An investigation into the antidiabetic and catalytic properties of oxovanadium(IV) complexes

Walmsley, Ryan Steven (2011) An investigation into the antidiabetic and catalytic properties of oxovanadium(IV) complexes. PhD thesis, Rhodes University.

[img]
Preview
Text
WALMSLEY-PhD-TR12-62.pdf

6Mb

Abstract

In part 1 of this thesis, the antidiabetic activity of a series of novel oxovanadium(IV) complexes was investigated. A range of bidentate N,O-donor ligands, which partially mimic naturally occurring bioligands, were prepared and reacted with the vanadyl ion to form the corresponding bis-coordinated complexes. Initially, 2-(2ˊ-hydroxyphenyl)-1R-imidazoline (where R = H, ethyl and ethanol) ligands were prepared. The aqueous pH-metric chemical speciation was investigated using glass electrode potentiometry which allowed for the determination of protonation and stability constants of the ligands and complexes, respectively. The species distribution diagrams generated from this information gave an indication of how the complexes might behave across the broad pH range experienced in the digestive and circulatory systems. This information was used to create an improved 2nd generation of ligands that were constructed by combining the imidazole and carboxylic acid functionalities. These corresponding bis[(imidazolyl)carboxylato]-oxovanadium(IV) complexes displayed a broader pH-metric stability. Both sets of complexes improved glucose uptake and reduced coagulation in vitro. In part 2 of this thesis, a range of homogeneous and heterogeneous oxovanadium(IV) catalysts were prepared. Firstly, Merrifield beads were functionalized with ligands from Part 1 and then reacted with vanadyl sulfate to afford the corresponding heterogeneous catalysts. These displayed promising catalytic activity for the peroxide facilitated oxidation of thioanisole, styrene and ethylbenzene as well as the oxidative bromination of phenol red. Smaller imidazolecontaining beads with higher surface areas than the Merrifield beads were prepared by suspension polymerization. These beads similarly demonstrated excellent catalytic activity for the oxidation of thioanisole and were highly recyclable. In attempt to increase the exposed catalytic surface area, while retaining the ease of separation achieved in the before mentioned systems, micron to nano sized electrospun fibers containing coordinating ligands were fabricated. The corresponding oxovanadium(IV) functionalized fibers were applied to the oxidation of thioanisole using a continuous flow system. The flexible and porous nature of the fiber mats was well suited to this approach. After optimization of the reactant flow rate and catalyst amount, near quantitative (> 99%) oxidation was achieved for an extended period. In addition, leaching of vanadium was mitigated by modification of the attached ligand or polymer material.

Item Type:Thesis (PhD)
Uncontrolled Keywords:Hypoglycemic agents, Ligands, Biochemistry, Complex compounds, Potentiometry, Proton transfer reactions, Stability, Imidazoles, Vanadium catalysts
Subjects:Q Science > QD Chemistry
Divisions:Faculty > Faculty of Science > Chemistry
Supervisors:Tshentu, Zenixole
ID Code:2950
Deposited By: Ms Chantel Clack
Deposited On:07 Jun 2012 06:20
Last Modified:18 Jul 2012 08:28
30 full-text download(s) since 07 Jun 2012 06:20
30 full-text download(s) in the past 12 months
More statistics...

Repository Staff Only: item control page