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Increased proliferation of nanotechnology has led to concerns regarding its implication to the water environment. Gold nanoparticles (AuNP) were used as a model nanomaterial to investigate the fate and dynamics of nanoparticles in the complex water environment. A column study was performed to examine the fate and transport of gold nanoparticles with two different coatings in porous media. The resulting data suggested that gold nanoparticles aggregate significantly in the porespace of the column interior, a finding that is not predicted by traditional colloidal filtration theory or Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Surface-enhanced Raman spectroscopy (SERS) was developed as a new technique to investigate AuNP aggregation in water with varying salt levels. The SERS technique proved valuable as an analytical technique, elucidating information about aggregation as well as AuNP surface interactions with dissolved halides in water. A thorough investigation examining Aunt aggregation with monovalent and divalent salts utilizing SERS, ultraviolet-visible light (UV-Vis) spectroscopy, and dynamic light scattering (DLS) was conducted. Each technique provided data describing different aspects of the dynamic behavior of AuNPs in complex water environments. Results suggest that in addition to attractive and repulsive interactions described by DLVO theory, chemical interactions between the AuNP surface and dissolved halides were also a significant driving force for aggregation and other transformative behaviors of AuNPs in water. The SERS technique developed in this work was shown to be a viable tool to help unveil the vastly complex dynamics of nanomaterial in the water environment. / Ph. D. / Nanotechnology is everywhere. It is in our smartphones, in our food, in our clothes, even if we do not recognize it is there. And this is a good thing, because nanotechnology – that is, technology that utilizes nanomaterials – can provide things that traditional technology often cannot. This is all because many nanomaterials have “superpowers” due to their size range: they are generally larger than what we may think of when we think of chemical molecules, but much smaller than macroscopic materials whose behaviors can be approximated by classic physics and chemistry. For example, we all know that gold has a shiny yellow metallic appearance. However, if we make little particles of gold – and these are going to be very tiny, with diameters about 10,000 times smaller than that of a strand of human hair (but about 100 times larger than what we would typically think of as molecules of chemicals) – and put them in water, the resulting mixture will be ruby-red like wine. One of the “superpowers” these gold nanoparticles possess is that they interact with light in a very different way than bulk gold. Currently, researchers in the biomedical field are producing promising work employing these particles in nextgeneration imaging, and much more. In this study, we were interested in what happens to these materials once they are released to the water environment. Because of the “superpowers” these gold nanoparticles possess, we really do not know how they will behave once they are released to either surface or groundwater because the physics and chemistry of those environments can be quite variable and complex. In this work, we have shown that traditional assumptions about particulate contaminants in water systems do not necessarily hold for gold nanoparticles. Laboratory simulations show that interactions between these particles and the surrounding environment that were once thought to be negligible, are in fact highly significant. As our title suggests, we are developing new and advanced “photonics” methods to help us discover the dynamic complexity dictating the fate of these gold nanoparticles once they are in the water environment. Photonics methods are techniques that employ light as a probing tool. These techniques use a well understood laser light source that is directed towards the particles in a water environment, and we then measure changes in the scattered light after it has interacted with the particles. The technique we have employed here (called surface-enhanced Raman spectroscopy, or SERS) simultaneously provides us information about different behaviors of gold nanoparticles in water, including how they may aggregate (that is, stick to one another and form big clumps) and how they interact with existing dissolved chemicals that may be present in the natural water environment. By pairing this method with other existing methods, we were able to paint a more complete picture of how these nanoparticles behave in the water environment, and we can answer some questions as to why they do not follow some previously held assumptions. In the end, the work in this dissertation will help future scientists continue to unlock the complexity of nanomaterial fate and dynamics in the water environment.

This Diploma Thesis is focused on study of electrochemical behavior of 2,4,6-trinitrotoluene (TNT) and 2,4,6-trinitrophenol (picric acid) on finding the optimum conditions for their determination using direct current voltammetry (DCV) and differential pulse voltammetry (DPV) at a mercury meniscus modified silver solid amalgam electrode (m-AgSAE) in the solution of Britton-Robinson (BR) and on finding of the limit of quantification (LQ) for these substances. Practical applicability of the newly developed methods was verified on direct determination of TNT and picric acid in model samples of drinking and river water. Moreover, the electrochemical behaviors of TNT and picric acid was studied using cyclic voltammetry (CV). Optimum medium for the determination of TNT at m-AgSAE was: methanol-BR buffer pH 4.0 (1:9). Upon the DCV it is proper to apply regeneration potentials Ereg,1= 0 mV and Ereg,2= -1100 mV and upon the DPV was apply regeneration potentials Ereg,1= 0 mV and Ereg,2= -600 mV were applied. The concentration dependence of the peak current was found to be linear for both techniques over the concentration range of 1·10-6 -1·10-4 mol/l with LQ of 0.54 µmol/l (for DCV) and 0.46 µmol/l (for DPV). The method developed for the determination of TNT were verified on the model samples of drinking...

The aim of presented Diploma Thesis was to study an electrochemical behavior of nitroimidazole drugs metronidazole and ornidazole and to find optimal conditions for their voltammetric determination at a mercury meniscus modified silver solid amalgam electrode using DC voltammetry (DCV) and differential pulse voltammetry (DPV). Voltammetric behavior of selected drugs was investigated in dependence on the pH of the medium used (realized using a Britton-Robinson buffer (BR buffer)) and a mechanism of the reduction of both drugs was investigated using cyclic voltammetry (CV). The optimum medium for voltammetric determination of studied nitroimidazole drugs at the m-AgSAE in a region of cathodic potentials was found to be the BR buffer of pH 8.0. Then, the concentration dependences were measured in this optimum medium in the concentration range from 2·10-7 mol/L to 1·10-4 mol/L. The limits of quantification (LQs) for both metronidazole and ornidazole were found in the concentration order of 10-7 mol/L by using DCV and DPV at the m-AgSAE. The applicability of the newly developed voltammetric methods of the determination of nitroimidazole drugs was verified on the model samples of drinking and river water, with LQ ≈ 2·10-7 mol/L for both DC voltammetry and differential pulse voltammetry at the m-AgSAE....

O cloridrato de ranitidina, um antagonista dos receptores H2 da histamina, foi determinado em comprimidos e injetáveis por espectrofotometria no ultravioleta, a 313nm, e por espectrofotometria no visível, a 615nm, utilizando o cloridrato da hidrazona da 3-metil-2-benzotiazolinona (MBTH) a 0,35% em HCl 0,M e cloreto férrico a 0,40% em HCl 0,1M, como reagentes de cor. Na espectrofotometria no ultravioleta a lei de Beer foi obedecida no intervalo de concentração de 5,0 a 18,0 µg/mL. Quatro amostras comerciais foram analisadas. Os coeficientes de variação foram 0,36% e 0,71% para comprimidos, e 0,51% e 0,24% para injetáveis. A média de recuperação foi 99,88%. Na espectrofotometria no visível a lei de Beer foi obedecida no intervalo de concentração de 1,44 a 5,76 µg/mL. Os coeficientes de variação foram 0,72% e 0,59% para comprimidos, e 0,53% e 0,61% para injetáveis. A média de recuperação foi 99,39%. Os resultados foram comparados estatisticamente e foram compatíveis para as amostras que se encontravam em bom estado de conservação. / Ranitidine hydrochloride, a histamine H2-receptor antagonist, was determined in tablets and injections by ultraviolet spectrophotometry at 313nm , and visible spectrophotometry using as color reagent 0,35% 3-methyl-2-benzothiazolinone hydrochloride in HCl 0,1M and 0,40% ferric chloride in HCl 0,1M. In ultraviolet spectrophotometry, Beer\'s law was obeyed in the range of concentration from 5,0 to 18,0 µg/mL. Four commercially available were analyzed. The coefficients of variation were 0,36% and 0,71% for tablets, and 0,51% and 0,24% for injections. The recovery average was 99,88%. In visible spectrophotometry, Beer\'s law was obeyed in the range of concentration from 1,44 to 5,76 µg/mL. The coefficients of variation were 0,72% and 0,59% for tablets, and 0,53% and 0,61% for injections. The recovery average was 99,39%. The results obtained by using the two methods were statistically compared and were compatible when samples were kept in good conditions of storage.

Dans le present travail de recherche notre équipe s'est interessé à l'étude de la composition chimique -au niveau moléculaire- d'un groupe d'échantillons résineuses provenant d'objects Aztecs et Mayas. Le but ultime de cette étude a été d'établir l'origin botanique de ces résines et d'avoir une vue d'ensemble des formulations utilisées dans les adhésifs ou les figurines, afin de mieux comprendre leurs propriétes physiques.Pour aboutir à cet objectif une stratégie analytique très spécifique a été créeé et mise en oeuvre. Cette stratégie a inclus l'analyse d'échantillons des résines archéologiques mais aussi de résines d'origine botanique certifiée et de résines commerciales, achetées dans des marchés traditionels au Mexique dans une région qui correspond a la one géographique occupée autre fois par l'empire aztèque.L'étude des matériaux a fait appel à des techniques tels que l'observation a l'échelle microscopique, la spectroscopie infrarouge (IRTF), la chromatographie liquide-DAD (HPLC-UV/Vis) et la chromatographie en phase gazeuse couplée à la spéctroscopie de masse (CPG-SM).L'étude moléculaire de ces échantillons, et plus précisement, l'étude leur fraction tritérpenique a permis de : Établir un profil moléculaire des résines pour chaque origine botanique étudiée Idéntifier précisement certain composées tritérpeniques présents dans toutes les échantillons Réperer les molécules tritérpeniques susceptibles d'être utilisées dans l'avenir comme des marqueurs moléculaires d'origine botanique pour les résines frais des espèces étudiées Suggèrer une origine botanique pour les échantillons archéologiques Aztèques Écarter des origines botaniques possibles pour l'échantillon Maya Avoir une vue d'ensemble de l'origine botanique des résines commercialisées au territoire mexicain sous le nom de «copal» Créer un protocole d'analyse simple pour permettre aux professionnels de la conservation et des biomatériaux d'établir l'origine botanique et un profil moléculaire des résines utilisées dans des expériences diverses Caractériser le comportement du copal lors du vieillisement naturel et artificiel Établir des molécules susceptibles de devenir marqueurs moléculairs pour les deux types de vieillisement Établir que l'origine botanique d'un échantillon résineux peut être retrouvée malgré son âge (archéologique) / In the present work, the molecular composition of series of resinous aztec and maya archaeological samples were investigated to determinate their nature.Thus an analytical strategy was specifically designed. This analytical strategy included the analysis of botanically certified resins, freshly collected. It included as well the analysis of commercial samples bought in Mexican traditional markets.The study of all the samples included microscopical techniques, Fourier Inverse Infrared Spectrometry (FTIR) , High Performance Liquid Chromatography coupled to Ultraviolet-visible spectrometry (HPLC-UV/Vis) and Gas Chromatography coupled to Mass Spectrometry (GC-MS).The molecular study of these samples, in particular of their trterpenic composition allowed to : establish the molecular profile of resins from certified botanical origin. Identifiy some of the triterpenic compounds present in samples; Identify triterpenic molecules that could be uses as molecular markers for each botanical origin. Find the botanical origin of archeological astec samples. Discard possible botanic origins for maya archaeological sample. Have an overview of the origin of commercial samples of mexican copal. Create a simple protocol that allows conservation and biomaterials professionals to establish the botanical origin of archaeological and commercial resins, used in conservation interventions. Observe the behavior of copal materials upon ageing, establishing potential markers for natural ageing in copal, under darkness. Asses the botanical origin of a sample can be found regardless the age of the resin

O cloridrato de ranitidina, um antagonista dos receptores H2 da histamina, foi determinado em comprimidos e injetáveis por espectrofotometria no ultravioleta, a 313nm, e por espectrofotometria no visível, a 615nm, utilizando o cloridrato da hidrazona da 3-metil-2-benzotiazolinona (MBTH) a 0,35% em HCl 0,M e cloreto férrico a 0,40% em HCl 0,1M, como reagentes de cor. Na espectrofotometria no ultravioleta a lei de Beer foi obedecida no intervalo de concentração de 5,0 a 18,0 µg/mL. Quatro amostras comerciais foram analisadas. Os coeficientes de variação foram 0,36% e 0,71% para comprimidos, e 0,51% e 0,24% para injetáveis. A média de recuperação foi 99,88%. Na espectrofotometria no visível a lei de Beer foi obedecida no intervalo de concentração de 1,44 a 5,76 µg/mL. Os coeficientes de variação foram 0,72% e 0,59% para comprimidos, e 0,53% e 0,61% para injetáveis. A média de recuperação foi 99,39%. Os resultados foram comparados estatisticamente e foram compatíveis para as amostras que se encontravam em bom estado de conservação. / Ranitidine hydrochloride, a histamine H2-receptor antagonist, was determined in tablets and injections by ultraviolet spectrophotometry at 313nm , and visible spectrophotometry using as color reagent 0,35% 3-methyl-2-benzothiazolinone hydrochloride in HCl 0,1M and 0,40% ferric chloride in HCl 0,1M. In ultraviolet spectrophotometry, Beer\'s law was obeyed in the range of concentration from 5,0 to 18,0 µg/mL. Four commercially available were analyzed. The coefficients of variation were 0,36% and 0,71% for tablets, and 0,51% and 0,24% for injections. The recovery average was 99,88%. In visible spectrophotometry, Beer\'s law was obeyed in the range of concentration from 1,44 to 5,76 µg/mL. The coefficients of variation were 0,72% and 0,59% for tablets, and 0,53% and 0,61% for injections. The recovery average was 99,39%. The results obtained by using the two methods were statistically compared and were compatible when samples were kept in good conditions of storage.

La miniaturisation toujours plus poussée des composants électroniques a atteint une limite en arrivant à l’échelle atomique. Afin de fabriquer des circuits à cette échelle, il est nécessaire de intéresser aux plus petits composants pouvant être intégrés : les molécules individuelles et les groupes d’atomes. Dans cette optique, les molécules de 1,4-bis(pyridin-4-ylethynyl) benzène (BPEB), Dibenzo[a,h]thianthrene (DBTH), de Bis{82,92,152,162,222,232- hexa-(2,4,6-trifluorophenoxy)[g,l,q]-5,10,15,20-tetraazaporphyrino)}[b,e]-benzene (H4Pc2) ont été conçues, synthétisées et caractérisées afin d’en étudier le transport de charges et les changements induits proche de la surface. Des techniques de SPM, tels que le STM, le nc-AFM et l’usage conjoint de l’AFM avec le STM ont été mises en pratique pour analyser les molécules reposant intégralement ou partiellement sur un substrat. L’interprétation des résultats expérimentaux a été faite au moyen de calculs de DFT. De plus, l’autoassemblage en solution de nouvelles mono-phthalocyanines métalliques fluorées, MPc (M= Mg2+, 2H+, Co2+) a été étudié.Tout d’abord, les mesures de conductance mirent en évidence, lors d’expériences de manipulation de fils moléculaires (BEPB), les changements de conformation associés aux transport des électrons à travers les molécules. De plus, le mouvement dit de “retournement papillon” (anglais: butterfly flapping) ayant lieu dans la classe des thianthrènes fut bloqué à basse température grâce à l’interaction avec le substrat. Ce blocage a permit de conduire la première étude stéréochimique de dérivés de thianthrènes chiraux (DBTH). Les analyses STM du DBTH ont montrées que le passage entre deux configurations de DBTH est reproductible et non-destructif. Par ailleurs, le nc-AFM utilisé à résolution sub-moléculaire a constitué un outils important pour réaliser une caractérisation complète et distinguer entre les différents isomères de configuration et de constitution déposés sur une surface. D’autre part, la structure moléculaire de la phthalocyanine binucléaire (H4Pc2) a été confirmée en utilisant un STM en mode “courant constant” et un AFM en mode “fréquence constante”. Ces résultats jettent les bases d’une prochaine étude de transport (travail en cours). En outre, l’étude de l’agrégation dans les molécules de MPc mit en évidence le rôle important de la capacité de coordination de l’atome central de la cavité Pc sur la formation d’agrégat. Finalement, des mesures électrochimiques ont démontrées que l’agrégation moléculaire peut bloquer le nature active de l’atome Co2+. Dans ce travail, il a été clairement montré que le SPM est une technique adéquate pour étudier les changements de conformations et de configurations associés aux courant tunnel d’électrons à travers des molécules, qu’elles soient planaire ou pas. Les études d’agrégation des interrupteurs magnétiques ont permis de mieux comprendre l’organisation supramoléculaire. Cette organisation est un point crucial pour le développement de futurs circuits basés sur une fabrication “bottom-up”. / The demand of downscaling of technology will reach its limit at the atomic length scale. This claim creates the necessity of investigating the smallest components suitable to become devices, single molecules or group of atoms. Therefore, 1,4-bis(pyridin-4-ylethynyl) benzene (BPEB), Dibenzo[a,h]thianthrene (DBTH) and Bis{82,92,152,162,222,232-hexa-(2,4,6-trifluorophenoxy)[g,l,q]-5,10,15,20-tetraazaporphyrino)}[b,e]-benzene (H4Pc2) have been designed, synthesized and characterized to investigate transport of charge through molecules and surface confined molecular switching. Scanning Probe Microscopy (SPM), such as STM, nc-AFM and combined STM/AFM were used to study the molecules on near-surface conditions. Density Functional Theory (DFT) calculations were used to interpret the experimental results. Moreover, the self-assembly of new fluorinated metalo mono-phthalocyanines, MPc (M= Mg2+, 2H+, Co2+) was investigated in solution.Firstly, conductance experiments performed while a molecular wire (BPEB) was being lifted up from a surface revealed the conformational changes associated to the transport of electrons through molecules. Secondly, the “butterfly” flapping motion in the class of the thianthrenes was blocked due to the interaction with a surface at low temperature. This block leads to the first stereochemical study of a quiral thianthere derivative (DBTH). The STM experiments on DBTH revealed a reproducible and non-destructive switching between two surface confined configurations of DBTH. In addition, nc-AFM with submolecular resolution has been proved to be a powerful tool for the full characterization and distinction of configurational and constitutional isomers on surfaces. Thirdly, the molecular structure of a binuclear phthalocyanine (H4Pc2) was confirmed through constant current STM and constant high _f AFM experiments. These results set the state of future spintronic transport experiments (ongoing work). On the other hand, the aggregation studies on MPc revealed that the coordination character of the central atom of the Pc cavity has an important effect on the formation of aggregates. Additionally, electrochemical experiments demonstrated that molecular aggregations can lead to the quenching of the electrochemical-active nature of a Co2+ atom.Herein it has been demonstrated that SPM are suitable techniques to study the conformational and configurational changes associated with the tunneling of electrons through planar and non-planar molecules in real space. Aggregation studies of magnetic switches were carried out to better understand the supramolecular organization under near surface conditions, a key point for the design of future devices based on the bottom up approach.

Die vorliegende Arbeit beschäftigt sich mit der Synthese, dem Reaktionsverhalten und der Elektrochemie von Bimetallocen- und Metallocen-haltigen Komplexen. Die Eignung von Bis(ethinyl)biferrocen- und Bis(ethinyl)biruthenocen-haltigen Brückenbausteinen, intramolekularen Elektronentransfer zwischen zwei identischen Eisen-, Ruthenium- und Osmium-Halbsandwich-Fragmenten zuzulassen, wurde mittels geeigneter Spektroskopiearten untersucht. Weiterhin wurden zwei verschiedene Übergangsmetallkomplexfragmente über den Bis(ethinyl)biferrocen-Brückenbaustein miteinander verknüpft um neuartige gemischte Übergangsmetallacetylide zu erhalten, an welchen ebenfalls Elektronentransferstudien durchgeführt werden konnten. Zusätzlich waren Biferrocenyl- und Metallocenyl-Phosphane Gegenstand der Untersuchungen. Es erfolgte einerseits die Koordination an PtCl2- und Pt(CCFc)2-Fragmente. Die so erhaltenen neuen heterometallischen Platin(II)-Bisacetylide wurden mittels Cyclovoltammetrie und UV-Vis-NIR-spektroelektrochemischen Methoden untersucht um herauszufinden, in welchem Ausmaß Ladungen delokalisiert vorliegen können. Die Biferrocenyl- und Ruthenocenyl-Phosphane wurden andererseits an PdCl2-Bausteine koordiniert und im Anschluss auf ihre Wirksamkeit als (Prä-)Katalysatoren in Palladium-vermittelten Heck- und Suzuki-C-C-Kupplungsreaktionen getestet.

Die Entwicklung von makrocyclischen Chelatoren, die mit Kupferionen thermodynamisch stabile und kinetisch inerte Komplexe bilden, ist in den letzten Jahren zunehmend in den Fokus der Forschung gerückt. Das ergibt sich insbesondere aus der Möglichkeit, Radiokupfernuklide aufgrund günstiger kernphysikalischer Eigenschaften sowohl für diagnostische (64Cu) als auch therapeutische (67Cu) Anwendungen einzusetzen. Hervorzuheben ist der Azamakrocyclus Cyclam (1,4,8,11-Tetraazacyclodecan), da dieser mit Kupfer(II)-Ionen Komplexe hoher thermodynamischer Stabilität bildet. Zudem weist der Chelator weitere Funktionalisierungsmöglichkeiten auf, um in Hinblick auf eine nuklearmedizinische Anwendung pharmakologisch relevante Moleküle wie beispielsweise Peptide oder Proteine (Antikörper oder Antikörperfragmente) kovalent zu binden und damit eine spezifische Anreicherung im Tumorgewebe zu ermöglichen. Allerdings erfordert das Maßschneidern der Eigenschaften von neuen bifunktionellen Chelatoren Kenntnisse über den Einfluss der Substituten auf die Stabilität der gebildeten Kupfer(II)-Komplexe. Die thermodynamische Stabilität lässt keine Aussagen über das Verhalten in vivo zu. Die Ursache für die kinetische Labilität in Säugetieren ist noch nicht vollständig verstanden, wird aber u. a. auf kupferbindende Enzyme bzw. Proteine zurückgeführt. Die Bioverteilung der Radiokupferkomplexe wird aber auch von weiteren Parameter, wie Hydrophilie, Ladung und Polarisierbarkeit beeinflusst. Mit dieser Arbeit wurde ein wesentlicher Beitrag zur Entwicklung von 64Cu Chelaten auf Basis von Cyclam-Propionsäure-Liganden geleistet. Diese Stoffklasse ist bisher synthetisch wenig erschlossen und Radiokupfer-markierte Komplexe zudem bisher gar nicht beschrieben. Daher ist es von besonderem Interesse die kinetische Stabilität Radiokupfer-markierter Cyclam-Propionsäure-Derivate zu untersuchen und mit einer Reihe bekannter Radiokupfer-markierter Cyclam-Essigsäure-Komplexe zu vergleichen. Es wurden vier N-funktionalisierte Cyclam-Derivate 13, 14b, 15 und 16, die eine unterschiedliche Anzahl an Propionsäuregruppen tragen, erfolgreich synthetisiert und in sehr hoher Reinheit (>99%) isoliert. Besonders hervorzuheben ist die erstmalige Synthese des trans-N,N´´-funktionalisierten Cyclam-Propionsäure-Derivates 14b in hoher Ausbeute (gesamt = 32%). Von den Verbindungen 13, 14b, 15 und 16 sind entsprechende Kupfer(II)-Komplexe hergestellt worden. Zur Aufklärung relevanter Fragestellungen bezüglich der chemischen und geometrischen Eigenschaften sind verschiedene spektroskopische Methoden (Röntgeneinkristallstrukturanalyse, IR, UV/VIS, Elektronenspinresonanz-Spektroskopie) anhand von den isolierten Kupfer(II)-Komplexen CuII-13, CuII-14b und CuII-16 herangezogen worden. Die röntgenkristallografischen Strukturaufklärungen der Komplexe CuII-14b und CuII-16 weisen eine verzerrt quadratisch-pyramidale Koordinationsgeometrie auf. Das Ligandenfeld wird innerhalb der Stickstoffebene mit steigendem Substitutionsgrad schwächer. Das wurde auch durch ESR-Messungen bestätigt. Nachweislich verursachen die zusätzlichen funktionellen Gruppen eine kleinere Ligandenfeldaufspaltung. Weiterhin nahm die kinetische Stabilität unter stark sauren Bedingungen mit steigendem Substitutionsgrad ab. Der Vergleich mit den bekannten oktaedrischen Kupfer(II)-Cyclam-Essigsäure-Komplexen zeigt, dass die quadratisch-pyramidalen Kupfer(II)-Cyclam-Propionsäure-Derivate unter stark sauren Bedingungen schneller dissoziieren. Als Ursache können die unterschiedlichen Konfigurationen diskutiert werden, da bei 4N+2-Geometrien die thermodynamisch bevorzugte trans III-Konfigurationen gebildet wird. Radiochemische Untersuchungen zur Bewertung der kinetischen Stabilität in vitro und in vivo sind mit den 64Cu-markierten Liganden 13, 14b, 15 und 16 durchgeführt worden. Hierfür ist ein In-vitro-Stabilitätstest basierend auf dem kupferbindenden Enzym Superoxid-Dismutase (SOD) bzw. humanem Serum für radiomarkierte Verbindungen entwickelt worden. In humanem Serum ist Albumin (~66 kDa) in sehr hoher Konzentration enthalten und eines der wichtigsten Transportproteine für extrazelluläre Kupfer-Ionen. Aufgrund seiner Abundanz im Blutplasma ist im Serum-Assay jeweils nur eine stark ausgeprägte Bande bei ca. 66 kDa detektiert worden. Dieser etablierte In-vitro-Stabilitätstest beruht im Gegensatz zu anderen herkömmlichen Analysemethoden (Radio-HPLC oder Radio-DC) auf dem Prinzip der Gelelektrophorese. Von großem Vorteil ist, dass mehrere Proben simultan untersucht werden können und die Ergebnisse zuverlässig und reproduzierbar sind. Die In-vitro-Ergebnisse zeigen einen ähnlichen Trend wie bei der säure-assoziierten Dissoziation, wobei die höchste Stabilität bemerkenswerterweise bei dem [64Cu]Cu-14b Komplex bestimmt wurde. Allerdings beruht der Mechanismus hier nicht auf einer Dissoziation sondern auf einer Transchelatisierung. Die Ergebnisse der Bioverteilungen in Wistar-Ratten korrelieren mit den In-vitro-Studien in humanem Serum. Der Komplex [64Cu]Cu 14b zeigte sowohl eine schnelle renale Blut-Clearence als auch eine sehr geringe Anreicherung in der Leber und stellt damit eine Alternative zu den kommerziell erwerblichen Liganden dar. Als geeignete Chelatoren bieten Cyclam-Monopropionsäure 13 und Cyclam-Dipropionsäure 14b die Möglichkeit, Radiokupfernuklide stabil zu binden und erlauben die mehrfache Einführung von EGFR-spezifischen Peptiden an das Grundgerüst. Als Grundgerüst wurde der Ligand 13 ausgewählt. Durch die Multifunktionalisierung sollen höhere Affinitäten zum Rezeptor und verbesserte metabolische Stabilitäten hervorgerufen werden. Für diese Verbindung liegen erste vielversprechende Ergebnisse vor, wobei hohe Affinitäten zu zwei EGFR-positiven Zelllinien bestimmt wurden.