La première partie de ce travail est consacrée à l'étude et à l'extension de la réaction de Devasia. Un nombre important de structures d'imidazolinones-5 insaturées-4, non accessibles directement par d'autres voies est ainsi réalisé. Le mécanisme de cette réaction et sa catalyse sont étudiés. Les structures des produits sont confirmées par les méthodes spectrométriques et analytiques habituelles. La stéréochimie des composés est déterminée en particulier par R.M.N.1H et 13C. La réactivité des molécules vis-à-vis de plusieurs réactifs est abordée. Au second chapitre nous décrivons une nouvelle voie d'accès à des delta-2-imidazolines polysubstituées et fonctionnalisées originales. La réaction est appliquée aux composés alpha-bromés alpha, bêta-insaturés possédant une fonction carbonylée ou nitrile. L'étude de cette réaction nous a permis de mettre en évidence un mécanisme particulier présentant des intermédiaires non classiques. La structure tridimensionnelle des molécules est déterminée par R.M.N.1H, 13C, dipolmétrie, CNDO-2 et cristallographie. La troisième et dernière partie traite de l'application de la réaction précédente, étendue au cas des amidines non substituées. Elle constitue dans ce cas une nouvelle voie d'accès aux (3H) pyrimidinones-4-disubstituées-2,6. Les structures moléculaires sont déterminées par les méthodes spectroscopiques et analytiques courantes. La réactivité des molécules est alors étudiée vis-à-vis de plusieurs réactifs. En particulier le réarrangement de type Dimroth concernant les (N-éthoxyméthylène et N-formylidène hydrazino)-4 (3H) pyrimidines est abordé et discuté.

<p>U ovoj disertaciji su prikazani rezultati kompleksnih istraživanja uticaja<br />kosmičkog zračenja na nuklearne spektre na nivou mora.<br />Utvrđivanje specifičnih vremenskih intervala u vremenskom spektru,<br />kojima odgovaraju tačno određene grupe događaja indukovane<br />kosmičkim mionima, omogućava adekvatno odbacivanje ometajućih<br />događaja u željenim energetskim oblastima detektovanih spektara, pri<br />antikoincidentnom režimu rada ultraniskofonskih sistema. U prvom<br />eksperimentu prikazanom u ovoj disertaciji,&nbsp; istraživana je mogućnost<br />vremenskog razlaganja detektovanih događaja,&nbsp; pomoću koincidentnog<br />sistema u čijem sklopu se nalazi HPGe detektor i&nbsp; plastični scintilator, u<br />povr&scaron;inskoj laboratoriji. Ustanovljeno je da se promptni i zakasneli<br />koincidentni događaji između plastičnog &ldquo;veto&rdquo; detektora i<br />germanijumskog detektora mogu jasno razdvojiti u dve grupe, za oko<br />100 ns. Dodatno, zakočno zračenje i&nbsp; anihilacioni događaji mogu se<br />razdvojiti u vremenu od (n,n&rsquo;) događaja, iako svi ovi događaji pripadaju<br />grupi zakasnelih događaja. Takođe, registrovani su&nbsp; i&nbsp; značajno zakasneli<br />anihilacioni događaji, koji nastaju usled raspada zaustavljenih pozitivnih<br />miona.<br />Drugi eksperiment prikazan u ovoj disertaciji baziran je na ultra-niskofonskom HPGe spektrometru relativne efikasnosti 100%.<br />Dodatkom dva plastična scintilatora i brzo-sporog koincidentnog kola,<br />istraživani su koincidentni događaji između plastičnih scintilatora i<br />HPGe spektrometra. Ovaj spektrometarski sistem MIREDO <em>(Muon<br />Induced Rare Event Dynamic Observatory</em>) prvenstveno je namenjen<br />proučavanju procesa indukovanih kosmičkim mionima u različitim<br />materijalima. Analiza ovakvih interakcija može biti od značaja za ultra-niskofonske eksperimente. Rezultati dobijeni za tri ispitivana materijala,<br />pakovana u<em> Marinelli</em> sud, prezentovani su i diskutovani.<br />U trećem eksperimentu prikazanom u ovoj disertaciji ispitan je<br />potencijalni uticaj solarnih&nbsp; neutrina&nbsp; na izmerenu brzinu&nbsp; radioaktivnog<br />raspada,&nbsp; merenjem varijacija u brzini brojanja<br />³H&nbsp; metodom tečnog&nbsp;scintilacionog brojanja. Kori&scaron;ćenjem sofisticiranog tečnog scintilacionog&nbsp;spektrometra&nbsp;<em> Quantulus</em>&nbsp; ustanovljeno je da na merenje<br />visokoenergetskog dela&nbsp;³H spektra može značajno uticati nestabilnost<br />instrumenta. Oscilatorni karakter izmerenog visokoenergetskog dela<br />³H&nbsp;spektra&nbsp; je registrovan, ali sa veoma malom amplitudom (manjom od<br />0.5%), koja se ne može jednostavno objasniti samo nestabilno&scaron;ću<br />instrumenta.&nbsp; Kada je meren ukupan&nbsp;³H spektar, nisu nađene značajne<br />varijacije u brzini brojanja.<br />Već duže vreme je poznato da je niskoenergetsko gama zračenje<br />kontinualne distribucije prisutno na otvorenom prostoru, u vazduhu na<br />povr&scaron;ini Zemlje. U prethodnim istraživanjima pretpostavljano je da&nbsp; ovo<br />zračenje potiče skoro isključivo od gama fotona koji su emitovani usled<br />prirodne radioaktivnosti i potom rasejani u nazad od strane vazduha<br />iznad zemlje. U četvrtom eksperimentu prikazanom u ovoj disertaciji<br />pokazano je da&nbsp; je&nbsp; ovo zračenje (u energetskom regionu 30 keV-300<br />keV), sa maksimumom na oko&nbsp; 90 keV, u značajnoj meri&nbsp; proizvedeno<br />kosmičkim zračenjem, sa fluksom fotona od oko 3000 m^-2s^-1. Takođe,<br />ustanovljeno je da dozama op&scaron;te populacije doprinosi ovo sveprisutno<br />niskoenergetsko gama zračenja kosmičkog porekla, zajedno sa<br />odgovarajućim fluksom niskoenergetskih elektrona i da ove komponente<br />ukupnih doza indukovanih kosmičkim zračenjem na nivou mora nisu<br />zanemarljive.</p> / <p>In this dissertation results of complex research on cosmic-ray impact on&nbsp;nuclear spectra at sea level are shown.&nbsp; The appropriate selection of&nbsp;coincidence time interval &nbsp;in low-background experiments that are based&nbsp;on the rejection of anticoincidence background events is very important&nbsp;for reducing the influence of cosmic-ray muons on acquired spectral&nbsp;data. In&nbsp; the first&nbsp; experiment&nbsp; presented in this dissertation,&nbsp; performed by&nbsp;the coincidence system of an HPGe detector and a plastic detect or&nbsp; in a&nbsp;surface laboratory, the time resolution of the detected events is explored.&nbsp;It is&nbsp; found that the prompt and delayed coincidence events between a&nbsp;plastic veto detector and a &nbsp;Ge detector can be sharply divided for&nbsp;approximately 100 ns in two groups. In addition, the bremsstrahlung&nbsp;and annihilation events can&nbsp; be time-resolved from the (n,n&rsquo;) events,&nbsp;although all of these events belong to the group of delayed events. Also,&nbsp;substantially delayed annihilation events, which are caused by the&nbsp;<br />decays of stopped positive muons, were detected.<br />The second experiment shown in this dissertation is based on the 100%&nbsp;relative efficiency ultra-low-background HPGe spectrometer. With the&nbsp;addition of two plastic scintillators and a fast-slow coincidence circuit,&nbsp;the coincidence events between the plastic detectors and the HPGe&nbsp;spectrometer have been investigated. This&nbsp; MIREDO (Muon Induced&nbsp;Rare Event Dynamic Observatory) spectrometer system is primarily&nbsp;<br />developed for the study of cosmic muon induced processes in different&nbsp;materials. Exploration of such interactions can be important for ultra-low&nbsp;background experiments. Results derived for three samples, placed in a&nbsp;Marinelli beaker, are presented and discussed.<br />In third experiment shown in this dissertation,&nbsp; the potential influence of&nbsp;solar neutrinos on measured decay rate is investigated by&nbsp; the liquid&nbsp;scintillation measurement of the count rate variations of&nbsp;³H. Making use of the sophisticated Quantulus liquid scintillation spectrometer, it is&nbsp;found that the&nbsp; measurement of the high-energy tail of&nbsp;³H spectrum may be significantly influenced by instrumental&nbsp; instability.&nbsp; The oscillatory behavior of measured high-energy tail of ³H spectrum&nbsp; is registered, but&nbsp;with very small amplitude (less than 0.5%), which cannot&nbsp; be easily&nbsp;<br />explained only by instrumental instability. When the total&nbsp;³H spectrum was measured, no significant variations in the count rate were found.&nbsp;<br />For a long time, it has been known that low-energy continuous gamma&nbsp;radiation is present in open air at the Earth&rsquo;s surface. In previous&nbsp;investigations it was assumed that this radiation is produced almost&nbsp;exclusively by gamma photons emitted due to the natural radioactivity,&nbsp;which are backscattered by air above ground.&nbsp; In the fourth experiment&nbsp;presented in this dissertation, it is&nbsp; shown&nbsp; that significant amount of this&nbsp;<br />radiation (related to energy region 30&nbsp; keV-300&nbsp; keV) that peaks at about&nbsp;90 keV, is produced by cosmic-rays, with the photon flux of about 3000&nbsp;m^-2s^-1.&nbsp; Also, it is found&nbsp; that the contribution of this omnipresent low&nbsp;energy gamma radiation of cosmic-ray origin, including the&nbsp;corresponding low-energy electron flux, to the doses of general&nbsp;<br />population are non-negligible components of overall doses induced by&nbsp;cosmic rays near sea level.</p>

This diploma thesis is oriented to analysis of physiological effect of synthetic estrogen ethinylestradiol (EE), which represents the main component of steroid-based substance used in hormonal contraception. From wide range of physiologically important protein molecules, which might be effected by this steroid, thesis focuses to the study of the sodium plus potassium activated, magnesium dependent adenosinetriphosphatase (Na+, K+ - ATPase), which is selectively inhibited by cardiac glycosides such as ouabain (g strophantine). Na+, K+ - ATPase represents an important plasma membrane bound enzyme, which catalyzes the active transport of sodium and potassium across plasma membrane. In the first part of this work, Na+, K+ - ATPase was determined by binding of radioactively labeled selective inhibitor of this enzyme [3H]ouabain, used for this purpose. In the second part of this work, plasma membrane fluidity was analyzed by steady-state fluorescence anisotropy of DPH. The effect of EE on [3H]ouabain binding was studied first under in vitro conditions by using human embryonic kidney cells (HEK293) which were cultivated for 24 hours in the presence of EE in tissue culture medium. Second, the effect of EE was also studied under in vivo conditions, by subcutaneous application of EE to the female rats of Wistar...

<p dir="ltr">Alpine glacier meltwater is an important source of recharge supporting groundwater flow processes in the high mountains. In the face of rapid ice loss, knowledge of response times of mountain aquifers to loss of glacial ice is critical in evaluating the sustainability of alpine water resources for human communities and alpine ecosystems. Glaciers are very sensitive to changes in climate, they advance during periods of global or regional cooling, and they retreat in response to global or regional warming conditions. When the glaciers grow, the equilibrium-line altitude separating the zone of accumulation and zone of ablation on the glacier moves downslope; it moves upslope when they retreat. The latter is not a sustainable condition for the glacier. Previous studies have shown that glacial meltwater is an important source of groundwater recharge. However, we lack fundamental information on the importance of glacial meltwater in mountain groundwater processes such as supporting baseflow generation to alpine streams, perennial flow to alpine springs, and the geochemical evolution of groundwater in mountain aquifers. Thus, continued glacial ice loss may have severe consequences for alpine hydrological and hydrogeological systems.</p><p dir="ltr">Glacier National Park (GNP) and Mount Hood National Forest (MH), both have alpine glaciers. These two study sites show different responses to climate change since their glaciers are in different states of retreat. GNP glaciers are in advanced stages of retreat compared to MH glaciers. Groundwater samples were collected from springs, seasonal snow, glacial ice, and glacial melt (subglacial flow) in GNP and MH. The samples were analyzed for a suite of environmental isotopes and geochemical tracers to address the following questions: 1) How are isotopic fingerprints of glacial meltwater preserved in mountain-block aquifers? What does the isotopic fingerprint of subglacial flow tell us about melting, meltwater processes, and mixing processes? 2) Is the preservation of the isotopic fingerprint of glacial meltwater affected by aspect controls on ice preservation? Aspect is defined as the compass direction of the slope where the glacier is found. 3) What controls groundwater flow and flowpath connectivity from high elevations (near glacier) to lower elevations? What geologic units support groundwater flow to local- and regional-scale springs and flowpath connectivity across spatial scales in each study site?</p><p dir="ltr">The flow of groundwater in mountainous terrain is heavily dependent on the hydraulic properties of the bedrock including presence/absence of dipping layers and structural features, primary and secondary porosity, and presence/absence of ongoing tectonic activity. Strontium isotopes (⁸⁷Sr/⁸⁶Sr) were used to identify the rock units that host groundwater flowpaths and to quantify flowpath connectivity across spatial scales in both study sites. The ⁸⁷Sr/⁸⁶Sr data show that flowpaths in GNP are primarily hosted in the Helena Formation and permeable facies in the Snowslip Formation. Groundwater also flows through alluvium and younger bedrock units, and there is some flow along or through the volcanic sill in the Helena Formation. Hydrostratigraphy also affects groundwater flow and the spatial distribution of alpine springs in GNP. At MH, the rock units hosting flowpaths are young reworked volcanic rock units that are Quaternary in age. Flowpaths in MH appear to be connected across spatial scales since warm springs emerging along the lower southern slopes of Mount Hood preserve stable isotopic signatures of glacial meltwater. In comparison, nearly all the sampled springs in GNP emerge on south-facing slopes. This is not an indication of ice preservation, instead it’s controlled by hydrostratigraphy. In fact, it’s unlikely that high-elevation groundwater is strongly connected to low-elevation sites due to hydrostratigraphy. There are more springs on south-facing slopes at MH as well; however, they do not preserve an isotopic signature of recharge from glacial meltwater except for the warm springs. Springs on north-facing slopes in MH, however, do preserve the signature.</p><p dir="ltr">Tritium (³H) and chlorine-36 (³⁶Cl/Cl) were measured to assess how the isotopic fingerprint of glacial meltwater is preserved in mountain aquifers. The ³H activities in spring water are elevated in GNP and it’s difficult to differentiate between modern precipitation and glacial meltwater. Tritium activities are lower in MH, but it’s also difficult to differentiate between potential endmembers. This discrepancy could imply that glacial meltwater doesn’t contribute to groundwater recharge, but this doesn’t support the Bayesian stable isotope mixing model results of an earlier study. Instead, I infer that englacial mixing processes are affecting the isotopic fingerprint of subglacial melt. An englacial mixing model (EMM) was developed to explain how the isotopic fingerprint of subglacial flow (glacial meltwater) changes in relation to the stage of retreat. The stage of retreat is important because it controls the proportion of glacial meltwater to runoff from snowmelt and rain that enters the englacial network from the surface of the glacier. Mixing occurs in the englacial network, and the mixed water is transported to the base of the glacier. Englacial mixing in conduits, fractures, and moulins affects the ³H and ³⁶Cl/Cl fingerprint of subglacial flow and will, in turn, affect the isotopic fingerprint of recharge from glacial meltwater. For this study, the ³H is not robust by itself; however, ³⁶Cl/Cl shows some additional benefits over ³H. The EMM suggests that the impact of englacial mixing and the influence of modern precipitation on the isotopic composition of subglacial flow increases as the glacier retreats in both GNP and MH. This model is novel to the best of our knowledge. Additional testing of the EMM should be prioritized in the near future.</p>

The 2-aryl-6,8-dibromoquinazolin-4(3H)-ones were prepared in a single-pot operation by condensing 6,8-dibromoanthranilamide and aryl aldehydes in the presence of molecular iodine in ethanol. Treatment of the 2-aryl-6,8-dibromoquinazolin-4(3H)-ones with thionylchloride in the presence of dimethylformamide afforded the corresponding 2-aryl-4-chloro-6,8-dibromoquinazolines. Palladium(0)-copper iodide catalysed Sonogashira cross-coupling reaction of 2-aryl-4-chloro-6,8-dibromoquinazolines with terminal alkynes at room temperature afforded series of 2-aryl-6,8-dibromo-4-(alkynyl)quinazolines. Further transformation of the 2-aryl-6,8-dibromo-4-(phenylethynyl)quinazolines via Suzuki-Miyaura cross-coupling with arylboronic acids occurred without selectivity to afford the corresponding 2,6,8-triaryl-4-(phenylethynyl)quinazolines. The compounds were characterized using a combination of NMR (1H and 13C) and IR spectroscopic techniques as well as mass spectrometry. The absorption and emission properties of 2,6,8-triaryl-4-(phenylethynyl)quinazolines were determined in solution. / Chemistry / M.Sc. (Chemistry)

Explosive materials have always been attracting the attention of scientists. Various explosives either in pure bulk form or as admixtures are synthesized and investigated from different points of view. However, because of dangerous character of these materials, their syntheses and properties have to be forecasted by theoretical studies. The new research trends of explosive materials generally include the designs of novel derivatives of well&ndash / known explosives to improve their detonation performances (heats of explosion, detonation velocities and detonation pressures) and thermal stabilities and decrease their sensitivities towards friction, electric spark, shock and impact either experimentally or theoretically. NTO (5&ndash / nitro&ndash / 2,4&ndash / dihydro&ndash / 3H&ndash / 1,2,4&ndash / triazol&ndash / 3&ndash / one) and PATO (3&ndash / picrylamino&ndash / 1,2,4&ndash / triazole) are very important secondary explosives that take place in the literature for many years in terms of their explosive properties. In this thesis study, new species of these explosives have been designed to enhance their detonation performances (ballistic properties) and to lower their sensitivities and reactivities computationally. Additionally, aromatic nitration reactions and their mechanisms for unprotonated and protonated PATO species have been analyzed. The ab initio quantum chemistry methods, Hartree&ndash / Fock (HF) and Density Functional Theory (DFT), have been used in the calculations with Pople basis sets. Novel NTO and PATO tautomeric species have been designed and investigated to enlighten the effects of tautomerism on their quantum chemical properties and detonation performances in the gas phase. Various aromatic nitration mechanisms (carbon and nitrogen mono&ndash / nitration mechanisms) of unprotonated tautomeric PATO species as well as PATO have been designed in gas phase and the reaction states (pre&ndash / transition states, transition states, intermediates and nitration products) have been detected belonging to these mechanisms. Nitrations in solution phase have also been analyzed. The reaction states have been detected for carbon and nitrogen mono&ndash / nitrations of protonated PATO species in the gas phase. The detonation performances of unnitrated and nitrated PATO products have been presented.

The 2-aryl-6,8-dibromoquinazolin-4(3H)-ones were prepared in a single-pot operation by condensing 6,8-dibromoanthranilamide and aryl aldehydes in the presence of molecular iodine in ethanol. Treatment of the 2-aryl-6,8-dibromoquinazolin-4(3H)-ones with thionylchloride in the presence of dimethylformamide afforded the corresponding 2-aryl-4-chloro-6,8-dibromoquinazolines. Palladium(0)-copper iodide catalysed Sonogashira cross-coupling reaction of 2-aryl-4-chloro-6,8-dibromoquinazolines with terminal alkynes at room temperature afforded series of 2-aryl-6,8-dibromo-4-(alkynyl)quinazolines. Further transformation of the 2-aryl-6,8-dibromo-4-(phenylethynyl)quinazolines via Suzuki-Miyaura cross-coupling with arylboronic acids occurred without selectivity to afford the corresponding 2,6,8-triaryl-4-(phenylethynyl)quinazolines. The compounds were characterized using a combination of NMR (1H and 13C) and IR spectroscopic techniques as well as mass spectrometry. The absorption and emission properties of 2,6,8-triaryl-4-(phenylethynyl)quinazolines were determined in solution. / Chemistry / M.Sc. (Chemistry)