Le présent mémoire décrit la synthèse et l’utilité de complexes Cu-NHC. En premier lieu, la synthèse de complexes de cuivre porteurs de ligand(s) de type carbène-N-hétérocyclique (NHC) via une génération décarboxylative de carbènes sera présentée. En effet, de précédents rapports font état de l’utilisation de carboxylates d’imidazol(in)ium en tant que précurseurs carbéniques sous conditions thermolytiques. Ainsi, la présente étude montre l’utilisation de ces espèces zwitterioniques pour la synthèse de complexes de cuivre(I) mono- et bis-NHC comportant divers substituants et contre-ions. Une seconde partie du projet se concentrera sur l’évaluation de complexes Cu-NHC en tant que catalyseurs pour la synthèse de 2,2’-binaphtols via une réaction de couplage oxydatif de naphtols. L’objectif de ce projet de recherche est d’étudier les effets de variations structurales de différents complexes Cu-NHC afin de construire un processus catalytique plus efficace. Les effets de la structure du catalyseur sur la réaction de couplage ont été évalués en variant son contre-ion, le nombre de ligands NHC se coordonnant au cuivre, ainsi que la nature des substituants du ligand. / The present thesis describes the synthesis and utility of NHC-Cu complexes. First, the synthesis of N-heterocyclic carbene (NHC) copper complexes via the decarboxylative generation of carbenes is presented. Indeed, literature precedents reported that imidazol(in)ium-2-carboxylates may be used as carbene precursors under thermolytic conditions. As such, the present study demonstrates how zwitterionic carboxylates may be utilized in the formation of both mono- and bis-NHC Cu complexes with various substitution patterns and counterions. Secondly, the NHC-Cu complexes were evaluated for the synthesis of 2,2’-binaphthols via the oxidative coupling of naphthol derivatives. The objective of the study was to investigate how structural variations to various NHC-Cu catalysts may generate a more efficient catalytic process. Effects of the structure of the catalyst on the coupling reaction have been studied by varying the number of NHC ligands coordinating to Cu, as well as the nature of the NHC ligand substituents and the counterions.

Techn. Hochsch., Diss., 2004--Aachen.

Polysaccharides, one of three types of natural polymer, are used by living organisms for energy storage, structural support, and other vital applications. In particular, acidic polysaccharides such as alginic acid and hyaluronan play important roles in lubrication and water storage. Isolation of polysaccharides is complicated by the difficulty of purification and lack of batch-to-batch consistency. Polysaccharide synthesis has also proved challenging due to their stereochemical complexity and high density of functional groups with similar reactivity. One solution is the synthesis of mimics that possess many of the properties of natural polysaccharides, including a rigid pyranose or furanose backbone and numerous hydroxyl or carboxylic acid groups. Synthesized polysaccharide mimics include polymers with ether linkages not seen in nature, non-ether linked sugar monomers, and polymers created from non-carbohydrate sources. These mimics have been used in various applications, including biolubrication, membrane synthesis, and DNA delivery. As a first approach to a polysaccharide mimic, a polymer with a rigid cyclic backbone and several pendant water-soluble functional groups was sought. High molecular weight ester-functionalized norbornene polymers were synthesized by ring-opening metathesis polymerization of 5-norbornene-2-ethyl ester. The resulting polymers were saponified and hydroxylated along the polymer backbone without a reduction in chain length. The chemical, thermal, and mechanical properties of the various polymers were measured, indicating high thermal stability and strong solid-like character. Even in their saponified and hydroxylated form, the polymers possessed very limited water solubility. Poly-amido-saccharides, a new type of carbohydrate polymer mimetic, were synthesized by the controlled anionic ring opening polymerization of a beta-lactam glucose monomer. The primary alcohol was oxidized to investigate the effects of an ionizable carboxylic acid group, such as those found in natural polysaccharides containing glucuronic acid. Circular dichroism revealed an ordered helical secondary structure in solution that was lost following ring opening. The oxidized poly-amido-saccharides were shown to stabilize lysozyme towards freezing and dehydration stresses better than currently used methods. Glycopolymers containing the poly-amido-saccharides on a poly(acrylamide) backbone were also synthesized and characterized as a model for more complex systems.

This thesis describes the synthesis of ruthenium based molecular clusters and their characterisation. Chapter 2 introduces the concept that the very large zero-field splitting (D = 2.9 cm–1) in the S = 5/2 ground state of [Ru2Mn(μ3-O)(tBuCO2)6(py)3] can be modelled by antisymmetric exchange effects. This is supported by measurement of the single ion D values from the Fe2Mn analogue. The same model is applied to the Ru2Ni analogue to describe the zero-field splitting in the S = 1 ground state, (DGS = +8.0 cm–1 from DNi = -4.0 cm–1) in Chapter 3.Chapters 3 and 4 give the full characterisation of each of the two families, [MIII2MII(μ3-O)(tBuCO2)6(py)3] (MIII = Ru or Fe, MII = Mn, Co, Ni or Zn), through IR, electronic absorption and NMR spectroscopy and are structurally characterised by X-ray diffraction. The total spin ground states and zero-field splitting of those ground states have been ascertained by SQUID magnetometry and EPR spectroscopy. Due to the redox activity of the Ru2M complexes chemical oxidations led to the isolation of [RuIII2CoIIIO(tBuCO2)6(py)3]+ (5) and [RuIIIRuIVNiIIO(tBuCO2)6(py)3]+ (6); the locus of their oxidation was determined with the aid of X-ray absorption spectroscopy (XAS).Chapter 5 shows that due to the ease of the substitution of the terminal ligand in Ru2M they can be linked to other molecular clusters with N-donor ligands, in this case [Cr7NiF8(tBuCO2)15(O2CC5H4N)][NH2Pr2] in order to synthesise [Ru2NiO(tBuCO2)6(py)(Cr7NiF8(tBuCO2)15(O2CC5H4N))2][NH2Pr2]2. In situ oxidation experiments have also been carried out to assess the switchabilty of the redox active linker. Chapter 6 demonstrates a new structural archetype for tetranuclear ruthenium mixed-metal complexes, with the formula, [Ru2M2(µ3-OH)2(tBuCO2)7(py)4], where M is either Co (1) or Ni (2). SQUID magnetometry and EPR spectroscopy have determined the spin ground states as, Seff = 1/2 in 1 and S = 3/2 in 2. The magnetic anisotropy in 2 has been determined as +2.02 cm–1 for the S = 3/2 ground state.

No description available.

No description available.

The 2-His-1-carboxylate facial triad is a common metal binding motif among nonheme iron(II) enzymes. Made up of two histidine side chain residues, and one carboxylate side chain of either a glutamate or aspartate residue occupying one face of the iron(II) octahedral coordinating sphere, the 2-His-1-carboxylate motif provides proximity of substrate(s) and molecular oxygen for important oxidation reactions in biological chemistry. Computational, structural, and kinetic analyses have afforded mechanistic details on how these enzymes control the oxidation reactions they catalyze; from the oxidation state of the metal center to the supporting interactions from secondary sphere amino acid residues. However, the extensive literature on the 2-His-1-carboxylate facial triad enzymes currently contains deficiencies in the area of fundamental, experimental thermodynamic analyses of metal and substrate binding in these systems. The focus of this study is to determine the energetics of substrate and metal binding to two representative enzymes of the 2-His-1-carboxylate facial triad-containing family. More specifically, we examine iron(II) binding to the alpha-ketoglutarate- dependent model system alpha-ketoglutarate/taurine dioxygenase, and substrate binding to a well-known extradiol dioxygenase, homoprotocatechuate 2,3-dioxygenase. Using isothermal titration calorimetry, we are able to determine equilibrium constants, enthalpies, entropies and Gibbs free energies for the binding reactions, affording new insight into what drives the reactions forward at the 2-His-1-carboxylate facial triad active site center.

Yes / Thermally responsive highly branched poly(N-isopropyl acrylamide)s (HB-PNIPAM) were prepared and end-functionalised to give polymers with acid or trihistidine end groups. These polymers exhibit a broad coil-to-globule transition across a wide temperature range which can be measured using covalently attached fluorescent tags. The acid chain ends provided a material with a distinct change in solution behaviour at pH close to the pKa of the carboxylate group. At pH 11 this polymer did not show a cloud point up to 50 °C but fluorescence measurements on the labelled polymers showed that a coil to glubule transition did take place. The globular state, above the LCST, appeared to be more swollen if the end group carried charge then when it was uncharged. A polymer with trihistidine and free carboxylate chain ends, which contained multiple charges at various pH, did show LCSTs at all pH and the polymer globule was shown to be swollen at each pH.

The structure/function relationship between bacteria and biocidal molecules in the vapor or solution phase is well-understood. However, the fundamental structure/function relationship between covalently-bound biocidal surface molecules and bacteria is not. While a number of antibacterial surfaces have been reported, detailed analysis of the molecular scale surface structure has not been performed. The lack of structural knowledge makes it difficult to determine how alterations to the surface affect the viability of the bacteria. Most of the antibacterial surfaces reported to date are composed of polymer systems. Controlling the properties of large surface-bound molecules like polymers is difficult. Self-assembled monolayers, or SAMs, of alkanethiols on gold have been used extensively in the past 20 years as model surfaces for investigation of a large breadth of surface phenomena. SAMs allow for control of the molecular scale surface structure and are amenable to a great number of characterization techniques. The primary objective of the work in this study is to establish the use of SAMs as a tool to investigate the fundamental relationship between surface structure and bacteria viability. The surfaces were characterized before interaction with bacteria by reflection-absorption infrared spectroscopy (RAIRS) and X-ray photoelectron spectroscopy (XPS). Determination of the viability of Escherichia coli on the surfaces was performed via the antibacterial assay. In the assay, a culture of E. coli was sprayed onto the surfaces using a chromatography sprayer. After addition of growth agar and overnight incubation, the number of colony forming units on the surface were counted. Statistical analyses were performed to compare the number of colony forming units on different surfaces. Surfaces were characterized after the assay by RAIRS. The RAIR spectra indicated that no significant change to the well-ordered alkane chain configuration was evident. The structural stability shown by the SAMs will allow for their use in future studies to determine fundamental relationship between surface structure and bacteria viability. / Master of Science

Die vorliegende Arbeit beschreibt die Synthese und Charakterisierung ethylenglykolfunktionalisierter Carboxylate der Münzmetalle sowie deren Verwendung als Präkursoren in der Herstellung von Nanopartikeln und leitfähigen Metallschichten. Ein Schwerpunkt der Arbeit liegt auf der Verwendung von Kupfer(II)-carboxylaten zur Herstellung von druckbaren Kupfertinten. Es wird gezeigt, wie zentrale Präkursoreigenschaften durch Variation der Carboxylatreste optimiert werden können. Einen zweiten Schwerpunkt bildet die Herstellung von Kupfernanopartikeln durch thermische Zersetzung ethylenglykolfunktionalisierter Kupfercarboxylate. Der Einsatz von Bis- und Tris(triphenylphosphan)kupfer(I)-carboxylaten ermöglicht hierbei die Herstellung von oxidfreien sphärischen Kupfernanopartikeln sowie von Kupferstäbchen unter einfachen experimentellen Bedingungen. Weitere Arbeiten widmen sich der Verwendung von ethylenglykolfunktionalisierten Silber(I)-carboxylaten zur Synthese von Silbernanopartikeln. Der entwickelte Prozess erlaubt die Herstellung blättchenförmiger Silbernanopartikel bei vergleichsweise niedrigen Temperaturen. Auch die Herstellung von blättchenförmigen Kupfersulfidpartikeln durch Thermolyse eines ethylenglykolfunktionalisierten Bis(triphenylphosphan)kupfer(I)-thiocarboxylates wird beschrieben. Schließlich wird gezeigt, wie thermolytisch hergestellte Goldnanopartikel an ethylenglykolfunktionalisierten Kohlenstoffnanoröhren abgeschieden werden können. Der Prozess wurde auf einem Wafer durchgeführt. Die erhaltenen Strukturen ermöglichen eine Verwendung als optischer Sensor.