In this thesis both an experimental and computational study of selected prospective materials for nonlinear optics is presented. The main focus was put on 2-aminopyrimidinium hydrogen- phosphite (AMPPO3), a salt with high SHG efficiency and Type I. phase matching properties. AMPPO3 had been studied by our research group and its favourable qualities such as easy preparation, colourlessness, great water solubility and good crystallinity motivated further in- terest and the attempts for the growth of bulk single crystals from thermostated aqueous solu- tions as presented here. The products are meant to be probed by laser in a specific direction to determine the maximum SHG efficiency, so far the polarized microscopy study revealing the extreme dispersion effects is provided. AMPPO3 is an example of H-bond stabilized framework with both organic and inorganic building blocks. The computational study was led as to understand the structure which is typical for one of the classes of compounds exhibiting nonlinear optical properties. DFT implemented in parallel CP2K was used and for the comparison three other optically active materials of sim- ilar composition were studied - urea, guanylurea hydrogenphosphite and 2-aminopyrimidine- boric acid 3/2 cocrystal. After the constrained geometry optimization and cell...

Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2018-06-12T11:22:07Z No. of bitstreams: 2 Dissertação - Felipe Cavalcanti Sampaio - 2013.pdf: 1683727 bytes, checksum: 6cab873178ad2e097fe434f4aa8fca34 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2018-06-12T12:21:36Z (GMT) No. of bitstreams: 2 Dissertação - Felipe Cavalcanti Sampaio - 2013.pdf: 1683727 bytes, checksum: 6cab873178ad2e097fe434f4aa8fca34 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-06-12T12:21:36Z (GMT). No. of bitstreams: 2 Dissertação - Felipe Cavalcanti Sampaio - 2013.pdf: 1683727 bytes, checksum: 6cab873178ad2e097fe434f4aa8fca34 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2013-01-15 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Purpose: to assess the surface and evaluate the chemical composition of root canal filling materials by scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX). Methods: eighteen polyethylene standard tubes were filled with the tested materials: Sealapex®, Sealer 26®, MTA Fillapex®, Pulp Canal Sealer®, Endofill® and AH Plus®. After 48 hours at 37°C and 95% relative humidity, the samples were surface-sputtered with gold, led to SEM and the images analyzed at 5,000X magnification. Then, the elements distribution and chemical composition were determined by EDX. The results were evaluated qualitatively (SEM images and elements distribution maps) and quantitatively (weight percentage). Results: the surface analysis revealed that the sealers presented different regularities, with an uniform distribution of elements, with particles of similar sizes and variable shapes in EDX microanalysis. Calcium oxide and hydroxide based sealers (Sealapex® and Sealer 26®) presented calcium peaks of 53.58wt.% and 65.00wt.%, respectively. MTA Fillapex® presented 30.58wt.% of calcium and high amounts of silicon (31.02 weight%) and bismuth (27.38 weight%). Zinc oxide and eugenol based sealers, Pulp Canal Sealer® and Endofill®, showed zinc quantities of 67.74wt% and 63.16wt.%, respectively. AH Plus® had higher amount of zirconium (64.24wt.%). The materials presented elements incompatible with the composition described by the manufacturer. Conclusions: the root canal sealers’ surfaces showed different. The elements presented uniform distribution, with particles of similar sizes and variable shapes. Chemical elements were found in the root canal sealers not described by the manufacturers. / Objetivo: analisar a superfície e avaliar a composição química de materiais obturadores do canal radicular por meio de microscopia eletrônica de varredura (MEV) e espectroscopia de dispersão de raios-X (EDX). Material e métodos: dezoito tubos de polietileno padronizados foram preenchidos com os materiais avaliados (n=3): Sealapex®, Sealer 26®, MTA Fillapex®, Pulp Canal Sealer®, Endofill® e AH Plus®. Após 48 horas a 37°C e umidade relativa de 95%, as amostras foram metalizadas com ouro, conduzidas ao MEV e as imagens da superfície analisadas em um aumento de 5.000X. A seguir, a distribuição dos elementos e composição química foram determinadas por meio de EDX. Os resultados foram avaliados qualitativamente (imagens do MEV e mapas de distribuição de elementos) e quantitativamente (porcentagem em peso). Resultados: a análise da superfície revelou que os cimentos apresentaram diferentes regularidades em imagens por MEV. As partículas apresentaram-se com distribuição uniforme dos elementos, com tamanhos similares e formas variáveis em microanálises por EDX. Os cimentos à base de óxido ou hidróxido de cálcio (Sealapex® e Sealer 26®) apresentaram quantidades de cálcio de 53,58%p (porcentagem de peso atômico) e 65,00%p, respectivamente, em microanálises por EDX. O cimento MTA Fillapex® apresentou 30,58%p de cálcio e elevadas quantidades de silício (31,02%p) e bismuto (27,38%p). Os cimentos contendo óxido de zinco e eugenol, Pulp Canal Sealer® e Endofill®, apresentaram zinco em quantidades de 67,74%p e 63,16%p, respectivamente. O AH Plus® apresentou maior quantidade de zircônia (64,24%p). Foram encontrados elementos não compatíveis com a composição descrita pelo fabricante. Conclusões: as superfícies dos cimentos endodônticos mostraram diferentes regularidades. As partículas apresentaram distribuição uniforme, com tamanhos similares, porém com formas variadas. Foram encontrados nos cimentos endodônticos elementos químicos que não foram descritos pelos fabricantes.

<p>  </p> <p>Atmospheric particles originate from all over the globe with wildly different sources such as sea spray aerosols of the ocean, mineral dust from deserts, biogenic emissions from forests, anthropogenic emissions of urban and industrial areas, volcanic eruptions, and many more. All of these particles can then be transported during which aging can occur where the external and internal chemical composition of particles and drastically be altered in which their physiochemical properties change or new particles as a whole are formed. Understanding what can cause this aging and correctly identifying how these particles change is vital for assessing climate in local areas. </p> <p>Chapter 3 focuses on dry intrusion (DI) and non-DI periods where vertical mixing of air occurs and allows for long range transport of particles. DI periods introduces populations of aged particles from far away sources into local regions. Identification and chemical characterization is performed for both of these periods to highlight the changes the DI period introduces in regards to particle morphology, chemical composition and lifetime. Analysis was performed via computer controlled scanning electron microscopy (CCSEM) for external information of the particles and scanning transmission x-ray microscopy (STXM) was used for internal information. The combination of these two techniques allows for a complete and thorough understanding of the particles during the two periods. </p> <p>Chapter 4 covers the first experiment done on a newly constructed cryogenic cooling cart which was created in the hopes to identify individual ice nucleating events of particles <em>in situ</em> when mimicking real world atmospheric conditions through temperature and humidity control. </p>

This thesis concerns the application of aberration corrected scanning transmission electron microscopy (STEM) to the quantitative analysis of industrial Pd-Pt core-shell catalyst nanoparticles. High angle annular dark field imaging (HAADF), an incoherent imaging mode, is used to determine particle size distribution and particle morphology of various particle designs with differing amounts of Pt coverage. The limitations to imaging, discrete tomography and spectral analysis imposed by the sample’s sensitivity to the beam are also explored. Since scattered intensity in HAADF is strongly dependent on both thickness and composition, determining the three dimensional structure of a particle and its bimetallic composition in each atomic column requires further analysis. A quantitative method was developed to interpret single images, obtained from commercially available microscopes, by analysis of the cross sections of HAADF scattering from individual atomic columns. This technique uses thorough detector calibrations and full dynamical simulations in order to allow comparison between experimentally measured cross section to simulated ones and is shown to be robust to many experimental parameters. Potential difficulties in its applications are discussed. The cross section approach is tested on model materials before applying it to the identification of column compositions of core-shell nanoparticles. Energy dispersive X-ray analysis is then used to provide compositional sensitivity. The potential sources of error are discussed and steps towards optimisation of experimental parameters presented. Finally, a combination of HAADF cross section analysis and EDX spectrum imaging is used to investigate the core-shell nanoparticles and the results are correlated to findings regarding structure and catalyst activity from other techniques. The results show that analysis by cross section combined with EDX spectrum mapping shows great promise in elucidating the atom-by-atom composition of individual columns in a core-shell nanoparticle. However, there is a clear need for further investigation to solve the thickness / composition dualism.

Nanomaterials display interesting physical and chemical properties depending on their shape, size and composition. Self assembly is an intriguing route to producing nanomaterials with controllable compositions and morphologies. DNA has been used to guide the self assembly of materials, resulting in: (1) metal nanowires; (2) metal or semiconductor nanorods; (3) carbon nanotubes; and (4) semiconductor, metal or biological nanoparticles. My work expands the range of DNA templated nanomaterials and develops novel ways of using DNA to pattern nanostructures on surfaces. I have performed the first synthesis of silver nanorods on single stranded DNA, an attractive material for localizing DNA coupled nanostructures through hybridization. I have demonstrated an ionic surface masking protocol to reduce ~70% of non specific metal deposition (a pervasive problem) during electroless plating of DNA with silver or copper. I have designed and constructed discrete three branched DNA junctions as scaffolding for self assembling three terminal, individually gateable nanotransistors. I have labeled these DNA structures with single streptavidin molecules, as a model for the placement of semiconductor nanocrystals at the junctions. Moreover, I have shown selective silver and copper plating of branched DNA constructs, with crystallinity that depends on plating conditions. I have fabricated DNA templated nickel nanostructures on surfaces and demonstrated their reversible interaction with a histidine labeled protein, as a model system for patterning histidine tagged nanostructures on surfaces. Previous methods were limited to decorating DNA scaffolds using streptavidin-biotin interactions. Finally, I have developed DNA shadow nanolithography, which uses angled thin film deposition and anisotropic etching to transfer patterns of surface aligned DNA onto substrates as nanoscale trenches with linewidths <30 nm. Nanotrenches can be post processed with microfabrication methods to modify their properties; I have constructed metal lines and nanopores from such trenches. This dissertation summarizes the principles and methods for synthesis and characterization of DNA templated nanomaterials. These biologically templated constructs may be useful in the fabrication of self assembled chemical and electrical sensors, and as structural materials for nanofabrication and nanopatterning on surfaces.

<p>U ovoj doktorskoj disertaciji izloženi su rezultati&nbsp;analize eksperimentalno i teorijski dobijene&nbsp;raspodele gustine naelektrisanja dva derivata&nbsp;tiosemikarbazida, 4-metil-3-tiosemikarbazida&nbsp;(MeTSC) i 4-metil-3-tiosemikarbazon 2-piridinformamida (TSC4). &nbsp;Analiza&nbsp;eksperimentalno dobijene gustine naelektrisanja je&nbsp;zasnovana&nbsp; na preciznim &nbsp;podacima dobijenim&nbsp;difrakcijom rendgenskog zračenja visoke&nbsp;rezolucije. Teorijska istraživanja bazirana su na&nbsp;teorijskim strukturnim faktorima dobijenim&nbsp;primenom programa CRYSAL09 polazeći od&nbsp;geometrije&nbsp; molekula određene nakon multipol&nbsp;utačnjavanja eksperimentalno dobijene gustine&nbsp;naelektrisanja. Za opisivanje eksperimentalne i&nbsp;teorijske ukupne elektronske gustine kori&scaron;ćen je&nbsp;Hansen-Coppens-ov multipol-model.&nbsp; Takođe je&nbsp;urađena i topolo&scaron;ka analizahemijskih veza i&nbsp;interakcija &nbsp;i ispitivana su elektrostatička svojstva&nbsp;atoma sumpora.</p><p>Analizom eksperimentalne gustine&nbsp;naelektrisanja kristalnih struktura MeTSC i TSC4&nbsp;uočeno je da deformaciona gustina slobodnih&nbsp;elektronskih parova S atoma ima &nbsp;oblik torusa, da&nbsp;je unutar njega raspodela elektronske gustine&nbsp;nehomogena i da položaj samog torusa može biti&nbsp;ortogonalan (SalTSC) ili pod uglom (MeTSC,&nbsp;<br />TSC4).&nbsp; Na osnovu raspodele deformacione&nbsp;gustine i elektrostatičkog potencijala, kao &nbsp;i na&nbsp;osnovu topolo&scaron;ke analize ukupne eksperimentalne&nbsp;gustine naelektrisanja &rho;_ktv&nbsp; i njenog Laplasijana &nabla;²&rho;_ktv zaključeno je da atom sumpora ima izrazitu&nbsp;fleksibilnost i sposobnost da prilagodi svoju&nbsp;elektronsku gustinu slobodnih elektronskih &nbsp;parova&nbsp;prostornom rasporedu donornih grupa koje&nbsp;učestvuju u interakcijama sa S akceptorom.&nbsp; U&nbsp;kristalnim strukturama MeTSC i TSC4 utvrđeno&nbsp;je da S atom istovremeno gradi četiri, odnosno&nbsp;prosečno &scaron;est međumolekulskih interakcija.</p><p>U cilju upotpunjavanja eksperimentalnih&nbsp;rezultata analizirana je teorijski dobijena gustina&nbsp;naelektrisanja oba molekula, a zatim su ispitivane&nbsp;karakteristike sumpora kao akceptora i to u&nbsp;sistemima različite složensti polazeći od&nbsp;izolovanih monomera, preko izdvojenih dimer do&nbsp;kristalnogokruženja. Ovom analizom je utvrđeno&nbsp;da se simultanim angažovanjem S atoma u vi&scaron;e&nbsp;interakcija ne umanjuje njegova akceptorska&nbsp;sposobnost.</p><p>Vodonične vezekoje uključuju S akceptor su&nbsp;ispitivane sa aspekta &nbsp;energijskih svojstava dimera&nbsp;koji suprisutni u MeTSCi TSC4, kaoi u dodatno&nbsp;konstruisanim&nbsp; sistemima&nbsp; MeTSC/MeOH&nbsp; i&nbsp;aceton/MeOH. Energijske&nbsp; karakteristike&nbsp; su&nbsp;proučavane u pogledu elektrostatičke energije&nbsp;interakcije (E_es) i kohezione energije(E_coh). Za&nbsp;<br />dva odabrana&nbsp; MeTSC/MeOH i aceton/MeOH&nbsp;sistema je primenjena metoda &nbsp;kuplovanih klastera&nbsp;kao&scaron;to&nbsp; je&nbsp;<em> ab initio</em>&nbsp; CCSD(T)&nbsp; metod.&nbsp; Za&nbsp;MeTSC/MeOH sistem je &nbsp;urađena potpuna&nbsp;optimizacija i za tako dobijenu ravnotežnu&nbsp;geometriju je izračunata energija sistema&nbsp;∆E_CCSD(T),CBS.</p> / <p>In this dissertation the analysis of the experimental and theoretically obtained electron &nbsp;density of two derivatives of thiosemicarbasides, 4-methyl-3-thiosemicarbaside (MeTSC) and 4-methyl-3-thiosemikabazone 2-piridinformamide (TSC4) are presented.&nbsp; The analysis of experimentally obtained electron density is based on &nbsp;accurate X-ray diffraction data of high resolution. Theoretically calculated electron densities are obtained from periodic quantum mechanical calculation using CRYSTAL09 and the accurate structural parameters from high resolution X-ray&nbsp;experiment. For the description of the theoretical and experimental electron density the Hansen-Coppens multipol model was used. Further topological analysis of chemical bonds and interactions was performed in order to explain the electrostatic properties of sulfur.</p><p>In this work it has been observed that in the experimentally obtained electron density of the MeTSC and TSC4 crystal structures, the deformational electron density of sulfur free electron pairs forms a toroidal shape. Further, this torus is not homogeneously filled but shows pronounced local accumulations and its position can be either orthogonal (like in SalTSC) or tilted (MeTSC, TSC4). Based on the distribution of the&nbsp;deformational electron&nbsp; density and electrostatic potential, as well as the topological analysis of the total electron density &rho;_ktv and its Laplasian &nabla;²&rho;_ktv&nbsp;it can be concluded that the S atom has a remarkable flexibility and ability to adapt his deformation electron density of free electron pairs into toruses corresponding to the position of donor groups surrounding him. In the crystal structures of MeTSC and TSC4 it was determined that the S atom participates in four and six interactions, respectively.</p><p>In order to supplement&nbsp; the experimentally obtained results a theoretically calculated electron density of both molecules (MeTSC and TSC4) was performed and the properties of the S atom as a hydrogen acceptor have been studied. The analysis was &nbsp;performed on systems of various complexity, starting with isolated monomers, then on &nbsp;dimers and up to the whole crystal packing. From this work it has been concluded that &nbsp;the acceptor capabilities of the S atom are not diminished with the increasing number &nbsp;of interactions.&nbsp;&nbsp;&nbsp;&nbsp;</p><p>The hydrogen bonding involving thioureido S&nbsp;acceptor is also investigated in terms of the energetic properties of the MeTSC and TSC4 dimers existing in the crystal structure, and additional MeTSC/MeOH and acetone/MeOH systems. Energetic features were thoroughly studied through electrostatic interactions energies (E_es) and &nbsp;cohesive energies (E_coh). For two selected MeTSC/MeOH and acetone/MeOH systems an ab initio approach&nbsp;employing the coupled-cluster singles and doubles augmented by a perturbational correction for connected triple excitations (CCSD(T)) method were applied. Finaly, for MeTSC/MeOH system full geometry optimization was &nbsp;performed and for resulting equilibrium geometry the energy of the system (∆E_CCSD(T),CBS) was calculated.</p>

<p>&nbsp;&nbsp; U ovoj doktorskoj disertaciji opisane su sinteze novih kompleksa prelaznih metala sa piridoksiliden-&nbsp; (PLAG), odnosno saliciliden-aminogvanidinom (SALAG). Dobijeni<br />kompleksi su okarakterisani elementalnom analizom, IR spektrima, konduktometrijskim i magnetnim merenjima, a većina i rendgenskom<br />strukturnom analizom. Osim toga, dobijene su i nove forme ovih &Scaron;ifovih baza, i to u vidu monokristala, čime su omogućena ispitivanja njihovih&nbsp; molekulskih i kristalnih struktura, kao i uporedna analiza sa koordinovanim ligandima.<br />&nbsp; &nbsp; Sa PLAG je sintetisano 7 novi&nbsp; kompleksa Cu(II), a pored toga po prvi put su<br />izolovani mono i bis(ligand) kompleksi Fe(III) i Co(III), mono(ligand) kompleksi&nbsp; V(V), kao&nbsp; i jedan kompleks Zn(II) u kojem ovaj potencijalno tridentatni&nbsp;<em> ONN&nbsp;</em> ligand,&nbsp; u<br />monoprotonovanoj formi,&nbsp; ima ulogu kontra-jona. Sa stanovi&scaron;ta geometrije zajedničko za izolovane komplekse Cu(II) i V(V) je da imaju kvadratno-piramidalnu strukturu, sa izuzetkom jednog kvadratno-planarnog kompleksa Cu(II), dok je u kompleksima Fe(III) i Co(III) nađeno očekivano oktaedarsko okruženje centralnog<br />jona. Pored ovih, sintetisano je i pet novih kompleksa sa SALAG, od kojih su dva<br />kompleksa Cu(II) i kompleks V(V) okarakterisani rendgenskom strukturnom<br />analizom, dok je mikrokristalnim bis(ligand) kompleksima Co(III) i Ni(III) na osnovu<br />fizičko-hemijskih karakteristika predložena odgovarajuća struktura.<br />&nbsp;&nbsp; Zajedničko za obe opisane &Scaron;ifove baze je da se koordinuju na&nbsp;<em> ONN&nbsp; </em>tridentatni način, i to preko atoma kiseonika deprotonovane fenolne grupe i atoma azota azometinske i imino grupe AG fragmeta. Posebno je nagla&scaron;eno da su&nbsp; sa<br />PLAG izolovana dva dimerna kompleksa Cu(II) u kojima je po prvi put nađena tetradentatna koordinacija ovog&nbsp; liganda, u koju je dodatno uključen atom kiseonika hidroksimetil-grupe PL-ostatka. Za razliku od SALAG, koji je u izolovanim kompleksima koordinovan isključivo kao monoanjon, nastao deprotonacijom fenolne<br />OH-grupe, za PLAG je osim ove, potvđena koordinacija u neutralnoj, zwitter-jonskoj, ali i dvostruko deprotonovanoj formi. Zwitter-jonska forma liganda nastaje migracijom atoma vodonika sa fenolnog hidroksila na piridinski atom azota PL-ostatka, dok deprotonacijom piridinskog ili hidrazinskog atoma azota, odnosno oba pomenuta atoma nastaju monoanjon i dianjon helatnog liganda, respektivno.<br />&nbsp;&nbsp; Na kraju, urađena su&nbsp; i ispitivanja antimikrobne aktivnosti odabranih jedinjenja<br />prema predstavnicima grampozitivnih i gramnegativnih bakterija, kao i dve kulture<br />kvasca. Tom prilikom nije utvrđena nikakva inhibitorna aktivnost&nbsp;&nbsp; prema primenjenim<br />bakterijskim sojevima, dok su u slučaju kvasaca izvesno mikrobicidno dejstvo pokazali samo kompleksi Cu(II).</p> / <p>This PhD thesis describes the syntheses of some new transition metal complexes with&nbsp; pyridoxilidene-&nbsp; (PLAG) and salicylideneaminoguanidine (SALAG). Obtained&nbsp; complexes are characterized by&nbsp;&nbsp; elemental analysis, IR&nbsp; spectroscopy,&nbsp; conductometric and magnetic measurements. Besides, the structural analysis of majority of the obtained complexes was performed. Some new forms of these Schiff&nbsp; bases are synthesized in form of single crystals, which made their X-ray analysis as well as comparison with coordinated forms possible.</p><p>With PLAG, 7 new Cu(II) complexes were obtained and for the first time mono and bis(ligand) complexes of Fe(III) and Co(III) as well&nbsp; mono(ligand)&nbsp; complexes&nbsp; of V(V) were isolated. Furthermore,&nbsp; the structure of Zn(II) complex in which PLAG in its monocationic form has a role of counter ion is presented. With the exception of one Cu(II) complex, all reported Cu(II) and V(V) complexes have a square-pyramidal geometry, whilst&nbsp; Fe(III)&nbsp; and Co(III)&nbsp; are situated in octahedral surroundings. Also, five new complexes of Cu(II), Co(III), Ni(II) and V(V) with SALAG were synthesized. In both&nbsp; Cu(II) complexes and V(V) complex the expected coordination mode and geometry were confirmed by X-ray analysis, while octahedral structure of bis(ligand) complexes with Co(III) and Ni(II) was proposed based on results of physico-chemical&nbsp; characterization.</p><p>Both PLAG and SALAG coordinate the metal ion in tridentate&nbsp; ONN&nbsp; manner, through the oxygen atom of deprotonated phenolic group and nitrogen atoms&nbsp; of azomethine and imino groups of AG moiety. It is also emphasized that in two dimeric Cu(II) complexes with PLAG tetradentate coordination mode was found, in which the oxygen atom of hydroxymethyl group of PL residue was additionally involved. Unlike SALAG, which is coordinated as monoanion in all of the examined complexes, PLAG can have one of three degrees of deprotonation. Zwitter-ion of PLAG is formed by migration of H-atom from phenolic oxygen to pyridine nitrogen, while the deprotonation of pyridine or/and hydrazine nitrogen, makes it mono-and dianion, respectively.</p><p>Also, microbiological tests on the selected compounds were preformed. Namely, antimicrobial activity of these compounds against some gram-positive and gram-negative bacteria, as well as some yeast cultures was examined and none of the samples showed antimicrobial activity against bacteria, whilst only Cu(II) complexes showed certain inhibitory effect against yeasts.</p>

Gegenstand der vorliegenden Arbeit ist die Synthese und Charakterisierung neuartiger elektrophiler Barbiturate. In diesen Zielverbindungen sollte die kovalente Verknüpfung eines elektrophilen bzw. Lewis-aciden Zentrums mit einer Wasserstoffbrückensequenz realisiert sowie deren gegenseitige Beeinflussung untersucht werden. Im Mittelpunkt standen dabei Barbitursäure-funktionalisierte Triarylmethylium-Ionen sowie Merocyanine. Die Charakterisierung der synthetisierten Verbindungen erfolgte mittels NMR-Spektroskopie, Einkristall-Röntgenstrukturanalyse sowie solvatochromen Messungen. Besonderes Augenmerk lag auf der Wechselwirkung mit verschiedenen Rezeptoren über Wasserstoffbrückenbindungen, wobei sowohl die Anzahl als auch die Stärke der Wasserstoffbrücken variiert wurden. Die Reaktion der elektrophilen Barbiturate mit ausgewählten Nucleophilen wurde NMR- und UV/Vis-spektroskopisch verfolgt. In ternären Systemen bestehend aus Elektrophil, Nucleophil und Rezeptor wurde systematisch der Einfluss der Komplexierung über Wasserstoffbrücken auf die Gleichgewichts- und Geschwindigkeitskonstante der Elektrophil-Nucleophil-Rekombination erfasst. Daneben erfolgte die Bestimmung der Nucleophilie-Parameter substituierter Barbiturat-Anionen unter Berücksichtigung des ambidenten Verhaltens dieser Nucleophile.

Les amas de galaxies sont l'une des plus grandes structures dans l'univers et jouent le rôle d'hôte de plusieurs phénomènes complexes. Bien qu'il existe beaucoup d'études portant sur leur formation et leur évolution, l'avènement récent de l'apprentissage automatique en astronomie nous permet d'investiguer des questions qui, jusqu'à maintenant, demeuraient sans réponse. Même si ce mémoire se concentre sur l'application de techniques d'apprentissage automatique aux observations en rayons X des amas de galaxies, nous explorons l'usage de ces techniques à son homologue à une échelle réduite : les galaxies elles-mêmes. Malgré le fait que les trois articles présentés dans ce mémoire se concentrent sur différents aspects de la physique, sur de différentes échelles et sur de différentes techniques, ils forment une base d'études que je continuerai pendant mon doctorat : l'usage des nouvelles techniques pour investiguer la physique des régions galactiques et extragalactiques. Dans le premier article, nous introduisons les premières observations en rayons X d'un amas de galaxies lointain qui détient des attributs particuliers comme une formation stellaire hors pair (∽ 900 M⊙/an). Dans cet article, nous employons les techniques traditionnelles en astronomie rayons X pour déterminer si ce taux de formation stellaire est dû à un courant de refroidissement désinhibé. Puisque l'objet est très lointain (z=1.7), il faut faire nos calculs sans beaucoup de photons et il faut donc utiliser les indices par procuration. Nous déterminons que la galaxie centrale est séparée d'une distance de plus de 50 kpc du coeur froid de l'amas. À cause de cette séparation, le trou noir supermassif central n'est pas alimenté et il ne peut pas prévenir le courant de refroidissement. Ceci est le premier exemple d'un amas de galaxies où nous observons l'échec de la rétroaction d'un trou noir supermassif. De plus, ceci nous fournit un autre mécanisme qui peut créer la lumière intra-amas. Dans le deuxième article présenté ici, nous examinons l'émission rayons X provenant du milieu intra-amas extrêmement chaud des amas de galaxies. Nous développons une méthode compréhensive qui détermine le nombre de composantes thermiques sous-jacentes dans un spectre de plasma. Notre nouvelle technique est basée sur une combinaison d'algorithmes d'apprentissage automatique non supervisé (analyse de composantes principales) et d'apprentissage automatique supervisé (arbre aléatoire). Nous créons un ensemble de 100 000 observations synthétiques et réalistes de Chandra qui représentent le gaz chaud dans les amas de galaxies voisines. Après la réduction de notre ensemble d'entraînement à ses 25 composantes principales, nous entraînons notre classificateur afin qu'il puisse déterminer le nombre de composantes thermiques sous-jacentes. Une fois l'étape d'entraînement terminée et l'optimisation des hyperparamètres terminée, nous appliquons la méthodologie à l'amas de galaxies de Persée. En plus de créer une carte de l'amas qui indique le nombre de composantes thermiques nécessaires afin de modéliser précisément l'émission du gaz chaud, nous avons développé un ensemble d'outils numériques qui calculent les températures associées. Nos résultats sont en accord avec plus d'une décennie d'études sur l'amas de galaxies de Persée et nous indiquent qu'il faut utiliser plusieurs composantes thermiques pour modéliser le milieu intra-amas correctement. Le troisième article présenté dans ce mémoire emploie de nouveau l'apprentissage automatique pour résoudre une question précédemment sans réponse nécessaire pour la caractérisation précise de la cinématique de gaz chaud dans les galaxies. Nous avons construit un réseau de neurones convolutif qui estime la vitesse et l'élargissement des raies d'émission d'un spectre de galaxies en visible. Une fois construit, nous l'appliquons aux données synthétiques qui répliquent les observations réelles de SITELLE du programme SIGNALS. En utilisant notre réseau bien entraîné, nous caractérisons l'émission d'une cible de SIGNALS : la galaxie M33. Nos résultats indiquent que notre algorithme surpasse les méthodes standards et s'adapte bien aux procédures d'ajustement spectral. En outre, notre méthodologie augmente la vitesse des calculs par plus d'un ordre de grandeur. Bien que l'algorithme soit entraîné spécifiquement pour SITELLE, on peut faire de petites modifications pour l'utiliser avec des autres interféromètres tels que MUSE et ses futurs analogues dans la prochaine génération de télescopes. Notez que j'ai mené à titre de premier auteur deux des trois articles présentés dans ce mémoire et apporté des contributions majeures au troisième. Les trois articles ont déjà été acceptés pour publication ou ont déjà été soumis et révisés une fois. / Galaxy clusters are one of the largest structures in the universe and host several complex physical phenomena. Although a wealth of knowledge already exists on their formation and evolution, the recent advent of machine learning in the astronomical sciences has allowed us to probe questions heretofore unanswered. While this thesis does focus heavily on the application of machine learning techniques to X-ray observations of galaxy clusters, it takes the techniques applied there to galaxy cluster's smaller counterparts: the individual galaxies themselves. Although the three papers presented here focus on distinct physics, scales, and techniques, they all form a basis of studies that I will continue during my doctorate: using new techniques to probe the underlying physics of galactic and extragalactic regions. The first paper introduced is a study of a galaxy cluster near the beginning of the epoch of cluster formation exhibiting peculiar attributes such as an elevated stellar formation rate (∽ 900M⊙/yr). In this paper, we employ traditional techniques in X-ray astronomy to determine whether or not the prodigious formation rate is due to an uninhibited cooling core. Since the object is so distant (z=1.7), we must execute our calculations with relatively few photons and thus rely on proxy measures. We determine that there exists a strong cooling flow offset by over 50 kpc from the central galaxy. Because of this offset, the AGN is not fueled and thus fails to heat up the cooling flow. This is the first example of a galaxy cluster in which we observe the failure of AGN feedback. Additionally, this provides another mechanism for the creation of intracluster light. The second article presented here focuses on X-ray emission from the hot intra-cluster medium within the galaxy cluster. We develop a comprehensive method for determining the number of underlying thermal components in the plasma's spectra. Our novel technique relies on a combination of an unsupervised learning algorithm (principal component analysis) and a supervised learning algorithm (random forest classification). We create a set of 100,000 realistic mock Chandra observations of the hot X-ray emitting gas in nearby galaxy clusters. After reducing our synthetic training set to its 25 most important principal components, we trained a random forest classifier to distinguish between the number of underlying thermal components. After successful testing and hyperparameter optimization, we applied the methodology third paper featured in this thesis once again employs machine learning to solve a previously undetermined question necessary for the accurate characterization of the kinematics of the warm gas in galaxies. We constructed a convolutional neural network to estimate the velocity and broadening parameters from the optical spectra of emission-line nebula and applied it to synthetic data replicating real SITELLE observations from the SIGNALS program. With a trained and optimized network in hand, we apply our methodology to a target of the SIGNALS program: the galaxy M33. Our results indicate our algorithm out-performs previous methods and nicely complements spectral fitting procedures. Moreover, the methodology increases calculation speeds by more than an order of magnitude -- thus greatly reducing the time needed to determine the kinematic parameters. Although the algorithm was trained for SITELLE data, this method can be readily ported to other IFUs such as MUSE. I have led two of the papers presented in this memoire and made major contributions to the third. All three papers have been either accepted for publication or have already been submitted and revised once. to the Perseus Cluster. In addition to creating a map of the cluster indicating the number of thermal components required to accurately model the thermal emission, we developed a suite of analysis routines to determine the temperatures of the underlying components. Our results are in agreement with over a decade of studies on the Perseus cluster and indicate that multiple temperature components are required for the accurate study of its intracluster medium.

Gegenstand der vorliegenden Arbeit ist die Synthese und Charakterisierung neuartiger elektrophiler Barbiturate. In diesen Zielverbindungen sollte die kovalente Verknüpfung eines elektrophilen bzw. Lewis-aciden Zentrums mit einer Wasserstoffbrückensequenz realisiert sowie deren gegenseitige Beeinflussung untersucht werden. Im Mittelpunkt standen dabei Barbitursäure-funktionalisierte Triarylmethylium-Ionen sowie Merocyanine. Die Charakterisierung der synthetisierten Verbindungen erfolgte mittels NMR-Spektroskopie, Einkristall-Röntgenstrukturanalyse sowie solvatochromen Messungen. Besonderes Augenmerk lag auf der Wechselwirkung mit verschiedenen Rezeptoren über Wasserstoffbrückenbindungen, wobei sowohl die Anzahl als auch die Stärke der Wasserstoffbrücken variiert wurden. Die Reaktion der elektrophilen Barbiturate mit ausgewählten Nucleophilen wurde NMR- und UV/Vis-spektroskopisch verfolgt. In ternären Systemen bestehend aus Elektrophil, Nucleophil und Rezeptor wurde systematisch der Einfluss der Komplexierung über Wasserstoffbrücken auf die Gleichgewichts- und Geschwindigkeitskonstante der Elektrophil-Nucleophil-Rekombination erfasst. Daneben erfolgte die Bestimmung der Nucleophilie-Parameter substituierter Barbiturat-Anionen unter Berücksichtigung des ambidenten Verhaltens dieser Nucleophile.