Thesis (M.Ch.E.)--University of Delaware, 2006. / Principal faculty advisor: Annette D.Shine, Dept. of Chemical Engineering. Includes bibliographical references.

This PhD Thesis involves the development of a new synthetic protocol for iron oxide silica composite nanoparticles useful in MRI and magnetic hyperthermia. Our approximation combines the sol-gel chemistry and supercritical fluids to obtain biocompatible, spherical composite particles, with narrow particle size distribution. The composite particles showed very high values of relaxivity. We have also studied the dependence of the specific absorption rate with iron concentration. This manuscript is organized into seven chapters. Chapter 1 provides a general introduction to magnetic nanoparticles, their properties, synthesis, stabilization and applications, with special interest in the biomedical field. The aim of the chapter is to place the reader in the scientific context of the thesis. Chapter 2 describes the synthesis of nanoparticles by thermal decomposition of an iron complex, Fe(CO)5, and their characterization in solid and colloidal dispersion. Silica coating is a convenient approach to stabilize nanoparticles in a biocompatible way. In this thesis we have developed a new synthetic protocol to coat iron oxide nanoparticles with silica that combines the sol-gel chemistry and supercritical fluids. To understand and control the details of this procedure, we first synthesized nano- and microparticles of silica. They are described in Chapter 3. Chapter 4 includes the synthesis of the composite γ-Fe2O3@SiO2 nanoparticles. The core is composed of clustered iron oxide nanoparticles (described in Chapter 2) surrounded by a silica shell. Chapter 4 also describes the material characterization, with special emphasis on the magnetic properties, which will be exploited in the biomedical applications. We also succeeded in synthesizing composite ε-Fe2O3@SiO2 nanospheres from the previous γ-Fe2O3@SiO2 particles. The evaluation of the materials described in Chapters 2 and 4 as contrast agents for magnetic resonance imaging and as mediators for magnetic hyperthermia is included in Chapter 5. Chapter 6 lists the main conclusions derived from the present thesis. Finally, Chapter 7 gathers the annexes. It includes four publications arising from the main subject of this thesis, as well as five other publications and a patent on projects that I worked during the time that has lasted my doctoral thesis. The annexes also include a brief description of the experimental techniques used and protocols for sample preparation.

Four in vitro models were used to measure the antioxidant activity of 11 citrus phytochemicals. The citrus limonoids and bergapten showed very weak antioxidant activity. The flavonoids demonstrated mild, to moderate, to strong antioxidant activity. In addition to some other commonly accepted structural features our data indicated that the hydroxyl group in position 6 of ring A could also increase the antioxidant activity of flavonoids. Compared with the active flavonoids, limonoids are highly oxygenated triterpenoids, with fewer hydroxyl groups to stabilize unpaired electrons (or scavenge free radicals). Bergapten lacks a hydroxyl group. This is the first report on the antioxidant activity of limonoids and neoeriocitrin. A feeding study using Syrian hamsters was followed to determine the effect of citrus limonoids and flavonoids on plasma cholesterol. Hamsters fed with limonin, limonin 17-Beta-D-glucopyranoside and grapefruit pulp significantly inhibited the increase of LDL/HDL-cholesterol (36.6%, 52.9% and 57% respectively) compared with the basal control (65.8%) and the pectin control (70%). Furthermore, hamsters fed with limonin had significantly larger LDL particle size (21.21 nm) compared with the control group (19.96 nm). Further studies demonstrated that LDLs from hamsters fed with limonin and limonin 17-Beta-D-glucopyranoside were less susceptible to oxidation. These data suggest that limonin, limonin 17-Beta-D-glucopyranoside and grapefruit pulp have potential inhibitory effects against atherogenesis. Supercritical CO2 (SC-CO2) was attempted to extract limonoids from grapefruit seeds and molasses. Limonin aglycone was successfully extracted with SC-CO2 directly from grapefruit seeds with the yield of 6.3 mg/g seeds at 48.3 MPa, 50˚C and 60 min with CO2 top feeding; and the limonin glucoside was extracted using SC-CO2 and ethanol as co-solvent from the defatted seeds with the yield of 0.73 mg/g seeds at 42 MPa, 52˚C, 45% ethanol (XEth=0.45) and 40 min with CO2 top feeding; and limonin glucoside also was extracted using SC-CO2 and ethanol with the yield of 0.61mg/g grapefruit molasses at 48.3 MPa, 50˚C and 10% ethanol (XEth=0.1), 40 min with CO2 top feeding. CO2 flow rate was around~5 l/min in experiments. The results demonstrated SC-CO2 extraction of limonoids from citrus juice industry byproducts has practical significance for future commercial production.

Thesis (Ph. D.)--University of Missouri-Columbia, 2001. / Typescript. Vita. Includes bibliographical references (leaves 136-143). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 2001. / Typescript. Vita. Includes bibliographical references (leaves 136-143). Also available on the Internet.

Thesis (Ph. D.)--Hong Kong University of Science and Technology, 2002. / Includes bibliographical references (leaves 145-150). Also available in electronic version. Access restricted to campus users.

Not available / text

This thesis presents investigations into the design and synthesis of nanomaterials in supercritical carbon dioxide (sc-CO₂) as well as novel experimental design methodologies. First, the process-structure-property relationships are studied for the deposition of materials from organometallic precursors in sc-CO₂. The materials that were investigated in these studies were: (1) the semiconductor material copper zinc tin sulfide (Cu₂ZnSnS₄, or CZTS), which has application in solar energy capture; (2) zinc sulfide nanoparticles deposited onto carbon nanotubes, which have application in optoelectronics; and (3) silver nanoparticles deposited on silicon and glass wafer surfaces, which find application as biosensors via surface enhanced Raman spectroscopy. Next, two novel experimental design methodologies were implemented. The first is termed layers of experiment with adaptive combined design (LoE/ACD), which efficiently optimizes a process that is expensive and time consuming to study by zooming in on the process optimum through successive layers. The mean silver nanoparticle size was optimized as a function of temperature in the sc-CO₂ system using the LoE/ACD approach. The second experimental design methodology is called initial experimental design (IED). The IED methodology was developed to choose the first round of experiments for a system that is expensive to study (in terms of time and money), poorly understood, and possesses a related, non-identical system that is well-studied. The IED approach was used to optimize the mean iridium nanoparticle size as a function of temperature given expert opinion, prior data, and an engineering model for silver nanoparticles synthesized in sc-CO₂.

Dissertation (Ph.D.)--Auburn University, 2004. / Abstract. Includes bibliographic references (269-292).

Thesis (M. S.)--Aerospace Engineering, Georgia Institute of Technology, 2007. / Ruffin, Stephen, Committee Member ; Seitzman, Jerry, Committee Member ; Menon, Suresh, Committee Chair.