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Syntheses and surface modifications of gold and iron oxide nanoparticles for organic and biomedical applications

Posted on:2007-02-10Degree:Ph.DType:Thesis
University:Southern Illinois University at CarbondaleCandidate:Fan, JindaFull Text:PDF
GTID:2451390005980176Subject:Chemistry
Abstract/Summary:
Gold nanoparticles (AuNPs) and gamma-Fe2O 3 were synthesized, modified and studied. The gold nanoparticles were examined with the intention of functionalization of AuNPs with biomolecules. By translating solid phase peptide synthesis concepts to nanoparticle supports, the employment of peptide synthesis on the surface of gold nanoparticles was explored. A pentapeptide was synthesized and an average coupling yield of 95% was achieved. The AuNPs were characterized by transmission electron microscopy (TEM), thermo-gravimetric analysis (TGA) and 1H NMR. The peptide synthesized was examined using 1H NMR, 19F NMR, HPLC and mass spectrometry (MS).; Uniform-sized highly crystalline gamma-Fe2O3 nanoparticles, stabilized with various organic ligands, were synthesized. The nanoparticles were examined by X-ray powder diffraction (XRD), superconducting quantum interference device magnetometry (SQUID), TEM, 1H NMR, thin layer chromatography (TLC), and MS. In addition, water dispersible gamma-Fe 2O3 nanoparticles were prepared and functionalized with biotin. The as-formed nanoparticles were able to isolate avidin-FITC from its incubation buffer magnetically with 96% efficiency.; gamma-Fe2O3/polymer core/shell structured magnetic nanoparticles were fabricated via either an atomic transfer radical polymerization (ATRP) method or a micro-emulsion polymerization approach. The cross-linked polymeric prevented the undesired site exchange reactions, leading to the improvement of the stability of the iron oxide nanoparticles.; N-Heterocyclic carbene (NHC) moieties were immobilized onto the core/shell nanocomposites via a coupling of imidazole with benzyl chloride on the polymeric shell. Subsequently, Pd-NHC complexes were formed on the magnetic nanoparticles. These nanoparticle-supported Pd catalysts are stable and demonstrate high catalytic activity in promoting Suzuki, Heck and Sonogashira cross-coupling reactions. More importantly, recovery of catalysts was easily achieved by using a permanent magnet. Isolated catalysts were used for subsequent new rounds of reactions without significant loss of their catalytic activity. The comparative kinetic studies have shown that the nanoparticle-supported catalysis proceeded much faster than its counterpart on solid phases.; Chiral BINOL derivatives with various spacer lengths were synthesized through multi-steps. The BINOL moieties were immobilized to gamma-Fe 2O3 nanoparticles and Ti-BINOLate complexes were formed in situ and used as magnetically recyclable chiral catalysts for asymmetric alkylation of benzaldehyde with diethyl zinc. The product was obtained in modest yields and enantioselectivity.
Keywords/Search Tags:Nanoparticles, Gold, 1H nmr, Synthesized, Catalysts
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