Chlorido(η 4-cyclo­octa-1,5-diene)(N,N′-diethyl­thio­urea-κS)rhodium(I)

In the title rhodium(I) complex, [RhCl(C8H12)(C5H12N2S)], N,N′-diethyl­thio­urea acts as a monodenate S-donor ligand. The rhodium(I) coordination sphere is completed by the Cl atom and the COD [= 1,5-cyclo­octa­diene] ligand inter­acting through the π-electrons of the double bonds. If the midpoints of these two bonds are taken into account, the Rh atom exhibits a distorted square-planar coordination. The syn conformation of the N,N′-diethyl­thio­urea ligand with respect to the Cl atom is stabilized by an intra­molecular N—H⋯Cl hydrogen bond. A weak inter­molecular N—H⋯Cl inter­action links mol­ecules along the a axis

Development of Particle Image Velocimetry for In-Vitro Studies of Arterial Haemodynamics

Atherosclerosis and related cardiovascular diseases (CVDs) are amongst the largest causes of morbidity and mortality in the developed world, causing considerable monetary pressure on public health systems worldwide. Atherosclerosis is characterised by the build up of vascular plaque in medium and large arteries and is a direct precursor to acute vascular syndromes such a myocardial infarction, stroke or peripheral arterial diseases. The causative factors leading to CVD still remain relatively poorly understood, but are becoming increasingly identifiable as a dysfunction of the endothelial cells that line the arterial wall. It is well known that the endothelium responds to the prevailing fluid mechanic (i.e. haemodynamic) environment, which plays a crucial role in the localised occurrence of atherosclerosis near vessel bends and bifurcations. In these areas, disturbed haemodynamics lead to flow separation and very low wall shear stress (WSS), which directly affects the functionality of the endothelium and impedes the transport of important blood borne agonists and antagonists. Detailed full field measurements assessing complex haemodynamics are sparse and consequently this thesis aims to address some of the important questions related to arterial haemodynamics and CVD by performing in-vitro flow measurements in physiologically relevant conditions. In particular, this research develops and uses state-of-the-art Particle Image Velocimetry (PIV) techniques to measure three-dimensional velocity and WSS fields in scaled models of the human carotid artery. For this purpose, the necessary theoretical and experimental concepts are developed and in-depth analyses of the underlying factors affecting the local haemodynamics and their relation to CVD are carried out. In the first part, a methodology for the construct of transparent hydraulic flow phantoms from medical imaging data is developed. The arterial geometries are reproduced in optically clear silicone and the flowing blood is modelled with a refractive index matched blood analogue. Subsequently, planar and Stereo-PIV techniques are developed and verified. A novel interfacial PIV (iPIV) technique is introduced to directly measure WSS by inferring the velocity gradient from the recorded particle images. The new technique offers a maximal achievable resolution of 1 pixel and therefore removes the resolution limit near the wall usually associated with PIV. Furthermore, the iPIV performance is assessed on a number of numerical and experimental test cases and iPIV offers a significantly improved measurement accuracy compared to more traditional techniques. Subsequently, the developed methodologies are applied in three studies to characterise the velocity and WSS fields in the human carotid artery under a number of physiological and experimental conditions. The first study focuses on idealised vessel geometries with and without disease and establishes a general understanding of the haemodynamic environment. Secondly, a physiological accurate vessel geometry under pulsatile flow conditions is investigated to provide a more realistic representation of the true in-vivo flow conditions. The prevailing flow structure in both cases is characterised by flow separation, strong secondary flows and large spatial and temporal variations in WSS. Large spatial and temporal differences exist between the different geometries and flow conditions; spatial variations appear to be more significant than transient events. Thirdly, the three-dimensional flow structure in the physiological carotid artery model is investigated by means of stereoscopic and tomographic PIV, permitting for the first time the measurement of the full 3D-3C velocity field and shear stress tensor in such geometries. The flow field within the model is complex and three-dimensional and inherently determined by the vessel geometry and the build up of an adverse pressure gradient. The main features include strong heliocoidal flow motions and large spatial variations in WSS. Lastly, the physiological implications of the current results are discussed in detail and reference to previous work is given. In summary, the present research develops a novel and versatile PIV methodology for haemodynamic in vitro studies and the functionality and accuracy is demonstrated through a number of physiological relevant flow measurements

Synthesis, coordination properties and application of new N,N-ligands based on bornyl and binaphthylazepine chiral backbones in palladium-catalyzed allylic substitution reactions

The synthesis of new imine-amine and diamine ligands, based on both the atropisomeric (Sa)- or (Ra)-1,1′-binaphthyl and (R)-bornyl backbones, and incorporating an ethylenediamino spacer, are reported. In addition, analogue ligands in which one chiral arm is replaced by the achiral NMe2 group were synthesized. These N,N-ligands when coordinated to a palladium metal centre form highly enantioselective catalysts for the asymmetric allylic alkylation of rac-2-acetoxy-1,3-diphenylpropene by dimethyl malonate. In one case, the synergic effect of the chirality elements in the palladium catalyst afforded the (S) substitution product with an enantiomeric excess (ee) of >99 %. Based on NMR studies of the active species in solution, a reliable explanation for the origin of the enantioselectivity of these palladium catalysts is also provided. New dinitrogen chiral ligands were synthesized and investigated in palladium-catalyzed allylic alkylation reactions. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.This work was supported by Ministero dell'Istruzione, dell'Università e della Ricerca (MIUR), PRIN 2007HMTJWP_005Peer Reviewe