This thesis reported synthesis of TiO2 nanostructures and Fe2O3 nanostructures and studied on self-assembling process. The morphologies, compositions, and physicochemical properties of the prepared samples were characterized by TEM, FESEM, XRD, FTIR, UV, and SQUID etc. Nanoparticles of transition metal oxides own their special function to become an interesting hot research topic in the recent decades. In particular, superparamagnetic iron oxide nanoparticles can be used as drug delivery agent and new hard disc drive materials. They have wide application in environment industry as well. Titanium dioxide nanoparticles can be applied in photocatalysts, UV protectors and dye sensitive solar cell etc. Their wide industrial applications for advanced technology development motivate scientists to develop simple, economical and novel synthetic methods, and explore their applications, so that the commercialization of the production of the nanomaterials becomes feasible. The objective of this project is to develop an effective, simple and economical technical route for synthesis of nanosized iron oxide and titanium oxide particles/rods/films. The approach and the progress are outlined as follows. Based on extensive literature reading on the project related area, a novel self-assembling technical route for iron oxide nanostructure and architecture was proposed which has been confirmed to be effective. Detailed experimental investigation on the synthesis of nanoparticles/rods, and instrumental characterization of the particle size, structure, and crystallites, etc. via TEM, FESEM, XRD, FTIR, UV, SQUID are conducted. Uniform nanorods of hematite iron oxide and titanium oxide nanospheres, and anatase TiO2 thin film with micropores have been successfully achieved. Some preliminary exploration for applications of the synthesized nanomaterials has also been carried out. Firstly, a novel assembled scheme of iron oxide nanostructure and architecture by selfassembling process was investigated. The sol-gel technical route was employed to synthesize nearly uniform nanorods of hematite particles. Morphologies and physicochemical properties of iron oxide nanostructure were characterized by analytical instrument. Secondly, titanium oxide nanospheres were synthesized via a hydrothermal process using titanium isopropoxide as the precursor. Titanium oxide nanospheres with inner nanospace andhighly organized crystallites in the shell structure and surface regions were synthesized. It demonstrated that the technical route developed in this work has a high versatility for structural engineering of various targeted morphological products. Thirdly, a simple process of preparing anatase TiO2 thin film with micropores was pursued. The synthesized nano thin film with micropores was used for the material of dye-sensitive solar cell; and effective electron transfer of titanium oxide electrode was confirmed by electrochemical voltammetry. Preparation of the titanium oxide electrode and its electrochemical analysis was studied. The application of the titanium oxide of microporous thin film material as a promoter for electrochemistry voltammetry measuring system was explored in this thesis. In conclusion, the iron oxide nanorods with superparamagnetic property were successfully synthesized by a simple method with low cost materials. Titanium oxide hollow nanospheres were achieved by the assistance of copolymer template. Titanium oxide thin film with microporous structure with significantly high efficiency in electron transfer was realized. Further researches on the synthesis of hybrid iron oxide and titanium oxide nanoparticles, their crystal growth architecture and mechanism, as well as exploration of their applications are recommended.

Stem cell therapies hold great promise for diseases such as stroke, where few effective treatment options exist. Clinical translation of experimental stem cell therapies requires the ability to monitor delivery and behaviour of cells non-invasively in-vivo with clinical imaging modalities such as MRI. This thesis presents the translation of established methods for labelling and imaging stem cells with specialized MRI systems to a more clinically relevant setting. A methodology for harvesting and labelling a cell population containing stem cells with iron oxide for detection with a clinical MRI system is presented and single cell detection is demonstrated in-vitro. The feasibility of detecting iron oxide labelled stem cells intravenously delivered in a rat model of stroke is tested. Results demonstrate that while MRI is highly sensitive to the presence and distribution of iron oxide containing cells in-vivo the true origin of these cells remains ambiguous with the current methodology.

Stem cell therapies hold great promise for diseases such as stroke, where few effective treatment options exist. Clinical translation of experimental stem cell therapies requires the ability to monitor delivery and behaviour of cells non-invasively in-vivo with clinical imaging modalities such as MRI. This thesis presents the translation of established methods for labelling and imaging stem cells with specialized MRI systems to a more clinically relevant setting. A methodology for harvesting and labelling a cell population containing stem cells with iron oxide for detection with a clinical MRI system is presented and single cell detection is demonstrated in-vitro. The feasibility of detecting iron oxide labelled stem cells intravenously delivered in a rat model of stroke is tested. Results demonstrate that while MRI is highly sensitive to the presence and distribution of iron oxide containing cells in-vivo the true origin of these cells remains ambiguous with the current methodology.

In this dissertation, research efforts mainly focused on exploring the applications of superparamagnetic iron oxide nanoparticles (SPIONs) in MR imaging and nanocatalysis via surface functionalization. A dopamine-based surface-functionalization strategy was established. The Simanek dendrons (G1 to G3), oligonucleotides and amino acids were loaded onto SPION surfaces via this approach to develop pH-sensitive MRI contrast agents, specific-DNA MR probes and a biomimetic hydrolysis catalyst. Dendron-SPION conjugates (G1 to G3) have good aqueous solubilities and high transverse relaxivities (>300 s-1*mM-1). They also showed interesting strong pH-sensitive R2 and R2* relaxivities, which were governed by the clustering states of dendron-SPIONs in different pH environments. Values of R2m and R2* m/R2m varied by over an order of magnitude around pH 5. The efficient cell-uptake (~3 million/cell) and low cytotoxicity of G1 to G3-SPIONs were demonstrated on HeLa cell cultures. The strong R2* effects were observed indicating the SPION clustering in HeLa cells. Two SPION-oligonuleotide conjugates were synthesized by coupling two half-match oligonucleotides onto domapine-capped SPIONs via SPDP linkers. They served as MR probes to detect a single-strand DNA with the same sequence to miRNA-21 based on the change of R2 values due to the DNA-bridged SPION clustering. The detection limit of the DNA could reach to 16.5 nM. A biomimetic hydrolysis nanocatalyst (i.e., Fe2O3-Asp-His complex) was developed by loading Asp and His-dopamine derivatives onto SPIONs. Paraoxon and nitrophenyl acetate were hydrolyzed under a mild condition (neutral pH, 37 °C) catalyzed by the Fe2O3-Asp-His complex. The two amino acids Asp and His cooperated with each other on the SPION surfaces to catalyze hydrolysis reactions. This catalyst could be recycled by a magnet and reused for four times without a significant loss of catalytic activity.

Dissertação (mestrado)—Universidade de Brasília, Instituto de Geociências, Programa de Pós-Graduação em Geologia, 2018. / Submitted by Raquel Almeida (raquel.df13@gmail.com) on 2018-05-15T16:26:56Z No. of bitstreams: 1 2018_VictorBotelhoPerezGarcia.pdf: 2313547 bytes, checksum: d593399c348afe0ec7985407648f4b34 (MD5) / Approved for entry into archive by Raquel Viana (raquelviana@bce.unb.br) on 2018-05-23T10:30:14Z (GMT) No. of bitstreams: 1 2018_VictorBotelhoPerezGarcia.pdf: 2313547 bytes, checksum: d593399c348afe0ec7985407648f4b34 (MD5) / Made available in DSpace on 2018-05-23T10:30:14Z (GMT). No. of bitstreams: 1 2018_VictorBotelhoPerezGarcia.pdf: 2313547 bytes, checksum: d593399c348afe0ec7985407648f4b34 (MD5) Previous issue date: 2018-05-23 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq). / O depósito GT-34, localizado a 12 km a SW da mina Sequerinho, Carajás, norte do Brasil, representa uma ocorrência incomum de Ni relacionado ao sistema Iron-OxideCopper-Gold (IOCG) regional. Ocorre ao longo de uma zona de cisalhamento subvertical de orientação NE-SW marcado por zonas de alteração alcáli-Fe encaixado em granitos a tonalitos. A aleração inicial Na-Mg e alteração Ca pervasiva formam, respectivamente, marialiate-ortopiroxênio e hornblenda-plagioclásio-clinopiroxênio. A mineralização de Ni ocorre na forma de brechas com a matriz rica em pentlandita-pirrotita-apatita e fragmentos arredondados compostos dominantemente por fragmentos da alteração Ca. Veios tardios de alteração K-Fe com magnetita ou hematita (alteração K-Fe (Mt) e alteração K-Fe (Hem), respectivamente) remobilizam parcialmente a mineralização, reprecipitando-a como calcopirita-pirrotita-magnetita (alteração K-Fe (Mt)) e como milerita-pirita-apatita (alteração K-Fe (Hem)). A alteração K-Fe (Mt) ocorre como veios irregulares ricos em flogopita-talco, enquanto a alteração K-Fe (Hem) ocorre como veios bem delimitados com K-feldspato-albita-quartzo-clorita-calcita-epidoto. As características iniciais do fluido associado a alteração Na-Mg precisam ser anidras para a estabilização do ortopiroxênio e de elevada salinidade para formação da marialita. Um fluido imiscível composto por CO2-NaCl é sugerido para a atingir tais características. A presença do ortopiroxênio indica temperaturas >700°C. Estudo experimentais indicam que marialiata não se forma a partir de fluidos ricos em NaCl a pressões >7 kbar a temperatura >700°C. A ausência de quartzo pode ocorrer devido a sua dissolução causada por fluidos ricos em NaCl sob pressões >5 kbar e temperaturas similares, também determinado experimentalmente. Cristais de zircão foram recuperados da alteração NaMg inicial e da alteração tardia K-Fe (Mt) fornecendo uma idade concordante de 2.724±4 Ga, corroborando a formação Neoarqueana do depósito GT-34, similar aos demais depósitos IOCG em Carajás. A temperatura >700°C e pressão entre 5–7 kbar, eventuais fluidos evaporíticos não podem estar presentes, sendo necessário uma fonte magmática. As idades obtidas nesse estudo se sobrepõe a idade do magmatismo bimodal Neoarqueano (2.75-2.70 Ga), suportando uma origem magmática-hidrotermal. As condições determinadas para o depósito GT-34 elevam a temperatura inicial do sistema IOCG de Carajás em pelo menos 200°C com pressões podendo chegar até 7 kbar, tornondo-o a mais profunda ocorrência associada ao sistema IOCG de Carajás conhecida até então. / The GT-34 deposit, which is located 12 km SW of the Sequerinho copper-gold mine, Carajás Province, northern Brazil, represents an unusual Ni occurrence related to a regional Iron-Oxide-Copper-Gold (IOCG) system. It occurs along a NE-SW-trending sub-vertical shear zone marked by progressive alkali-Fe alteration zones hosted in tonalite to granite intrusions. Initial Na-Mg and pervasive Ca alteration forms the unique marialite-orthopyroxene and hornblende-plagioclase-clinopyroxene associations, respectively. Nickel mineralization occurs as breccias in a pentlandite-pyrrhotite-apatiterich matrix with rounded fragments chiefly of Ca-alteration parageneses. Late-stage veins of K-Fe magnetite and hematite (K-Fe (Mt) and K-Fe (Hem)) alterations partially remobilize the mineralization, reprecipitating as chalcopyrite-pyrrhotite-magnetite and as millerite-pyrite-apatite, respectively. Potassium-Fe (Mt) occurs as irregular phlogopitetalc-rich veins, while K-Fe (Hem) occurs as sharp K-feldspar-albite-quartz-chloritecalcite-epidote veins. Initial fluid characteristics associated with Na-Mg alteration require anhydrous conditions for orthopyroxene stability and high salinity for marialite formation. An immiscible CO2-NaCl fluid is therefore associated with such conditions. The presence of orthopyroxene indicates temperatures >700°C. Experimental studies indicate that marialite does not form with NaCl-rich fluid at pressures >7 kbar under such temperatures. The absence of quartz might be caused by NaCl dissolution at pressures >5 kbar, as determined experimentally with the same temperature conditions. Zircon crystal were recovered from the initial Na-Mg alteration and late-stage K-Fe (Mt) alteration yielding a concordant 2.724±4 Ga age, corroborating the GT-34 Neoarchean formation similar to other IOCG deposits in Carajás. At >700°C and 5–7 kbar, an eventual evaporitic fluid source would not be present, making a magmatic fluid source necessary. The age constrains obtained in this study overlaps the bimodal Neoarchean magmatism (2.75-2.70 Ga), supporting a magmatic-hydrothermal origin. Determination of such conditions raises the initial temperature of the Carajás IOCG system at least 200°C and pressure up to 7 kbar, making GT-34 the deepest IOCG-related occurrence known to date for this province.

Title: Nanoparticles based on 3d metal oxides - correlation of structure and magnetism Author: RNDr. Simona Kubíčková Department: Institute of Physics CAS, v.v.i. Supervisor: doc. RNDr. Jana Kalbáčová Vejpravová, Ph.D., Institute of Physics CAS, v.v.i. Abstract: The thesis is focused on the correlation of the magnetic response of iron oxide nanoparticles (NPs) with their internal structure. Several complementary methods were used and compared that bring insight into the relative crystallinity of the investigated NPs. The main goal was devoted to the elucidation of the origin of the so-called spin canting angle determined by In-field Mössbauer Spectroscopy (IFMS) by examination of samples with different internal structure. It has been observed that the IFMS is not an unambiguous method to study the surface effects in the NPs as the IFMS is sensitive only to the average value of all spins and does not distinguish between the surface and core effects. Moreover, the IFMS was performed on the epsilon phase of the iron(III) oxide NPs in order to inspect the peculiar behavior of this phase in an external magnetic field. Keywords: iron oxide nanoparticles, magnetism, In-field Mössbauer Spectroscopy, spin canting

No description available.

Using the maximum bubble pressure method of density determination, the density-composition relationship of iron silicates in contact with solid iron at 1410°C has been determined. The "iron oxide" in an iron silicate has been replaced by calcium oxide, manganous oxide, cobaltous oxide, nickel oxide and calcium fluoride and the density-composition relationships occurring have been obtained. The calculated oxygen density-composition relationships have been interpreted in terms of the effects of silica concentration and cationic species on the anionic configuration occurring in the melts and this interpretation has been correlated with recently-developed thermodynamic models of silicate anion configuration in basic binary silicate systems. / Thesis / Doctor of Philosophy (PhD)

No description available.

Yes / In order to meet the environmental legislations related to sulfur content, it is important to find an alternative techniques for deep removal of sulfur components from fuels. So, in this study, a novel nano-catalyst based on iron oxide (Fe2O3) as active component prepared over composite support (γ-Alumina + HY-zeolite) is developed here for efficient removal of sulfur compounds from fuel via oxidation process. The precipitation method is employed first to prepare the composite support and then the impregnation method is utilized to generate a novel synthetic homemade (Fe2O3/ composite support) nanocatalysts that has not been developed in the literature (iron oxide over composite support). The characterizations of the prepared catalysts display that the surface area of the catalyst increases with increasing the amount of Y-zeolite in composite support. The effectiveness of the catalysts is tested by utilizing oxidative desulfurization (ODS) operation under several operating conditions. The results of the experimental work show that the activity of oxidative desulfurization enhances with increasing Y-zeolite, temperature, and batch time under moderate operating conditions. The oxidative desulfurization efficiency followed the order: CAT-1 < CAT-2 < CAT-3. The CAT-3 performed the high removal of sulfur compounds (90.73%) at 100 min and 423 K. The best values of the kinetic parameters of the ODS process are then determined based on experimental data and model based techniques within gPROMS package. Finally, the reactor model is used to determine the optimal operating conditions while maximizing the removal of sulfur compounds leading to cleaner fuel. Where, 99.3% of the sulfur removal has achieved at batch time of 190.6 min, temperature of 543.56 K and initial sulfur content at 0.8668 wt% in the presence of CAT-3 based on the optimal kinetic parameters (order of reaction (n) of 1.9865719, activation energy (EA) at 29.942 KJ/mol and pre-exponential factor (ko) with 622.926 wt-0.9865719. min-1).