<p>The object of this work is to obtain a fundamentalunderstanding of the principal issues concerning the handlingof an aqueous WC-Co powder suspension.</p><p>The WO3 surface layer on the oxidised tungsten carbidepowder dissolves at pH>3 with the tungsten concentrationincreasing linearly with time. Adding cobalt powder to thetungsten carbide suspension resulted in a significant reductionof the dissolution rate at pH<10. Electrokinetic studiesindicated that the reduced dissolution rate may be related tothe formation of surface complexes; the experiments showed thatCo species in solution adsorb on the oxidised tungsten carbidepowder.</p><p>The surface forces of oxidised tungsten and cobalt surfaceswere investigated using the atomic force microscope (AFM)colloidal probe technique. The interactions at various ionicstrengths and pH values are well described by DLVO theory. Theadsorption of cobalt ions to tungsten oxide surfaces resultedin an additional non-DLVO force and a reduced absolute value ofthe surface potential. It was shown that the adsorption ofpoly(ethylene imine) (PEI) to the WO3 surfaces induces anelectrosteric repulsion.</p><p>The properties of spray-dried WC-Co granules were related tothe WC primary particle size, and the poly(ethylene glycol)(PEG) binder and PEI dispersant content in aqueous WC-Cosuspensions. The granule characterisation includes a new methodfor measuring the density of single granules. The increase inthe fracture strength of granules produced from suspensionsthat were stabilised with PEI was related to a more densepacking of the WC-Co particles.</p><p>The AFM was used to study the friction and adhesion ofsingle spray-dried WC-Co granules containing various amounts ofPEG binder. The adhesion and friction force between two singlegranules (intergranular friction) and between a granule and ahard metal substrate (die-wall friction) have been determinedas a function of relative humidity. The granule-wall frictionincreases with binder content and relative humidity, whereasthe granule-granule friction is essentially independent of therelative humidity and substantially lower than the granule-wallfriction at all PEG contents.</p><p><b>Key words:</b>Hard Metal, Cemented Carbide, WC-Co, TungstenCarbide, Cobalt, Oxidation, Dissolution, Surface Complexation,XPS, AFM, Colloidal Probe, Hamaker Constant, Cauchy, WO3,CoOOH, ESCA, Zeta-Potential, Surface Potential, Poly(ethyleneimine), PEI, Suspension, van der Waals, Steric, Spray-Dried,Poly(ethylene glycol), Strength, Density, Friction, Adhesion,Granule, PEG, Pressing, FFM.</p>

No description available.

Self-assembly processes were used to construct supramolecular architectures based on metal-ligand interactions. The structures formed strongly depend on the used metal ion, the ligand type, the chosen counter ion and solvent as well as on the experimental conditions. The focus of the studies was the design of multifunctional N-donor ligands and the characterization of their complexing and structural properties. This work was divided into three distinct main parts: The bis(2-pyridylimine), the bis(2-hydroxyaryl) imine and the tripodal imine / amine ligand approach. In the first part a series of bis(2-pyridylimine) derivatives having different linking elements were employed as building blocks for novel supramolecular architectures. Reaction of individual d-block metal salts with these ligands has led to the isolation of coordination polymers, a metallamacrocycle, double-stranded helicates, triple-stranded helicates as well as of circular meso-helicates. The nature of the spacer in the Schiff base ligands, the noncovalent weak interactions, such as hydrogen bond, face-to-face π-π and edge-to-face CH-π interactions, are all important factors influencing the architecture of the final products. Topological control of the assembly process of the hexanuclear meso-helicates is clearly associated with the bidentate coordination of the sulfate anion which directs the formation of a double- rather than a triple-stranded helicate around the octahedrally coordinated Cu(II). Surprisingly, the variation of the linker function in the ligands, which significantly changes the linking angle of the pyridylimine strands, has only a little influence of the resulting structure. Also the use of a mixture of ligands does not influence the meso-helicate topology; the result is the symmetrically mixed meso-helicate. The new iron(II) triple helicate [Fe2(L5)3](PF6)4 14 {L5 = bis[4-(2-pyridylmethyleneimino)phenyl]-1,1-cyclohexane} in its chloride form binds strongly to DNA as confirmed by induced circular dichroism signals in both the metal-to-ligand charge transfer (MLCT) and in-ligand bands of the helicate. The induced CD spectrum gives some evidence that [Fe2(L5)3]4+ interacts with the DNA in a single binding mode, which is consistent with major groove binding. The cytotoxicity of the new iron(II) triple helicate 14 was evaluated on human lung cancer A549 cells and compared with that of cisplatin and that of the previously reported iron(II) triple helicate [Fe2(L1)3]4+{L1 = bis[4-(2-pyridylmethyleneimino)phenyl]methane}. The first results show some distinguishing features for 14 obviously caused by the existing structural differences of the complexes. In the second part of the thesis, novel uranyl complexes of the bis(2-hydroxyaryl) imine ligands have been synthesized and characterized. 1D coordination polymers and mononuclear structures were formed. In all complexes a distorted hexagonal bipyramidal coordination geometry around the uranyl centre is observed. The imine nitrogen atoms of the ligands do not bind to the metal centre but interact strongly with the hydroxy group via H-bonding. DFT calculations made with L8 ( α,α’-Bis(salicylimino)-m-xylene) are in good agreement with the X-ray crystal structure data. Liquid-liquid extraction studies involving selected ligands and Eu(III) or U(VI) indicate remarkably high selectivity for U(VI) over Eu(III) at weak acidic pH conditions. We believe that the study made opens up new possibilities for uranyl ion extraction which could be interesting in view of the treatment of nuclear waste. In the third part of the thesis, a series of multifunctional tripodal ligands with different N-donor centres were used for U(VI) and lanthanide, Nd(III), Eu(III) and Yb(III), binding and extraction. Reaction of these metal ions with selected tripodal ligands afforded complexes which were characterized by ESI mass spectroscopy. The complex composition was found to be 1:1 in all cases. The extraction behaviour of the tripodal ligands towards Eu(III) and U(VI) was studied both in the absence and presence of octanoic acid as co-ligand using the extraction system Eu(NO3)3 or UO2(NO3)2–buffer–H2O/ ligand–CHCl3. These separation systems show a remarkably high selectivity for U(VI) over Eu(III). It is interesting to note that the addition of the octanoic acid to the extraction system leads to high synergistic effects. A series of Eu(III) extraction experiments were done to clarify the composition of the extracted complexes. The results clearly point to the formation of various species with changing composition.

Die bisher gängigen PVC-Membranen ionenselektiver Elektroden weisen eine Reihe von Schwachstellen auf: Sie haften nur durch Adhäsion am Substrat, sodass sich bei miniaturisierten Elektroden die Membran ablösen kann; Membranbestandteile wie der Weichmacher, das Ionophor oder der Ionenaustauscher können bei der Verwendung ausgewaschen werden, sodass sich die chemischen und physikalischen Eigenschaften der Membran verschlechtern; auf der Membranoberfläche kann sich auf Grund ihrer Hydrophobie ein Biofilm ausbilden, der die Membran abschirmt. Diese Schwachstellen bewirken eine Dysfunktionalität der ionenselektiven Elektrode, weshalb im Rahmen dieser Arbeit ein Glycopolymerfilm entwickelt worden ist, der diese Schwachstellen nicht aufweist. Die in dieser Arbeit entwickelte Membran, die auf einem multifunktionalen Glycopolymer beruht, zielt auf die Egalisierung der Schwachstellen konventioneller ionenselektiver PVC-Membranen. Die entwickelte Membran kommt dabei ohne Weichmacher aus, reduziert die Ausbildung von Biofilmen, bindet kovalent an das darunterliegende organische Substrat und durch die kovalente Anbindung des Ionophors wird dessen Auswaschen verhindert. Um eine kovalente Bindung der Membran an organische Vermittlerschichten zu erreichen, wie sie bei All-solid-state-Elektroden zum Einsatz kommen, werden zunächst die photovernetzbaren Glycopolymere 12a–c entwickelt, bei denen etwa neun Photovernetzereinheiten über PEG-Spacer an den PEI25-Kern gebunden sind. Drei PEG-Spacer mit unterschiedlicher Länge werden hinsichtlich ihres Einflusses auf die Filmbildung untersucht: Sie besitzen vier (12a), acht (12b) und zwölf Ethylenglycoleinheiten (12c). Dabei zeigt sich, dass eine Spacerlänge von zwölf Ethylenglycoleinheiten für eine effektive Photovernetzung notwendig ist, weshalb für die folgenden Strukturen nur PEG12-Spacer eingesetzt werden. Um eine kovalente Anbindung des Ionophors an das Glycopolymer zu erreichen, werden verschiedene Syntheserouten genutzt und auf ihre Wirkung hin analysiert. Die frühe direkte Anbindung des Calix[4]arenderivats 3 an den PEI25-Kern der Glycopolymere 17a–c erweist sich als nachteilig, da hierdurch darauffolgende Syntheseschritte beeinträchtigt werden. Anderseits zeigen diese Glycopolymere, dass sich die Calix[4]areneinheiten nicht negativ auf die Glycopolymerfilmbildung auswirken. Zur Überwindung der erwähnten Probleme werden in den multifunktionalen Glycopolymeren 22a und 22b die Calix[4]arene wie der Photovernetzer am Ende der Syntheseroute über PEG12-Spacer angebunden. Dies erfolgt dabei über den upper rim des Calix[4]arens, da somit der lower rim, an dem sich ionenkomplexierenden Gruppen befinden, nicht beeinflusst wird. Neben der Struktur des Glycopolymers wird auch eine Methode zur Glycopolymerfilmbildung auf Modellsubstraten entwickelt. Hierfür werden Siliziumwafer mit einer hydrophilen organischen Vermittlerschicht aus (3-Glycidyloxypropyl)-trimethoxysilan (GOPS) eingesetzt. Bei der Filmbildung zeigt sich, dass die alleinige Bestrahlung mit UV-Licht nicht ausreichend ist, um eine stabile Vernetzung zu generieren. Erst nach vorausgehendem Tempern (1 h bei 120 °C) werden Filme mit einer Dicke von (42±8) nm für das Glycopolymer 12c erhalten. Die Glycopolymere 12a und 12b, die kürzere PEG-Spacer enthalten, bilden deutlich dünnere Filme aus. Für die vollständige Vernetzung ist eine Bestrahlungszeit von einer Stunde notwendig, was einer Energiedosis von etwa 290 J/cm² entspricht. Trotz möglicher freier Aminogruppen in der Struktur bilden die Glycopolymere 17a–c, bei denen unterschiedlich viele Calix[4]arene direkt an den PEI25-Kern gebunden sind, stabile Filme aus. Die sich ergebenden Schichtdicken zeigen dabei weder im Vergleich zum Glycopolymer 12c noch untereinander signifikante Unterschiede. Die Filmbildung auf dem hydrophilen GOPS wird demzufolge durch die direkt angebundenen Calix[4]arene nicht beeinträchtigt. Auf Grund des erwarteten amphiphilen Charakters der Glycopolymere 17a–c wird ihre Filmbildung nicht nur auf hydrophilen, sondern auch auf hydrophoben Modellsubstraten untersucht. Hierzu werden Siliziumwafer mit hydrophoben Vermittlerschichten aus Benzophenonsilan (BPS) und Poly-α-methylstyrol (PαMS) eingesetzt. Auf den hydrophoben Vermittlerschichten bilden die Glycopolymere 17a–c deutlich dünnere Filme aus als auf dem hydrophilen GOPS. Die Calix[4]areneinheiten sind demnach durch die Maltosehülle abgeschirmt und es treten kaum Wechselwirkungen mit den hydrophoben Substratoberflächen auf. Im Gegensatz dazu ermöglicht die Anbindung der Calix[4]arene über PEG12-Spacer den Glycopolymeren 22a und 22b auf hydrophilen wie hydrophoben Vermittlerschichten in etwa gleich dicke Filme auszubilden. Offensichtlich liegt bei diesen Glycopolymeren eine amphiphile Peripherie vor, sodass sich die Glycopolymere besonders zur Beschichtung von All-solid-state-Elektroden mit verschiedenen Mediatorschichten eignen. Die photovernetzten Glycopolymerfilme quellen auf Grund ihrer hydrophilen Eigenschaften. Der Quellungsgrad q liegt dabei niedriger, wenn hydrophobe Calix[4]arene in die Struktur eingebunden sind: q(17c) = 2,3 im Vergleich zu q(12c) = 3,6. Erfolgt die Anbindung der Calix[4]arene direkt an den PEI25-Kern, ist die Glycopolymerstruktur unflexibel, sodass der Quellungsprozess bis zu sieben Stunden benötigt. Durch die Anbindung der Calix[4]arene über PEG12-Spacer wird die Flexibilität der Glycopolymere hingegen nicht beeinträchtigt, sodass der Quellungsprozess weniger als zwei Stunden benötigt. PVC-Membranen verlieren schon nach kurzer Zeit ihre ionenselektiven Eigenschaften, weil etwa der Weichmacher aus den Membranen diffundiert und diese dadurch spröde werden. Die Glycopolymerfilme sind hingegen über einen Zeitraum von mindestens 100 Tagen gegenüber sauren (pH = 4), neutralen und basischen (pH = 10) Lösungen stabil. Die entwickelten Glycopolymere werden im Rahmen einer Kooperation mit dem Kurt-Schwabe-Institut (KSI) in Meinsberg auf All-solid-state-Elektroden als ionenselektive Membranen eingesetzt. Die Graphitelektroden werden dafür mit einer Mediatorschicht aus leitfähigem Polypyrrol (PPy) und dem Glycopolymer 17c beschichtet. Die All-solid-state-Elektroden werden hinsichtlich ihres Ansprechverhaltens gegenüber verschiedenen Ionen untersucht. Die Anbindung und Vernetzung erfolgt nach der für die Modellsubstrate optimierten Methode. Jedoch werden die Bedingungen für das Tempern angepasst, um eine Beschädigung der All-solid-state-Elektrode auszuschließen: 12 h bei 45 °C statt 1 h bei 120 °C. Dabei bildet sich ein inhomogener Belag aus, bei dem Teile der PPy-Schicht frei bleiben. Im Vergleich zur reinen und zur mit Polypyrrol (PPy) beschichteten Graphitelektrode zeigt die Elektrode, die mit einem Glycopolymerfilm versehen ist, trotz der Inhomogenität stabile und reproduzierbare Potentiale. Diese sind jedoch nicht von der Konzentration der Kationen, sondern von der der Anionen abhängig. Durch die Auftragung einer Ionentauscherschicht auf die ionenselektive Membran soll das Vordringen der Anionen in die Membran der All-solid-state-Elektrode unterbunden werden. Dadurch soll das Ansprechverhalten der All-solid-state-Elektrode auf die Kationen gelenkt werden. Entsprechende Arbeiten werden am KSI durchgeführt.

Self-assembly processes were used to construct supramolecular architectures based on metal-ligand interactions. The structures formed strongly depend on the used metal ion, the ligand type, the chosen counter ion and solvent as well as on the experimental conditions. The focus of the studies was the design of multifunctional N-donor ligands and the characterization of their complexing and structural properties. This work was divided into three distinct main parts: The bis(2-pyridylimine), the bis(2-hydroxyaryl) imine and the tripodal imine / amine ligand approach. In the first part a series of bis(2-pyridylimine) derivatives having different linking elements were employed as building blocks for novel supramolecular architectures. Reaction of individual d-block metal salts with these ligands has led to the isolation of coordination polymers, a metallamacrocycle, double-stranded helicates, triple-stranded helicates as well as of circular meso-helicates. The nature of the spacer in the Schiff base ligands, the noncovalent weak interactions, such as hydrogen bond, face-to-face π-π and edge-to-face CH-π interactions, are all important factors influencing the architecture of the final products. Topological control of the assembly process of the hexanuclear meso-helicates is clearly associated with the bidentate coordination of the sulfate anion which directs the formation of a double- rather than a triple-stranded helicate around the octahedrally coordinated Cu(II). Surprisingly, the variation of the linker function in the ligands, which significantly changes the linking angle of the pyridylimine strands, has only a little influence of the resulting structure. Also the use of a mixture of ligands does not influence the meso-helicate topology; the result is the symmetrically mixed meso-helicate. The new iron(II) triple helicate [Fe2(L5)3](PF6)4 14 {L5 = bis[4-(2-pyridylmethyleneimino)phenyl]-1,1-cyclohexane} in its chloride form binds strongly to DNA as confirmed by induced circular dichroism signals in both the metal-to-ligand charge transfer (MLCT) and in-ligand bands of the helicate. The induced CD spectrum gives some evidence that [Fe2(L5)3]4+ interacts with the DNA in a single binding mode, which is consistent with major groove binding. The cytotoxicity of the new iron(II) triple helicate 14 was evaluated on human lung cancer A549 cells and compared with that of cisplatin and that of the previously reported iron(II) triple helicate [Fe2(L1)3]4+{L1 = bis[4-(2-pyridylmethyleneimino)phenyl]methane}. The first results show some distinguishing features for 14 obviously caused by the existing structural differences of the complexes. In the second part of the thesis, novel uranyl complexes of the bis(2-hydroxyaryl) imine ligands have been synthesized and characterized. 1D coordination polymers and mononuclear structures were formed. In all complexes a distorted hexagonal bipyramidal coordination geometry around the uranyl centre is observed. The imine nitrogen atoms of the ligands do not bind to the metal centre but interact strongly with the hydroxy group via H-bonding. DFT calculations made with L8 ( α,α’-Bis(salicylimino)-m-xylene) are in good agreement with the X-ray crystal structure data. Liquid-liquid extraction studies involving selected ligands and Eu(III) or U(VI) indicate remarkably high selectivity for U(VI) over Eu(III) at weak acidic pH conditions. We believe that the study made opens up new possibilities for uranyl ion extraction which could be interesting in view of the treatment of nuclear waste. In the third part of the thesis, a series of multifunctional tripodal ligands with different N-donor centres were used for U(VI) and lanthanide, Nd(III), Eu(III) and Yb(III), binding and extraction. Reaction of these metal ions with selected tripodal ligands afforded complexes which were characterized by ESI mass spectroscopy. The complex composition was found to be 1:1 in all cases. The extraction behaviour of the tripodal ligands towards Eu(III) and U(VI) was studied both in the absence and presence of octanoic acid as co-ligand using the extraction system Eu(NO3)3 or UO2(NO3)2–buffer–H2O/ ligand–CHCl3. These separation systems show a remarkably high selectivity for U(VI) over Eu(III). It is interesting to note that the addition of the octanoic acid to the extraction system leads to high synergistic effects. A series of Eu(III) extraction experiments were done to clarify the composition of the extracted complexes. The results clearly point to the formation of various species with changing composition.

Delivery of siRNAs for the treatment of tumors critically depends on the development of efficient nucleic acid carrier systems. The complexation of dendritic polymers (dendrimers) results in nanoparticles, called dendriplexes, that protect siRNA from degradation and mediate non-specific cellular uptake of siRNA. However, large siRNA doses are required for in vivo use due to accumulation of the nanoparticles in sinks such as the lung, liver, and spleen. This suggests the exploration of targeted nanoparticles for enhancing tumor cell specificity and achieving higher siRNA levels in tumors. In this work, we report on the targeted delivery of a therapeutic siRNA specific for BIRC5/Survivin in vitro and in vivo to tumor cells expressing the surface marker prostate stem cell antigen (PSCA). For this, polyplexes consisting of single-chain antibody fragments specific for PSCA conjugated to siRNA/maltose-modified poly(propylene imine) dendriplexes were used. These polyplexes were endocytosed by PSCA-positive 293TPSCA/ffLuc and PC3PSCA cells and caused knockdown of reporter gene firefly luciferase and Survivin expression, respectively. In a therapeutic study in PC3PSCA xenograft-bearing mice, significant anti-tumor effects were observed upon systemic administration of the targeted polyplexes. This indicates superior anti-tumor efficacy when employing targeted delivery of Survivin-specific siRNA, based on the additive effects of siRNA-mediated Survivin knockdown in combination with scFv-mediated PSCA inhibition. Among non-viral vectors, cationic polymers, such as poly(propylene imine) (PPI), play also a prominent role in plasmid DNA delivery. However, limitations of polycationic polymer-based DNA delivery systems are (i) insufficient target specificity, (ii) unsatisfactory transgene expression, and (iii) undesired transfer of therapeutic DNA into non-target cells. We developed single-chain antibody fragment (scFv)-directed hybrid polyplexes for targeted gene therapy of prostate stem cell antigen (PSCA)-positive tumors. Besides mono-biotinylated PSCA-specific single-chain antibodies (scFv(AM1-P-BAP)) conjugated to neutravidin, the hybrid polyplexes comprise β cyclodextrin-modified PPI as well as biotin/maltose-modified PPI as carriers for minicircle DNAs encoding for Sleeping Beauty transposase and a transposon encoding the gene of interest. The PSCA-specific hybrid polyplexes efficiently delivered a GFP gene in PSCA-positive tumor cells, whereas control hybrid polyplexes showed low gene transfer efficiency. In an experimental gene therapy approach, targeted transposition of a codon-optimized p53 into p53 deficient HCT116p53-/-/PSCA cells demonstrated decreased clonogenic survival when compared to mock controls. Noteworthily, p53 transposition in PTEN-deficient H4PSCA glioma cells caused nearly complete loss of clonogenic survival. These results demonstrate the feasibility of combining tumor-targeting hybrid polyplexes and Sleeping Beauty gene transposition, which, due to the modular design, can be extended to other target genes and tumor entities.

Two-dimensional (2D) membranes are emerging candidates for osmotic energy conversion. However, the trade-off between ion selectivity and conductivity remains the key bottleneck. Here we demonstrate a fully crystalline imine-based 2D polymer (2DPI) membrane capable of combining excellent ionic conductivity and high selectivity for osmotic energy conversion. The 2DPI can preferentially transport cations with Na+ selectivity coefficient of 0.98 (Na+/Cl− selectivity ratio ~84) and K+ selectivity coefficient of 0.93 (K+/Cl− ratio ~29). Moreover, the nanometer-scale thickness (~70 nm) generates a substantially high ionic flux, contributing to a record power density of up to ~53 W m−2, which is superior to most of nanoporous 2D membranes (0.8~35 W m−2). Density functional theory unveils that the oxygen and imine nitrogen can both function as the active sites depending on the ionization state of hydroxyl groups, and the enhanced interaction of Na+ versus K+ with 2DPI plays a significant role in directing the ion selectivity.

Aufgrund ihrer Eigenschaften und möglicher Anwendungen werden Siliciumkomplexe mit O,N,O´-Ligandsystemen in der Literatur beschrieben. Jedoch fehlen bisher Untersuchungen zur Strukturaufklärung. Im Rahmen dieser Arbeit wurden zahlreiche Silicium-, Germanium- und Zinnkomplexe mit chiralen O,N,O´-Liganden synthetisiert und strukturanalytisch charakterisiert. Dazu wurden die Liganden durch Kondensationsreaktionen von enantiomerenreinen Aminosäuren mit aromatischen ortho-Hydroxyaldehyden bzw. Acetylaceton hergestellt. Die weitere Umsetzung der Liganden mit Elementhalogeniden der Gruppe 14 führte zu den angestrebten Komplexverbindungen. Alle hergestellten Verbindungen wurden umfassend charakterisiert (NMR-, UV/Vis-, IR-Spektroskopie, Elementaranalyse, Einkristallstrukturanalyse, Drehwert). Quantenchemische Berechnungen an einfachen Modellverbindungen sowie an hergestellten Silicium- und Zinnkomplexen führten zu einem grundlegenden Verständnis der Festkörper-NMR-Parameter dieser Verbindungsklasse.

Överkonsumtionen av engångsartiklar i fossilbaserad plast är ett av dagens stora miljöproblem. Således finns en efterfrågan på strategier för framställning av biobaserade plaster i allmänhet och härdplaster i synnerhet. Tidigare forskning har visat att vanillin-baserade resin, genom UV-härdning och dynamisk iminkemi, kan användas i framställningen av härdplaster som är termiskt bearbetningsbara, kemiskt återvinningsbara och självläkande. Följaktligen är Digital Light Processing (DLP) 3D-utskrivning en möjlig och flexibel friformframställningsmetod med stor noggrannhet för sådana härdplaster.  Mot denna bakgrund framställdes, i detta projekt, tre olika UV-härdbara, biobaserade monomerer, i form av vitrimerresin, genom en tvåstegsreaktion: metakrylering av vanillin följt av iminbildning med tre olika aminer (etylendiamin, EDA; 2,2′-etylendioxi bisetylamin, EDEA och trimetylolpropan trispolypropylenglykol aminterminerad eter, T-403). De tre olika monomererna analyserades för att identifiera den mest lämpade för friformframställning av härdplast med DLP 3D-printning. Monomeren framställd med EDA kunde inte UV-härdas till en härdplast. De två andra monomererna, å andra sidan, härdades framgångsrikt till härdplaster med god termisk stabilitet (upp till ungefär 300 °C) samtidigt som de var termiskt bearbetningsbara. Vidare visade dessa härdplaster lovande resultat vad gäller självläkning och kemisk återvinningsbarhet. Härdningen av monomeren syntetiserad med EDEA krävde minst tidsåtgång. Utöver detta visade denna härdplast god stabilitet i ett flertal vanliga lösningsmedel samtidigt som den, till följd av dess dynamiska iminbindningar, kemiskt kunde återvinnas i hexylamin. Slutligen visades det hur detta resin framgångsrikt kunde användas i DLP 3D-utskrivning av härdplast. / One of the main causes of the petrochemical depletion is the overconsumption of single-use plastic products. New strategies based on the production of plastics (in particular thermosets) starting from bio-based resources are, therefore, demanded. Previous research has shown how vanillin-based vitrimer resins can be photocured into thermally reprocessable, chemically recyclable and self-healable imine thermosets; and the potential of the light-assisted 3D-printing techniques for the photocuring of resins with great accuracy and flexibility.  In this study, three different photocurable biobased vitrimer resins were synthesized through a two-step procedure involving the methacrylation of vanillin and the Schiff-base reaction with two different diamines (ethylenediamine, EDA; 2,2′-(Ethylenedioxy) bis(ethylamine), EDEA) and a triamine (trimethylolpropane tris[poly(propylene glycol), amine terminated] ether, T-403). The resins were analyzed in order to find the most suitable one for DLP 3D-printing. The resin with EDA, as diamine, could not be successfully UV-cured into a thermoset. The other two thermosets showed good thermal stability, up to about 300 °C, while still being thermally reprocessable. In addition, the thermosets were promising in terms of self-healability and chemical recyclability. The thermoset obtained from the Schiff-base resin synthesized with the diamine EDEA provided the shortest curing time. This resin also displayed good solvent resistance against common solvents and potential chemical recyclability in hexylamine through an imine exchange reaction. As a final step, the possibility to obtain tridimensional thermosets by curing this resin with a DLP 3D-printing was successfully demonstrated.

Les cyclopropanes sont des motifs d’une grande importance puisqu’ils sont présents dans plusieurs molécules biologiquement actives en plus d’être de puissants intermédiaires dans la synthèse de molécules complexes. Au cours de cet ouvrage, nous avons développé une nouvelle méthode générale pour la synthèse d’ylures d’iodonium de malonates, soit d’importants précurseurs d’esters cyclopropane-1,1-dicarboxyliques. Ainsi, à l’aide de ces ylures, une méthode très efficace pour la synthèse d’esters cyclopropane-1,1-dicarboxyliques racémiques a été développée. Des travaux ont aussi été entrepris pour la synthèse énantiosélective de ces composés. Par ailleurs, les esters cyclopropane-1,1-dicarboxyliques ont été utilisés dans le développement de deux nouvelles méthodologies, soit dans une réaction de cycloaddition (3+3) avec des imines d’azométhines et dans la formation d’allènes par l’addition-1,7 de cuprates. Nous avons aussi poursuivi l’étude synthétique du cylindrocyclophane F impliquant l’utilisation de cyclopropanes pour le contrôle des centres chiraux. Ainsi l’addition-1,5 d’un cuprate sur un ester cyclopropane-1,1-dicarboxylique a été utilisée comme l’une des étapes clés de notre synthèse. L’autre centre chiral a pu être contrôlé par l’hydrogénolyse sélective d’un cyclopropylméthanol. Ces études ont, par ailleurs, mené au développement d’une nouvelle réaction d’arylcyclopropanation énantiosélective utilisant des carbénoïdes de zinc générés in situ à partir de réactifs diazoïques. Cette méthode permet d’accéder très efficacement aux cyclopropanes 1,2,3-substitués. De plus, nous avons développé la première réaction de Simmons-Smith catalytique en zinc menant à un produit énantioenrichi. / Cyclopropanes are important scaffolds as they are present in many biologically actives compounds and they are useful intermediates in the synthesis of complex molecules. In this thesis, we developed a novel general method for the synthesis of iodonium ylides of malonates, which are important precursors in the synthesis of cyclopropane-1,1-dicarboxylic esters. From these ylides, a method to generate racemic cyclopropane-1,1-dicarboxylic esters very efficiently was developed. Further works was also achieved on an asymmetric version of this reaction. Cyclopropane-1,1-dicarboxylic esters were used to develop two new methods: a (3+3) cycloaddition reaction with azomethine imines and the formation of allenes by the 1,7-addition of cuprates. We also continued our studies towards the total synthesis of cylindrocyclophane F, which use the cyclopropanes to control all chiral centers. The 1,5-addition of a cuprate on a cyclopropane-1,1-dicarboxylic ester was utilized as one of the key steps of our synthesis. The other chiral centre was controlled by the hydrogenolysis of a cyclopropylmethanol. Moreover, these studies led to the development of a novel highly enantioselective arylcyclopropanation reaction using zinc carbenoids generated in situ from diazo compounds. This method allows the efficient access to 1,2,3-substituted cyclopropanes. Moreover, we developed the first Simmons-Smith reaction using a catalytic amount of zinc to produce an enantioenriched product.