No description available.

The development of artificial metal-based catalytic systems for phosphate ester hydrolysis is the central focus of this work. Currently, significant efforts are concentrated in this field of research as phosphate esters are remarkably stable linkages and are found in the molecules of life DNA and RNA, as well as in toxic compounds, such as nerve agents, pesticides and herbicides. The thesis describes the design and synthesis of a series of N-functionalised azamacrocyclic ligands suitable for metal chelation. An efficient strategy is described, where an aminal precursor is used for the selective N-alkylation of a cyclen moiety, in order to obtain non-bridged and ethylene-bridged cyclen-based ligands. Thereafter, the synthesis of the tetraamine Co(III) and Zn(II) aqua-hydroxo complexes is detailed, followed by a study of the coordination chemistry of Co(III)-based cyclen complexes. Moreover, the redox behaviour of such complexes is investigated by means of cyclic voltammetry. The hydrolytic activity of these complexes towards phosphate ester substrates is then presented. The hydrolytic activity of the cyclen-based Co(III) complexes is shown to be extremely sensitive to modest changes in the ligand structures, even though they do not affect the coordination geometry. Cyclen-based Zn(II) complexes appear to have no appreciable activity towards hydrolysis of phosphate mono- and di-esters under the same experimental conditions. The effect of incorporating polymerisable tetraamine Co(III) complexes into the nanogels on their hydrolytic efficiency is also investigated using molecular imprinting technique. The design and synthesis of structurally similar tripodal 'click' ligands, suitable for the preparation of a range of d-block metal complexes is then presented. The coordination chemistry of the complexes of these structurally similar ligands is explored using a range of techniques including single crystal X-ray crystallography, EPR and UV-Vis spectroscopies and cyclic voltammetry. Due to their poor aqueous solubility various ways to improve this are also examined. Future developments of the metal-based catalysts are then discussed including key issues to be addressed to achieve their potential applications in biological systems.

No description available.

Foi estudado o mecanismo da hidrólise de benzoatos de fenila substituídos catalisada pela 1-oxi-1,2-benziodoxol-3(1H)-ona (ânion o-iodosobenzoato, IBA-), em microemulsão água/óleo (mE A/O) de cloreto de benzil-hexadecil-dimetil-amônio (CBzCl) em benzeno. Duas séries de ésteres foram utilizadas: 4-X-benzoatos de 4-nitrofenila (X= NO2, CN, Cl e H) e 4-nitrobenzoatos de Y-fenila (Y= 4-NO2, 3-NO2, 4-CN, 3-CN, 4-Cl e H). Os resultados de IV (detecção do intermediário 1-(4-X-benzoiloxi)-1,2-benziodoxol-3(1H)-ona, benzoil-IBA), ausência de catálise pelo grupo abandonador, e efeito isotópico cinético de solvente inverso mostraram que a catálise pelo IBA- é nucleofílica, ocorrendo em duas etapas: - ataque do IBA- sobre o éster produzindo o intermediário benzoil-IBA e o fenol correspondente; - hidrólise desse intermediário formando os produtos finais da reação, ácido benzóico substituído e IBA-. A intensa absorção do solvente (benzeno) no UV impediu a observação do intermediário benzoil-IBA, por isso somente a primeira etapa da reação (ataque do IBA- sobre o éster, formando o intermediário benzoil-IBA) foi estudada nesta Dissertação. A natureza da etapa lenta da reação, o ataque do IBA- para formar o intermediário tetraédrico éster-IBA, foi determinada pela aplicação da equação de Hammett. Uma comparação entre os dados obtidos em mE A/O e em misturas binárias de solventes orgânicos e água mostrou que a reação aparentemente é pouco sensível a efeitos do meio. As constantes catalíticas de velocidade em mE A/O, em 14% CH3CN/H2O, em 35,1% CH3CN/H2O e em 56,5% CH3OH/H2O são similares. A entalpia de ativação para a reação micelar é cerca de 3 kcal.mol-1 menor que para as reações em meio aquoso, mas isso é compensado por uma diminuição da mesma ordem no termo entrópico. A sensibilidade da reação à substituição no grupo acila aumenta ao se transferir a reação das misturas binárias aquosas para a mE A/O, ao passo que aos substituintes no grupo fenila permanece praticamente igual em todos os meios. Esses efeitos aparentemente são ocasionados por uma dessolvatação parcial tanto do IBA- (em maior intensidade) como do estado de transição (em menor intensidade) na região interfacial da mE A/O. O mecanismo de catálise pelo IBA- parece ser o mesmo, com a mesma etapa lenta (ataque do IBA- sobre o éster) em todos os meios estudados. As diferenças observadas para a reação na mE A/O (maior sensibilidade à substituição no grupo acila do éster, entalpias e entropias menores que nos outros meios) devem ser resultantes da dessolvatação parcial do IBA- nesse meio. / The mechanism of hydrolysis of the following two series of phenylbenzoate esters catalyzed by 1-oxi-1,2-benziodoxol-3(1H)-one (o-iodosobenzoate anion, IBA-), was studied in water-in-oil microemulsion (W/O mE) of benzylhexadecyl- dimethylammonium chloride (CBzCl) in benzene. 4-nitrophenyl 4-X-benzoates (X= NO2, CN, Cl and H) and Y-nitrophenyl 4-nitrobenzoates (Y= 4-NO2, 3-NO2, 4-CN, 3-CN, 4-Cl and H). The following results show that IBA- is acting as a nucleophilic catalyst: detection of the intermediate 1-(4-X-benzoyloxi)-1,2-benziodoxol-3(1H)-one (benzoyl-IBA) by FT-IR; absence of catalysis by the leaving group; and inverse kinetic solvent isotopic effect. The reaction proceeds by a two-step mechanism: - nucleophilic attack of IBA- on the ester, resulting in the formation of benzoyl-IBA and liberation of the corresponding phenol; - hydrolysis of this intermediate, giving the final products of the reaction, substituted benzoates and IBA-. Absorbance by the solvent precluded observation of the reaction intermediate, consequently only the first part of the reaction (i.e., micellar attack of IBA- on the ester) was studied in this Dissertation. The nature of the rate determining step, formation of the tetrahedral intermediate (Ester-IBA), was determined from application of the Hammett equation. A comparison between the data in W/O microemulsions and in binary organic solvent-water mixtures showed that the reaction is rather insensitive to medium effects. The catalytic rate constants in W/O microemulsion, in 14% CH3CN/H2O, in 35,1% CH3CN/H2O, and in 56,5% CH3OH/H2O are very similar. The activation enthalpy of the micellar reaction is 3 kcal.mol-1 lower than the value in aqueous media, but this is compensated by a decrease of the same order in the entropic term. The sensitivity of the reaction to substitution in the acyl group increases in going from aqueous media to the W/O microemulsions, while the sensitivity to substitution in the phenyl moiety is almost the same in all media. These effects are apparently caused by a partial desolvation of both IBA- and the transition state in the interfacial region, the former desolvation being more pronounced. The catalysis mechanism by IBA- seems to be the same, with the same rate determining step (nucleophilic attack of IBA- on the ester), for all the studied systems. The differences observed for the reaction in W/O mE (greater sensitivity to substitution in the ester acyl group, lower values of enthalpy and entropy) are a result of the partial desolvation of IBA- in this system.

Foi estudado o mecanismo da hidrólise de benzoatos de fenila substituídos catalisada pela 1-oxi-1,2-benziodoxol-3(1H)-ona (ânion o-iodosobenzoato, IBA-), em microemulsão água/óleo (mE A/O) de cloreto de benzil-hexadecil-dimetil-amônio (CBzCl) em benzeno. Duas séries de ésteres foram utilizadas: 4-X-benzoatos de 4-nitrofenila (X= NO2, CN, Cl e H) e 4-nitrobenzoatos de Y-fenila (Y= 4-NO2, 3-NO2, 4-CN, 3-CN, 4-Cl e H). Os resultados de IV (detecção do intermediário 1-(4-X-benzoiloxi)-1,2-benziodoxol-3(1H)-ona, benzoil-IBA), ausência de catálise pelo grupo abandonador, e efeito isotópico cinético de solvente inverso mostraram que a catálise pelo IBA- é nucleofílica, ocorrendo em duas etapas: - ataque do IBA- sobre o éster produzindo o intermediário benzoil-IBA e o fenol correspondente; - hidrólise desse intermediário formando os produtos finais da reação, ácido benzóico substituído e IBA-. A intensa absorção do solvente (benzeno) no UV impediu a observação do intermediário benzoil-IBA, por isso somente a primeira etapa da reação (ataque do IBA- sobre o éster, formando o intermediário benzoil-IBA) foi estudada nesta Dissertação. A natureza da etapa lenta da reação, o ataque do IBA- para formar o intermediário tetraédrico éster-IBA, foi determinada pela aplicação da equação de Hammett. Uma comparação entre os dados obtidos em mE A/O e em misturas binárias de solventes orgânicos e água mostrou que a reação aparentemente é pouco sensível a efeitos do meio. As constantes catalíticas de velocidade em mE A/O, em 14% CH3CN/H2O, em 35,1% CH3CN/H2O e em 56,5% CH3OH/H2O são similares. A entalpia de ativação para a reação micelar é cerca de 3 kcal.mol-1 menor que para as reações em meio aquoso, mas isso é compensado por uma diminuição da mesma ordem no termo entrópico. A sensibilidade da reação à substituição no grupo acila aumenta ao se transferir a reação das misturas binárias aquosas para a mE A/O, ao passo que aos substituintes no grupo fenila permanece praticamente igual em todos os meios. Esses efeitos aparentemente são ocasionados por uma dessolvatação parcial tanto do IBA- (em maior intensidade) como do estado de transição (em menor intensidade) na região interfacial da mE A/O. O mecanismo de catálise pelo IBA- parece ser o mesmo, com a mesma etapa lenta (ataque do IBA- sobre o éster) em todos os meios estudados. As diferenças observadas para a reação na mE A/O (maior sensibilidade à substituição no grupo acila do éster, entalpias e entropias menores que nos outros meios) devem ser resultantes da dessolvatação parcial do IBA- nesse meio. / The mechanism of hydrolysis of the following two series of phenylbenzoate esters catalyzed by 1-oxi-1,2-benziodoxol-3(1H)-one (o-iodosobenzoate anion, IBA-), was studied in water-in-oil microemulsion (W/O mE) of benzylhexadecyl- dimethylammonium chloride (CBzCl) in benzene. 4-nitrophenyl 4-X-benzoates (X= NO2, CN, Cl and H) and Y-nitrophenyl 4-nitrobenzoates (Y= 4-NO2, 3-NO2, 4-CN, 3-CN, 4-Cl and H). The following results show that IBA- is acting as a nucleophilic catalyst: detection of the intermediate 1-(4-X-benzoyloxi)-1,2-benziodoxol-3(1H)-one (benzoyl-IBA) by FT-IR; absence of catalysis by the leaving group; and inverse kinetic solvent isotopic effect. The reaction proceeds by a two-step mechanism: - nucleophilic attack of IBA- on the ester, resulting in the formation of benzoyl-IBA and liberation of the corresponding phenol; - hydrolysis of this intermediate, giving the final products of the reaction, substituted benzoates and IBA-. Absorbance by the solvent precluded observation of the reaction intermediate, consequently only the first part of the reaction (i.e., micellar attack of IBA- on the ester) was studied in this Dissertation. The nature of the rate determining step, formation of the tetrahedral intermediate (Ester-IBA), was determined from application of the Hammett equation. A comparison between the data in W/O microemulsions and in binary organic solvent-water mixtures showed that the reaction is rather insensitive to medium effects. The catalytic rate constants in W/O microemulsion, in 14% CH3CN/H2O, in 35,1% CH3CN/H2O, and in 56,5% CH3OH/H2O are very similar. The activation enthalpy of the micellar reaction is 3 kcal.mol-1 lower than the value in aqueous media, but this is compensated by a decrease of the same order in the entropic term. The sensitivity of the reaction to substitution in the acyl group increases in going from aqueous media to the W/O microemulsions, while the sensitivity to substitution in the phenyl moiety is almost the same in all media. These effects are apparently caused by a partial desolvation of both IBA- and the transition state in the interfacial region, the former desolvation being more pronounced. The catalysis mechanism by IBA- seems to be the same, with the same rate determining step (nucleophilic attack of IBA- on the ester), for all the studied systems. The differences observed for the reaction in W/O mE (greater sensitivity to substitution in the ester acyl group, lower values of enthalpy and entropy) are a result of the partial desolvation of IBA- in this system.

No description available.

The FT-Raman techniques were developed to quantify reactions that follow on mixing aqueous solutions of bis-(1,3-diaminopropane)diaquacobalt( III) ion ([Co(tn)2(0H)(H20)]2+) and p-nitrophenylphosphate (PNPP). For the development and validation of the kinetic modelling technique, the well-studied inversion of sucrose was utilized. Rate constants and concentrations could be estimated using calibration solutions and modelling methods. It was found that the results obtained are comparable to literature values. Hence this technique could be further used for the [Co(tn)2(0H)(H20)]2+ assisted hydrolysis of PNPP. It was found that rate constants where the pH is maintained at 7.30 give results which differ from those where the pH is started at 7.30 and allowed to change during the reaction. The average rate constant for 2:1 ([Co(tn)2(0H)(H20)]2+:PNPP reactions was found to be approximately 3 x 104 times the unassisted PNPP hydrolysis rate. / Chemistry / M. Sc. (Chemistry)

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-05-04T19:26:38Z No. of bitstreams: 1 lucasfagundesesteves.pdf: 10750065 bytes, checksum: 8871e6f0092a5a329a1cc8099f9a0382 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-05-17T13:33:34Z (GMT) No. of bitstreams: 1 lucasfagundesesteves.pdf: 10750065 bytes, checksum: 8871e6f0092a5a329a1cc8099f9a0382 (MD5) / Made available in DSpace on 2017-05-17T13:33:34Z (GMT). No. of bitstreams: 1 lucasfagundesesteves.pdf: 10750065 bytes, checksum: 8871e6f0092a5a329a1cc8099f9a0382 (MD5) Previous issue date: 2016-02-29 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Esta tese propõe uma investigação teórica do mecanismo de quebra hidrolítica de um modelo para diésteres de fosfato, o íon BDNPP [bis(2,4-dinitrofenil)fosfato], catalisada por um complexo dinuclear de cobre(II) (R1). Esse complexo metálico foi originalmente planejado para mimetizar a estrutura e as propriedades catalíticas do sítio ativo das catecóis oxidases (COs), revelando um caso interessante de promiscuidade catalítica em sistemas biomiméticos. As possibilidades de mecanismo foram cuidadosamente avaliadas através de cálculos de Teoria do Funcional da Densidade (DFT) em fase gás e em fase aquosa com cálculos no ponto dentro do modelo contínuo polarizável (PCM). Dois mecanismos principais foram encontrados. O Mecanismo 1 (Concertado) corresponde a uma reação do tipo SN2 que envolve o ataque da ponte µOH, situada entre os íons Cu(II), ao centro fosfórico da molécula de BDNPP, enquanto que o Mecanismo 2 (Associativo) ocorre através de sucessivas transferências de próton entre o átomo de oxigênio desta mesma ponte com o átomo de oxigênio terminal do grupo fosfato, passando pela formação de um intermediário pentacoordenado estável. O Mecanismo 1 envolve dois possíveis caminhos reacionais para a liberação do íon DNPP [(2,4-dinitrofenil)fosfato] gerado após a quebra hidrolítica. O primeiro caminho reacional (p1) envolve uma transferência de próton – que ocorre entre o átomo de oxigênio que compunha a ponte µ-OH e o átomo de oxigênio terminal do grupo fosfato – imediatamente após a quebra hidrolítica, seguido pela entrada de duas moléculas de água, sendo a etapa de transferência de próton determinante da velocidade. O segundo caminho reacional (p2) envolve a entrada de duas moléculas de água imediatamente após a quebra hidrolítica sem que haja a reação de transferência de próton, sendo a etapa de quebra hidrolítica a etapa determinante da velocidade. Dentre as propostas de mecanismo estudadas o caminho reacional p2 dentro do Mecanismo 1 corresponde ao mais provável, uma vez que possui a menor barreira de reação (ΔG‡ = 23,7 kcal mol-1, em solução aquosa). A constante de velocidade observada experimentalmente, Kobs, vale 1,7 × 10-5 s-1, indicando que o valor calculado teoricamente (K1 = 2.6 × 10-5 s-1) está em excelente acordo com o valor experimental. O efeito isotópico cinético (KIE) foi avaliado para o caminho reacional p2 dentro do Mecanismo 1 com o intuito de entender as alterações estruturais envolvidas na formação do TS1-i (Estado de transição para o Mecanismo 1), caracterizando perfeitamente o mecanismo descrito. O efeito explícito da inclusão de moléculas do solvente foi avaliado de maneira preliminar para apenas uma estrutura do ciclo catalítico para a quebra hidrolítica de ésteres de fosfato, através da utilização do método de Monte Carlo. Os resultados permitem uma análise detalhada da organização das moléculas de solvente ao redor do complexo, podendo servir de ponto de partida para uma análise mais elaborada dos mecanismos reacionais utilizando modelos explícitos para o solvente. O mecanismo de oxidação de catecóis – representado pelo substrato modelo, o 3,5-di-tercbutilcatecol (DTBC) – no sítio ativo do complexo R1 foi avaliado através de cálculos quanto-mecânicos. Embora não tenham sido obtidos resultados conclusivos acerca da cinética da reação, os aspectos estruturais das principais espécies envolvidas no ciclo catalítico foram analisados. / In this thesis the theoretical investigation of the hydrolytic cleavage mechanism of a phosphate diester, BDNPP [bis(2,4-dinitrophenyl)phosphate] in the active site of the dinuclear copper complex, labelled as R1, has been proposed. The metal complex was originally designed to mimic the active site structure as well the catalytic properties of catechol oxidase, revealing an interesting case of catalytic promiscuity in biomimetic systems. The mechanistic possibilities have been carefully evaluated through Density Functional Theory (DFT) calculations in gas phase and in aqueous solution using continuum solvation models with single point calculations within the Polarizable continuum model (PCM). Two reaction mechanisms have been proposed. The Mechanism 1 (Concerted) is a SN2 type mechanism which involves the direct attack of the µ-OH bridge between the two copper(II) ions towards the phosphorus center whereas, the Mechanism 2 (Associative) occurs through two successive proton transferences between the oxygen atom of the bridging hydroxo ligand and another oxygen atom of the phosphate model forming a stable pentacoordinate intermediate. There are two reactions paths for Mechanism 1 to release the DNPP (2,4-dinitrophenylphosphate) ion generated after the hydrolytic cleavage. The first reaction path (p1) involves a proton transfer immediately after the hydrolytic cleavage, being the proton transfer the rate-determining step, followed by the entry of two water molecules. The second reaction path (p2) comprises the entry of two water molecules just after the hydrolytic cleavage without any proton transfer, being the hydrolytic cleavage the rate limiting step. The most probable catalytic path occurs via Mechanism 1, following the second reaction path (p2) once it involves the lowest free energies activation barrier (ΔG‡ = 23.7 kcal mol-1, in aqueous solution). The experimental rate constant, Kobs is 1.7 × 10-5 s-1, indicating that the calculated value, (K1 = 2.6 × 10-5 s-1) is in a very good accordance with the experimental value. Kinetic Isotope Effect (KIE) analysis for the second reaction path (p2) within the Mechanism 1 has also been considered in order to understand the changes taking place in TS1-i (transition state of Mechanism 1) and perfectly characterize the mechanism here described. The solvent effect using explicit water molecules were evaluated in a preliminary fashion for one structure within the catalytic cycle of hydrolytic cleavage of phosphate ester, using the Monte Carlo method. The obtained results allows a detailed analysis of the water molecules organization around the complex, serving as a starting point for an more elaborated study of the reaction mechanisms by using explicit solvent models. The oxidation of catechols – represented herein by the model substrate, 3,5-di-tercbuthylcatechol (DTBC) – in the active site of the R1 complex were evaluated by using quantum-mechanical calculations. The results are not conclusive for the kinetic, but the structural aspects for the main species in the catalytic cycle were studied.

Für eine effiziente und nachhaltige Nutzung von Georeservoiren sind bestmögliche Reservoirmanagementverfahren erforderlich. Oft setzen diese Verfahren auf Tracer-Tests. Dabei enthalten die aufgezeichneten Tracersignale integrale Informationen der Reservoireigenschaften. Tracer-Tests bieten somit eine leistungsfähige Technik zur Charakterisierung und Überwachung der bewirtschafteten Georeservoire. Im Gegensatz zu Tracer-Tests mit konservativen Tracern, welche bereits etablierte Testroutinen zur Verfügung stellen, ist die Verwendung von reaktiven Tracern ein neuer Ansatz. Aufgrund unpassender physikalisch-chemischer Modelle und/oder falschen Annahmen ist die Analyse und Interpretation von reaktiven Tracersignalen jedoch oft verzerrt, fehlinterpretiert oder sogar unmöglich. Reaktive Tracer sind dennoch unersetzbar, da sie durch die gezielte Ausnutzung selektiver und spezifischer Reaktionen mögliche Metriken von Reservoirtestverfahren auf einzigartige Weise erweitern. So liefern reaktive Tracer für ein integriertes Reservoirmanagement geforderten Aussagen über Reservoirmetriken wie z.B. Wärmeaustauschflächen oder in-situ Temperaturen. Um Unsicherheiten bei der Auswertung von Tracerexperimenten zu reduzieren, werden theoretische und experimentelle Untersuchungen zu hydrolysierenden Tracern vorgestellt. Diese Tracer sind durch ihre Reaktion mit Wasser charakterisiert. Einerseits können sie als thermo-sensitive Tracer Informationen über Temperaturen und abgekühlte Anteile eines beprobten Reservoirs liefern. Für die Interpretation von thermo-sensitiven Tracerexperimenten sind die Kenntnis der zugrunde liegenden Reaktionsmechanismen sowie bekannte Arrhenius-Parameter Voraussetzung, um die verwendete Reaktion pseudo erster Ordnung nutzen zu können. Darüber hinaus ermöglichen die verwendeten Verbindungen durch ihre Fluoreszenzeigenschaften eine Online-Messung. Um die Empfindlichkeit und praktischen Grenzen thermo-sensitiver Tracer zu untersuchen, wurden kontrollierte Laborexperimente in einem eigens dafür entwickelten Versuchsaufbau durchgeführt. Dieser besteht aus zwei seriell geschalteten Säulen, die beide mit Sand gefüllt sind und jeweils auf eine eigene Temperatur eingestellt werden können. Somit ist es möglich, verschiedene thermische Einstellungen zu betrachten. Die untersuchten experimentellen Szenarien imitieren größtenteils Feldanwendungen: Durchflussexperimente sowie auch Experimente mit einer Umkehr der Fließrichtung. Darüber hinaus wurde untersucht, ob thermo-sensitive Tracer auch sensitiv gegenüber der Position der Temperaturfront sind. Dabei wurden die Tracer kontinuierlich oder gepulst injiziert. Die Ergebnisse bestätigen die zugrunde liegende Theorie experimentell. Wenn die pH-Abhängigkeit der Hydrolyse bei der Analyse berücksichtigt wird, kann eine Temperaturschätzung mit einer Genauigkeit und Präzision von bis zu 1 K erreicht werden. Die Schätzungen sind von Verweilzeit und gemessenen Konzentrationen unabhängig. Weiterhin lässt sich eine Schätzung über den ausgekühlten Anteil des Systems erhalten. Durch die steuerbaren und definierten Laborbedingungen ist es erstmals möglich, die geforderte Anwendbarkeit von thermo-sensitiven Tracern belastbar nachzuweisen. Des Weiteren wird eine zweite Anwendung hydrolysierender Tracer vorgeschlagen. Beim Lösen von CO2 für „Carbon Capture and Storage“-Anwendungen hängt die Effizienz maßgeblich von der Grenzfläche zwischen CO2 und der Sole in tiefen Reservoiren ab. Somit ist diese Metrik wichtig, um die Effizienz der CO2 Auflösung in Wasser zu bewerten. Die gezielt entwickelten Kinetic-Interface-Senitive-Tracer (KIS-Tracer) nutzen, zusätzlich zur Hydrolyse an der Grenzfläche, die unterschiedlichen Lösungseigenschaften von Tracer und Reaktionsprodukt im entsprechenden Fluid. Somit lassen sich potentiell Aussagen über die Dynamik der Grenzfläche machen. Neben dem grundlegenden Konzept sowie den theoretischen Tracer-Anforderungen wird eine erste Anwendung im Laborexperiment vorgestellt. Diese zeigt das erfolgreiche, zielorientierte Moleküldesign und bietet eine experimentelle Basis für ein makroskopisches numerisches Modell, mit welchem numerische Simulationen verschiedener Testszenarien durchgeführt werden, um das Zusammenspiel von KIS-Tracer und dynamischer Grenzfläche zu untersuchen. Aufgrund der Temperaturabhängigkeit der Reaktionsgeschwindigkeit hydrolysierender Tracer werden in der Regel auch thermische Signale aufgezeichnet. Der letzte Teil prüft die Möglichkeit, Informationen aus den aufgezeichneten Temperaturen zu extrahieren. Für ein idealisiertes Einzelkluftsystem wird eine Reihe von analytischen Lösungen diskutiert. Aus thermischen Injektion-/Entzugsversuchen können damit räumliche und zeitliche Profile abgeleitet werden. Mit der Verwendung von mathematisch effizienten Inversionsverfahren wie der iterativen Laplace-Transformation lassen sich rechentechnisch effiziente Realraum-Lösungen ableiten. Durch die Einführung von drei dimensionslosen Kennzahlen können die berechneten Temperaturprofile auf Bruchbreite oder Wärmetransportrate, wechselnde Injektions-/ Pumpraten und/oder auf in der Nähe beobachtbare räumliche Informationen analysiert werden. Schließlich werden analytische Lösungen als Kernel-Funktionen für nichtlineare Optimierungsalgorithmen vorgestellt. Zusammenfassend bearbeitet die vorliegende Arbeit den Übergang zwischen Tracerauswahl und Traceranwendung. Die Ergebnisse helfen Planungs- und Analyseunsicherheiten zu reduzieren. Dies wird bezüglich der Empfindlichkeit gegenüber Temperaturen, Kühlungsanteilen, flüssig/flüssig-Grenzfläche, Kluftbreite und Wärmetransportrate gezeigt. Somit bieten die vorgestellten Tracerkonzepte neue Metriken zur Verbesserung von Reservoirmanagementverfahren. Die experimentellen Ergebnisse und die neuen analytischen Modelle ermöglichen einen tiefen Einblick in die kollektive Rolle der Parameter, welche die Hydrolyse und den Wärmetransport in Georeservoiren kontrollieren.