Year of Award
Master of Philosophy (MPhil)
Department of Chemistry.
Leung, Ken C. F.
Drug delivery systems ; Heterogeneous catalysis ; Magnetite
This thesis describes the preparation and characterization of core-shell noble metal-magnetite hybrid hollow nanocomposites utilizing hierarchical architecture. The hollow magnetite (hFe3O4) nanoparticles were prepared by hydrothermal method, forming the cavity via Oswald ripening. Further surface modifications involved both inorganic and organic coatings, conferring the intracellular drug delivery ability and the catalytic enhancement. In the first part, a series of hierarchical core-shell nanostructures flower-like hFe3O4@AlOOH was synthesized through solvothermal method and sol-gel process. The formation of cavity accessible hFe3O4@γ-AlOOH was achieved using silica-templated solvothermal treatment where the Kirkendall effect was observed. The morphologies of the as-prepared nanocomposites were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), dynamic light scattering (DLS), thermogravimetric analysis (TGA) and Fourier-transform infrared spectroscopy (FTIR). Then, the nano-encapsulation of platinum drug using hollow magnetite and its derivatives, has been developed with improved loading efficiency via co-solvent system. A dimethylformamide/water co-solvent system was found to be the most efficient system to encapsulate water-insoluble cisplatin. The platinum content was further quantitatively and qualitatively analyzed by inductively coupled plasma mass spectrometry (ICP-MS) and FTIR spectroscopy. The enhancement of loading efficiency could be driven by emulsification due to the diffusion of hydrophobic cisplatin into the hollow cavity of iron oxide nanoparticles. By incorporating water, the loading efficiency of hFe3O4 and hFe3O4@γ-AlOOH increased from 1-2% to 27% and from 6% to 54%, respectively. The grafting of cisplatin on AlOOH nanoflakes might account for the high loading efficiency of flower-like hFe3O4@AlOOH. As a complement to naked hFe3O4, a cell-penetrating poly(disulfide)s (CPD)-decorated hollow iron oxide nanoparticle was synthesized by immobilizing both cysteine and MPTMS as an initiator, followed by in situ polymerization to form hFe3O4-Cys-CPD-CONH2 and hFe3O4-MPS-CPD-CONH2. The morphologies were characterized by TEM/energy-dispersive X-ray spectroscopy (TEM/EDX) and the compositions of the as-prepared iron oxide nanocomposites were characterized by TGA, FTIR and X-ray photoelectron spectroscopy (XPS) and ICP-MS. The CPD coating not only serve as a protective layer, but also prevent the encapsulated cisplatin from a premature release. The hFe3O4-MPS-CPD-CONH2 exhibit promising features for the intracellular delivery of cisplatin, demonstrating a glutathione (GSH)-responsive drug release. Comparing with other hFe3O4 nanoparticles, an enhancement of cellular uptake of hFe3O4-MPS-CPD-CONH2 could be observed by optical microscope, showing rapid accumulation of the hFe3O4-MPS-CPD-CONH2 nanocomposites in the primary human renal proximal tubular epithelial cells (HRPTEpiCs) cell in 2 h. At 24 h, hFe3O4 (F), hFe3O4-MPS (FS) and hFe3O4-MPS-CPD-CONH2 (FSC) together with cisplatin treatment did not cause any significant cytotoxicity to the cells when the particle concentration is less than 10 µg/mL. Interestingly, FSCC showed a certain extent of toxicity with increasing Fe and Pt concentration along with the treated time. It may suggest that the hFe3O4-MPS-CPD-CONH2 nanoparticle, as a cisplatin carrier, could enhance the drug efficiency by increasing cellular uptake of the nanoparticles in HRPTEpiCs together with the boosted cytotoxicity. Based on these data, cisplatin- hFe3O4-MPS-CPD-CONH2 (FSCC) treatments with the concentration less than 20 µg/mL and duration no more than 24 h could maintain around 70% of the cell viability of the HRPTEpiCs. The hypothesis, at which CPD serves as an efficient carrier for intracellular cisplatin delivery, could be confirmed by both microscopic images and the cell viability test. In the second part, a series of Au/Fe3O4 hybrid nanocomposites was prepared to investigate their catalytic efficiencies using 4-nitrophenol reduction as a model system. The flower-like hFe3O4@γ-AlOOH@SiO2-NH2@Au was prepared by using protonated ammonium on hFe3O4@γ-AlOOH@SiO2-NH2 to entangle gold nanoparticles (AuNPs) via electrostatic attraction. In comparison to numerous of catalytic studies, the turnover frequency (TOF) of hFe3O4@γ-AlOOH@SiO2-NH2@Au shows a superior conversion rate up to 7.57 min-1 (4-nitrophenol per Au per min) for the 4-nitrophenol using sodium borohydride as a reductant. A rapid conversion of 4-nitrohpenol was observed using flower like composites that converted the 4-nitrophenol within 2 min. Our result suggests that silica residue hinders the reduction rate of the 4-nitrophenol. A significant deviation from pseudo first order was observed for densely AuNPs-functionalized nanoflower system, hFe3O4@γ-AlOOH@SiO2-NH2@Au2X, which is different from most of the 4-nitrophenol reductions reported in literature. The hFe3O4@γ-AlOOH@SiO2-NH2@Au also demonstrates catalytic activity when heated up to 800 °C before reduction. The recyclability was examined using magnetically recycled hFe3O4@γ-AlOOH@SiO2-NH2@Au, which showed insignificant decrease in the catalytic efficiency. To prove the concept, platinum nanoparticles (PtNPs) immobilized hFe3O4@γ-AlOOH@SiO2-NH2@Pt and hFe3O4@γ-AlOOH@SiO2-NH2@Pt/Au were also prepared via electrostatic attraction to verify the feasibility of endowing modular functionality via post modification.
Includes bibliographical references (pages 86-97).
Li, Wai Chung, "Preparation and characterization of noble metal-magnetite hybrid nano/micro composites towards drug delivery and heterogeneous catalysis" (2019). Open Access Theses and Dissertations. 668.
Available for download on Sunday, October 17, 2021