposure to gaseous NH2Cl. This sensor can detect NH2Cl in the range from 60 to 250 ppb in a very humid atmosphere (≈ 80%). Used to probe the quality of pool water, this sensor can detect NH2Cl in water with a detection limit of 0,1 µmol•L-1. A preliminary study of the CHCl3 detection was also conducted to identify probe-molecules capable of reacting with chloroform to form colored products. The reagents of the Fujiwara reaction were selected. The study of the 2,2’-bipyridine reactivity in solution in the presence of a strong base allowed highlighting the simultaneous formation of two colored compounds, whose formation depends on the nature of the reaction environment.

Ce travail a été consacré à l'étude des sous-produits de désinfection formés lors de la chloration des eaux de piscine publiques. En effet, parallèlement à son action désinfectante, le chlore réagit sur les composés organiques et minéraux introduits dans l'eau des bassins par les baigneurs (urine, sueur, ...) pour former des sous-produits indésirables (chloramines et composés organohalogénés).Des analyses d'urée, principal composé précurseur de chloramines inorganiques, ont été effectuées dans une cinquantaine d'eaux de piscine. Les concentrations mesurées ont été comprises entre 0,14 et 3,67 mg/L (valeur moyenne : 1,08 mg/L ; écart-type : 0,70 mg/L). L'étude de la réactivité du chlore sur l'urée (cinétique et consommation de chlore) effectuée sous différentes conditions expérimentales a mis en évidence une très grande stabilité de l'urée en présence de chlore libre dans les eaux de piscines.Les analyses de sous-produits de chloration ont démontré que l'hydrate de chloral représente l'un des sous-produits de chloration majoritaire avec les acides dichloroacétique et trichloroacétique. Cette étude a aussi permis de déterminer la constante cinétique d'hydrolyse de l'hydrate de chloral dans l'eau, l'influence du pH et de la température sur la vitesse d'hydrolyse, ainsi que les potentiels de formation d'hydrate de chloral à partir de quelques constituants de l'urine.La dernière partie de ce travail a porté sur l'étude de la réactivité de l'ozone sur le chlore et sur des sous-produits de chloration ainsi que sur l'étude de l'incidence d'une préozonation des eaux de piscines (en absence et en présence de chlore libre) sur la formation des sous-produits organohalogénés lors d'une post-chloration. / The aim of this work was to study of the formation of disinfection by-products during the chlorination of public swimming pools water. In parallel to its disinfecting action, chlorine reacts with organic and inorganic compounds introduced into the swimming pool water by bathers (urine, sweat, ...) to form undesirable by-products (chloramines and organohalogenated matters).A statistical study of the presence of urea, the major component of urine and sweat, and the main precursor compound of inorganic chloramines, in public swimming poolwater has been made. Measured concentrations were between 0.14 and 3.67 mg/L (mean value: 1.08 mg/L, s.d: 0.70 mg/L). The study of the reactivity of chlorine with urea (kinetic and chlorine consumption) made under different experimental conditions, showed a very high stability of urea in the presence of free chlorine in the pools water.Analysis of chlorination by-products showed that chloral hydrate, with the dichloro and the trichloroacetic acids, is one of the major chlorination by-products found. This study also determined the kinetic rate constant of hydrolysis of chloral hydrate in water, the influence of the pH and the temperature on the rate of hydrolysis and the potential of chloral hydrate formation from some constituents of the urine.The last part of this work was focused on the study of the reactivity of ozone on chlorine and some disinfection by-products, as well as the study of the impact of preozonation of swimming pools water (in absence and presence of free chlorine) on the formation of organohalogenated by-products during a post-chlorination.

Historically, chlorination has been widely utilized as a primary and secondary disinfectant in municipal water supplies. Although chlorine disinfection is effective in inactivating pathogenic microbes, the use of chlorine creates the unintentional formation of regulated chemicals. On January 4, 2006, the United States Environmental Protection Agency (EPA) promulgated the Stage 2 Disinfectants/Disinfection by-product rule (DBPR) that focuses on public health protection by limiting exposure to four trihalomethanes (THM) and five haloacetic acids (HAA5), formed when chlorine is used for microbial pathogen control. This thesis examines post-aeration TTHM formation when employing spray-aeration processes to remove semi-volatile TTHMs from chlorinated potable water supplies. A bench scale air stripping unit was designed, constructed and operated to evaluate spray aeration for the removal of the four regulated trihalomethane (THM) species from potable drinking water including bromodichloromethane, bromoform, dibromochloromethane, chloroform. The study was conducted using finished bulk water samples collected from two different water treatment facilities (WTFs) located in Oviedo and Babson Park, Florida. Both treatment plants treat groundwater; however, Oviedo's Mitchell Hammock WTF (MHWTF) supply wells contain dissolved organic carbon and bromide DBP precursors whereas the Babson Park WTF #2 (BPWTF2) supply well contains dissolved organic carbon DBP precursors but is absent of bromide precursor. Three treatment scenarios were studied to monitor impacts on total trihalomethane (TTHM) removal and post-treatment (post-aeration) TTHM formation potential, including 1) no treatment (non-aerated control samples), 2) spray aeration via specially fabricated GridBee® nozzle for laboratory-scale applications, 3) spray aeration via a commercially available manufactured BETE® nozzle used for full-scale applications. Select water quality parameters, chlorine residual, and total trihalomethane concentrations were monitored throughout the study. The GridBee® spray nozzle resulted in TTHM removals ranging from 45.2 ± 3.3% for the BPWTF2 samples, and 37.7 ± 3.1% for the MHWTF samples. The BETE® spray nozzle removed 54.7±3.9% and 48.1±6.6% of total trihalomethanes for the Babson Park and Mitchell Hammock WTF samples, respectively. The lower percent removals at the MHWTF are attributed to the detectable presence of bromide and subsequent formation of hypobromous acid in the samples. Post spray aeration TTHM formation potentials were monitored and it was found that the MHWTF experienced significantly higher formation potentials, once again due to the presence of hypobromous acid which led to increases in overall TTHM formation over time in comparison with the Babson Park WTF #2 TTHM formation samples. In addition, chlorine residuals were maintained post spray aeration treatment, and initial chlorine residual and trihalomethane concentrations did not significantly impact overall spray nozzle performance. Among other findings, it was concluded that spray nozzle aeration is a feasible option for the Babson Park WTF #2 for TTHM compliance. For Oviedo's Mitchell Hammock WTF spray aeration was successful in removing TTHMs, however it was not effective in maintaining DBP rule compliance due to the excessive nature of DBP formation in the water samples. This study was not intended to serve as an assessment of varying nozzle technologies; rather, the focus was on the application of spray aerators for TTHM removal and post-formation in drinking water systems.

In this thesis, large organic molecules (DM15N, DM18N, Cu(dbm)2) were deposited. These molecules are cannot be deposited by thermal sublimation due the fact that they decompose at lower temperature than they sublime. The employed molecules to single molecular magnets, which can be potentially used as quantum bites (qubit). The new method of deposition atomic layer injection made by Bihur Crystal company was introduced and tested. The method uses liquid solution with molecules which is driven by argon gas through pulse valve to the sample placed in ultra-high vacuum chamber. During the deposition, droplets of solution are formed on the sample surface. The solvent can be removed by light annealing or by keeping the sample in the vacuum for couple of days. The molecules were investigated by x-ray photoelectron spectroscopy and by scanning electron microscopy to determine fragmentation of the molecules, to study topography of the resultant surface and homogeneity of the deposited layer. We found conditions at which the intact molecules are deposited on the sample surfaces and form molecular nano- and micro- crystals.