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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

New routes for the activation of hydrocarbons by transition metal complexes

McLean, T. D. January 1984 (has links)
No description available.
2

Meeting the challenges: carbon-hydrogen bond activation and cancer treatment

Wang, Hongwang January 1900 (has links)
Doctor of Philosophy / Department of Chemistry / Stefan Bossmann / My thesis is divided into two parts. The first part is focused on studies of N-heterocyclic carbene (NHC) palladium(IV) intermediates, which are involved in oxidative addition mediated C-C, and C-O bond formation processes as well as in C-Cl bond forming reactions via a reductive elimination process. Bis-NHC-Pd(II) complexes have been reported as effective catalysts to mediate direct conversion of methane into methanol. However, a H-D exchange study revealed that the bis-NHC-Pd(II) complexes are not the active species responsible for the C-H bond activation reaction. This unexpected result implies that the high oxidation state bis- NHC-Pd(IV) species may be the real catalyst! The oxidative addition of methyl iodide to the bis- NHC-Pd(II)-Me2 complex led to the successful observation of the formation of a transient trimethyl bis-NHC-Pd(IV) intermediate by both 1H-NMR and 13C-NMR spectroscopy. Different oxidants such as O2, PhI(OAc)2, PhI(OTFA)2 and Cl2 reacted with the bis-NHC-Pd(II)-Me2 complex, and competitive C-C and C-O bond formations, as well as C-C and C-Cl bond formations were observed. Dioxygen triggered C-C bond formation under dry condition and both C-C and C-O bond formation in the presence of H2O gave strong indications that the bis-NHCPd( II)-Me2 complex can be oxidized to a bis-NHC-Pd(IV) intermediate by dioxygen. The reaction between the hypervalent iodine regents PhI(OAc)2 and PhI(OTFA)2 and the bis-NHCPd( II)-Me2 complex gave only reductive elimination products. Therefore, this system can act as a model system, which is able to providing valuable information of the product forming (functionalization) step of the C-H bond activation system. The reaction between chlorine and the bis-NHC-Pd(II)-Me2 complex resulted in a relatively stable bis-NHC-Pd(IV)-Cl4 complex, which was characterized by 1H-NMR spectroscopy and mass spectroscopy. The structure of bis- NHC-Pd(IV)-Cl4 was unambiguously established by X-ray crystallography. The second part of this thesis describes the synthesis of functionalized bimagnetic core/shell iron/iron oxide nanoparticles for the treatment of cancer. Biocompatible dopamineoligoethylene glycol functionalized bimagnetic core/shell Fe/Fe3O4 nanoparticles were prepared via ligand exchange, and purified by repeated dispersion/magneto-precipitation cycles. A porphyrin (TCPP) has been tethered to the stealth nanoparticles to enhance their uptake by tumor cells and (neural) stem cells. The stealth nanoparticles have been delivered in a mouse model to tumor sites intravenously by using the EPR (enhanced permeation and retention) effect. Magnetic hyperthermia proved to be very effective against B16-F10 mouse melanomas in Charles River black mice. After hyperthermia, the nanoparticles have shown a significant effect on the growth of tumor (up to 78% growth inhibition).

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