Thesis (Ph. D.)--University of Wisconsin--Madison, 1970. / 2 folded maps in pocket. Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

The electrical and magnetic properties of magnetite from 100-300°K have been studied. Specimens were obtained from natural crystals of local origin and fabricated in the form of rectangular bars. When this was not possible, due to excessive cracks in the crystal, the electrical properties of the resulting irregularly shaped disc were measured by use of the Van der Pauw theorem. Observation of the temperature variation of the resistivity showed that the resistivity increased as the temperature was decreased and that it increased by a factor 24 over a 10°K temperature interval when the specimen was cooled below 115°K. This phenomenon is related to an order-disorder transition at this temperature, in which the crystalline symmetry changes from cubic to orthorhombic. One specimen did not show the resistivity transition, probably due to excessive impurity content, which would prevent ordering from occurring. The results are explained qualitatively by the Verwey model, which postulates a conduction mechanism involving the jumping of electrons between octahedral sites of the Fe₃O₄ unit cell, as opposed to the conventional band type of conduction. An attempt was made to measure the Hall mobility of the specimens, but a Hall voltage was not detected within the sensitivity of the apparatus. An upper limit of 1 cm²/volt-sec. for the mobility was established. A negative magnetoresistance effect was observed in both specimens and was measured as a function of temperature for both transverse and longitudinal magnetic fields. A pronounced minimum at the transition temperature was observed for one specimen, while the other showed no change here. The AC permeability was observed over the transition region and again a sharp decrease was observed on cooling through the transition. Normal induction curves were obtained for the specimen at various fixed temperatures from the permeability data, from which it was deduced that the specimen was much harder to saturate below the transition. The permeability on warming was found to be independent of the magnetic state of the sample while cooling through the transition, and it was again observed that one crystal did not undergo the phase transition at 115°K. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

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.

No description available.

Synthetic nanomagnetite has been suggested as a potential reactant for the in-situ treatment of contaminated groundwater. Although the application of nanomagnetite for environmental remediation is promising, a full understanding of its reactivity has been deterred by the propensity of the nanoparticles to aggregate and form clusters. To characterize the factors responsible for this aggregation behavior, we determined the magnetic properties of magnetite using a superconducting quantum interference device (SQuID). Importantly, because magnetite readily reacts with O2 to produce maghemite, we analyzed the effect of oxidation on its magnetic properties. We observed that oxidation caused a decrease in the saturation magnetization and the anisotrophic barrier of magnetite resulting in less significant magnetic interactions between particles. Consequently, a decrease in the aggregation of magnetite clusters and a potential increase in stability are expected after oxidation. To support these findings, an extended series of experiments to measure the aggregation and the sedimentation of clusters of unoxidized and oxidized magnetite nanoparticles were conducted. Although the individual particle diameter remained constant after oxidation, the cluster size and the aggregation and sedimentation kinetics of magnetite were determined to be different. Oxidized samples of magnetite tended to have lower aggregation rates and were more resistant to sedimentation. These findings can be used to have a better understanding of the overall fate, transport, and reactivity of nanomagnetite, and to gain new insights on its role as a remediation agent in the subsurface environment. / Ph. D.

Polylactide-siloxane triblock copolymers with pendent carboxylic acid functional groups have been designed and synthesized for study as magnetite nanoparticle dispersion stabilizers. Magnetic nanoparticles are of interest in a variety of biomedical applications, including magnetic field-directed drug delivery and magnetic cell separations. Small magnetite nanoparticles are desirable due to their established biocompatibility and superparamagnetic (lack of magnetic hysteresis) behavior. For in-vivo applications it is important that the magnetic material be coated with biocompatible organic materials to afford dispersion characteristics or to further modify the surfaces of the complexes with biospecific moieties. The synthesis of the triblock copolymers is comprised of three reactions. Difunctional, controlled molecular weight polymethylvinylsiloxane oligomers with either aminopropyl or hydroxybutyl endgroups were prepared in ring-opening redistribution reactions. These oligomers were utilized as macroinitiators for ring-opening L-lactide to provide triblock materials with polymethylvinylsiloxane central blocks and poly(L-lactide) endblocks. The molecular weights of the poly(L-lactide) endblocks were controlled by the mass of L-lactide relative to the moles of macroinitiator. The vinyl groups on the polysiloxane center block were further functionalized with carboxylic acid groups by adding mercaptoacetic acid across the pendent double bonds in an ene-thiol free radical reaction. The carboxylic acid functional siloxane central block was designed to bind to the surfaces of magnetite nanoparticles, while the poly(L-lactide)s served as tailblocks to provide dispersion stabilization in solvents for the poly(L-lactide). The copolymers were complexed with magnetite nanoparticles by electrostatic adsorption of the carboxylates onto the iron oxide surfaces and these complexes were dispersible in dichloromethane. The poly(L-lactide) tailblocks extended into the dichloromethane and provided steric repulsion between the magnetite-polymer complexes. / Master of Science

Neste trabalho são investigados o designer e a fabricação nanomateriais magnéticos e luminescentes sofisticados bifuncionais baseados em Fe3O4 e complexos de RE3+. Portanto, novos nanomateriais Fe3O4@calix-Eu(TTA) e Fe3O4@calix-Tb(ACAC) emissores vermelho e verde superparamagnéticos foram preparados pelo método one-pot. Neste caso, o ligante calixareno quimicamente modicado como surfactantes para estabilizar as nanopartículas de Fe3O4. O ligante calixareno proporciona uma superfície quimicamente modificada e estabilidade coloidal das nanopartículas magnetitas. Consequentemente, as nanopartículas funcionalizadas (Fe3O4@calix) foram coordenadas aos íons TR3+ por meio da síntese one-pot, usando ligantes TTA e ACAC como sensibilizadores (efeito antena) para produzir nanofósforos altamente luminescentes. Além do mais, nanocompósitos bifuncionais óptico e magnético Fe3O4@SiO2-TTA-Eu(L), L: TTA, TC, AB e AMB bem como Fe3O4@SiO2-TTA-Tb(AB ou AMB) foram também preparados por meio de um protocolo de múltiplas etapas, utilizando as nanopartículas Fe3O4 como precursoras. Elas foram modificas com camadas de sílica, usando o método Stöber modificado e ligados com complexos de TR3+ para produzir nanocompósitos luminescentes e magnéticos. As técnicas de difração de raios X pelo método do pó (XPD), Espalhamento de Raios-X a baixo ângulo (SAXS), microscopia eletrônica de transmissão (TEM) e microscopia de eletrônica de varredura (MEV) foram utilizas para determinar as estruturas, morfologias, distribuições de tamanhos e monodispersividade dos materiais sintetizados. Estes novos nanomateriais bifuncionais Fe3O4@calix-Eu(TTA), Fe3O4@calix-Tb(ACAC), Fe3O4@SiO2-TTA-Eu(L) e Fe3O4@SiO2-TTA-Tb(AB ou AMB) apresentam propriedades fotônicas e superparamagnéticas muito interessantes. As propriedades magnéticas (ZFC/FC e M-H) obtidas nas temperaturas de 2, 5 e 300 K foram investigadas a fim de obter informações sobre o efeito da cristalinidade na magnetização de saturação e das temperaturas de bloqueios. Também foram estudadas a influência dos íons TR3+ sobre a magnetização dos nanomateriais. Apesar da magnetita atuar como um forte supressor de luminescência, as camadas do ligante calixareno modificado e da sílica sobre as nanopartículas de Fe3O4 compensam esta desvantagem. Do mesmo modo foi considerada a discussão sobre a transferência de energia intramolecular do estado tripleto T1 dos ligantes TTA e ACAC para os níveis excitados dos íons Eu3+ e Tb3+ nos nanomateriais Fe3O4@calix-Eu(TTA) e Fe3O4@calix-Tb(ACAC). As eficiências quânticas de emissão (η) dos compostos Fe3O4@calix-Eu(TTA) e Fe3O4@SiO2-TTA-Eu(L) foram calculadas e discutidas, bem como suas características estruturais baseadas nos níveis de energia e parâmetros de intensidades experimentais dos sistemas contendo o íon Eu3+. Estes novos nanomateriais podem atuar como camadas emissores vermelha e verde para dispositivos moleculares conversores de luz e magnéticos (MLCMDs). / The design and fabrication of sophisticated bifunctional luminescent and magnetic nanomaterials based on Fe3O4 and RE3+ complexes are sought for. Accordingly, novel red-green emitting superparamagnetic Fe3O4@calix-Eu(TTA) and Fe3O4@calix-Tb(ACAC) nanomaterials were prepared through on-pot method. In this regard, the chemically modified calixarene ligand was used as a surfactant to stabilize the Fe3O4 nanoparticles. The calixarene ligand provides colloidal stability and chemically modifiable surface to the magnetite nanoparticles. Thus, this ligand functionalized Fe3O4@calix nanoparticles were further coordinated to the RE3+ ions via one-pot synthesis, using TTA and ACAC ligands as sensitizers (antenna effect) to produce highly luminescent nanophosphors. In addition, bifunctional optical and magnetic Fe3O4@SiO2-TTA-Eu(L), L: TTA, TC, AB and AMB as well as Fe3O4@SiO2-TTA-Tb(AB or AMB) nanocomposites were also synthesized through multistep synthetic protocol, utilizing Fe3O4 nanoparticles as precursors. They were modified with silica shell, using modified Stöber method and further grafted with RE3+ complexes to produce the luminescent and magnetic nanocomposites. The X-ray powder diffraction (XPD), small angle x-ray scattering (SAXS), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) techniques were used to determine the structures, morphologies, size distribution and monodispersity of the synthesized materials. These novel Fe3O4@calix-Eu(TTA) and Fe3O4@calix-Tb(ACAC) as well as Fe3O4@SiO2-TTA-Eu(L) and Fe3O4@SiO2-TTA-Tb(AB or AMB) magnetic luminescent nanomaterials show interesting superparamagnetic and photonic properties. The magnetic properties (M-H and ZFC/FC measurements) at temperatures of 2, 5 and 300 K were explored in order to investigate the extent of coating and crystalinity effect on the saturation magnetization and blocking temperatures. The influence of the RE3+ ions on the magnetization of the optical and magnetic nanomaterials was also studied. Even though magnetite is a strong luminescence quencher, the coating of the Fe3O4 nanoparticles with synthetically modified calixarene ligand (calix) and silica shell have overcome this difficulty. Moreover, the intramolecular energy transfer from the T1 excited triplet states of TTA and ACAC ligands to the emitting levels of Eu3+ and Tb3+ in the Fe3O4@calix-Eu(TTA) and Fe3O4@calix-Tb(ACAC) nanomaterials are discussed. The emission quantum efficiencies (η) for the Fe3O4@calix-Eu(TTA) and Fe3O4@SiO2-TTA-Eu(L) nanomaterials are also calculated and discussed, as well as the structural features based on the energy levels and experimental intensity parameters, in the case of the Eu3+ ion. These novel nanomaterials may act as the emitting layer for the red and green light for magnetic and light converting molecular devices (MLCMDs).

De acordo com a literatura recente, a eletroquímica de partículas magnéticas e fenômenos de colisões em superfícies eletródicas resultam em curvas voltamétricas e amperométricas com perfis completamente destoados do convencional. Alguns modelos teóricos propõem explicações, no entanto, ainda se observa a necessidade de aquisição de mais dados experimentais. Visando contribuir com esta área, esta Dissertação de Mestrado aborda a manipulação de micropartículas e nanopartículas de magnetita modificadas com azul da Prússia (Fe3O4-PB), bem como o estudo das propriedades eletroquímicas das partículas na presença de um campo magnético externo. Filmes constituídos por micropartículas sobre eletrodos de carbono (grafite) foram obtidos por duas técnicas distintas, drop coating e magneto-deposição. Para ambos os métodos, os filmes apresentaram dois picos nos voltamogramas, um de oxidação (0,12 V) e outro de redução (-0,05 V), que estão associados ao par redox azul da Prússia/branco da Prússia. Para o filme obtido via drop coating, observaram-se correntes de pico mais elevadas. Também, micropartículas de Fe3O4-PB individuais foram isoladas (single particle) com auxílio de um microscópio óptico e analisadas por voltametria, onde se verificou o aparecimento de picos com os mesmos valores de potenciais. Utilizando os dois estados de comutação de campo (0,2 Tesla), ligado e desligado, foi possível controlar a presença e a ausência da partícula no eletrodo. Também, observaram-se diferenças nos valores de densidade de corrente nos cronoamperogramas para cada micropartícula de Fe3O4-PB e que a morfologia da micropartícula interfere significativamente na resposta eletroquímica. Por fim, e agora se tratando da eletroquímica de nanopartículas de Fe3O4-PB sobre um ultramicroeletrodo (UME) de ouro, controlaram-se as colisões das mesmas em diferentes condições experimentais, como na presença e na ausência de um campo magnético externo paralelo a superfície do eletrodo e com intensidades variadas (0,1 e 0,2 Tesla). Na ausência do campo, as nanopartículas que chegaram ao UME colidiram e se acumularam, gerando sinais eletroquímicos do tipo corrente staircase. Na presença de um campo de 0,1 T, observaram-se vários transientes de correntes (spikes) associados às colisões das nanopartículas, eventos esses não observados frequentemente na presença do campo de 0,2 T. Assim, esses resultados abrem a discussão da necessidade de se aperfeiçoarem os modelos que explicam os perfis das curvas voltamétricas e amperométricas para esses sistemas. / According to recent literature, the electrochemistry of magnetic particles and collision phenomena on surfaces result in unconventional voltammetric and amperometric responses. Some theoretical models has been proposed; however, experimental data are required for improve that. In order to contribute to this research area, this Master\'s Dissertation describes the manipulation of microparticles and nanoparticles of magnetite modified with Prussian blue (Fe3O4-PB), as well as the study of electrochemical properties of them in presence of an external magnetic field. Carbon (graphite) electrodes modified with microparticles were obtained by using two different techniques, (i) magneto-deposition and (ii) drop coating. For both, two peaks in the voltammograms were observed, related to oxidation (0.12 V) and reduction (-0.05 V), which are associated with redox couple Prussian blue / Prussian white. Higher peaks currents were observed for the film obtained via drop coating. Also, individual Fe3O4-PB microparticles (single particles) were isolated by using an optical microscope and analyzed by voltammetry, where there was the appearance of peaks with the same potential values. However, using two commutations magnetic states, \"switch on\" and \"switch off\", it was possible to monitor the presence and the absence of the particle on electrode. Also, there were differences in the values of current density in the chronoamperograms for each Fe3O4-PB microparticle, and the morphology of the microparticle significantly interfered in the electrochemical response. Finally, it was performed several electrochemical experiments regarding to collisions of Fe3O4-PB nanoparticles on a gold ultramicroelectrode. Controlled collisions in different experimental conditions were carried out, such as in the presence and absence of an external magnetic field parallel to the surface electrode, and also with intensities fields of 0.1 and 0.2 Tesla. In the absence of the field, the nanoparticles reached the UME and collided, resulting in electrochemical signals of this type staircase, due to accumulation of them. On the other hand, in the presence of a 0.1 T, we observed several transient currents (spikes) associated with the collisions of the nanoparticles. These events were not observed in the presence of the field of 0.2 T. Thus, these findings allow us to the discussion for improvements on the models for these systems, in order to explain the profiles of voltammetric and amperometric responses.

Neste trabalho são investigados o designer e a fabricação nanomateriais magnéticos e luminescentes sofisticados bifuncionais baseados em Fe3O4 e complexos de RE3+. Portanto, novos nanomateriais Fe3O4@calix-Eu(TTA) e Fe3O4@calix-Tb(ACAC) emissores vermelho e verde superparamagnéticos foram preparados pelo método one-pot. Neste caso, o ligante calixareno quimicamente modicado como surfactantes para estabilizar as nanopartículas de Fe3O4. O ligante calixareno proporciona uma superfície quimicamente modificada e estabilidade coloidal das nanopartículas magnetitas. Consequentemente, as nanopartículas funcionalizadas (Fe3O4@calix) foram coordenadas aos íons TR3+ por meio da síntese one-pot, usando ligantes TTA e ACAC como sensibilizadores (efeito antena) para produzir nanofósforos altamente luminescentes. Além do mais, nanocompósitos bifuncionais óptico e magnético Fe3O4@SiO2-TTA-Eu(L), L: TTA, TC, AB e AMB bem como Fe3O4@SiO2-TTA-Tb(AB ou AMB) foram também preparados por meio de um protocolo de múltiplas etapas, utilizando as nanopartículas Fe3O4 como precursoras. Elas foram modificas com camadas de sílica, usando o método Stöber modificado e ligados com complexos de TR3+ para produzir nanocompósitos luminescentes e magnéticos. As técnicas de difração de raios X pelo método do pó (XPD), Espalhamento de Raios-X a baixo ângulo (SAXS), microscopia eletrônica de transmissão (TEM) e microscopia de eletrônica de varredura (MEV) foram utilizas para determinar as estruturas, morfologias, distribuições de tamanhos e monodispersividade dos materiais sintetizados. Estes novos nanomateriais bifuncionais Fe3O4@calix-Eu(TTA), Fe3O4@calix-Tb(ACAC), Fe3O4@SiO2-TTA-Eu(L) e Fe3O4@SiO2-TTA-Tb(AB ou AMB) apresentam propriedades fotônicas e superparamagnéticas muito interessantes. As propriedades magnéticas (ZFC/FC e M-H) obtidas nas temperaturas de 2, 5 e 300 K foram investigadas a fim de obter informações sobre o efeito da cristalinidade na magnetização de saturação e das temperaturas de bloqueios. Também foram estudadas a influência dos íons TR3+ sobre a magnetização dos nanomateriais. Apesar da magnetita atuar como um forte supressor de luminescência, as camadas do ligante calixareno modificado e da sílica sobre as nanopartículas de Fe3O4 compensam esta desvantagem. Do mesmo modo foi considerada a discussão sobre a transferência de energia intramolecular do estado tripleto T1 dos ligantes TTA e ACAC para os níveis excitados dos íons Eu3+ e Tb3+ nos nanomateriais Fe3O4@calix-Eu(TTA) e Fe3O4@calix-Tb(ACAC). As eficiências quânticas de emissão (η) dos compostos Fe3O4@calix-Eu(TTA) e Fe3O4@SiO2-TTA-Eu(L) foram calculadas e discutidas, bem como suas características estruturais baseadas nos níveis de energia e parâmetros de intensidades experimentais dos sistemas contendo o íon Eu3+. Estes novos nanomateriais podem atuar como camadas emissores vermelha e verde para dispositivos moleculares conversores de luz e magnéticos (MLCMDs). / The design and fabrication of sophisticated bifunctional luminescent and magnetic nanomaterials based on Fe3O4 and RE3+ complexes are sought for. Accordingly, novel red-green emitting superparamagnetic Fe3O4@calix-Eu(TTA) and Fe3O4@calix-Tb(ACAC) nanomaterials were prepared through on-pot method. In this regard, the chemically modified calixarene ligand was used as a surfactant to stabilize the Fe3O4 nanoparticles. The calixarene ligand provides colloidal stability and chemically modifiable surface to the magnetite nanoparticles. Thus, this ligand functionalized Fe3O4@calix nanoparticles were further coordinated to the RE3+ ions via one-pot synthesis, using TTA and ACAC ligands as sensitizers (antenna effect) to produce highly luminescent nanophosphors. In addition, bifunctional optical and magnetic Fe3O4@SiO2-TTA-Eu(L), L: TTA, TC, AB and AMB as well as Fe3O4@SiO2-TTA-Tb(AB or AMB) nanocomposites were also synthesized through multistep synthetic protocol, utilizing Fe3O4 nanoparticles as precursors. They were modified with silica shell, using modified Stöber method and further grafted with RE3+ complexes to produce the luminescent and magnetic nanocomposites. The X-ray powder diffraction (XPD), small angle x-ray scattering (SAXS), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) techniques were used to determine the structures, morphologies, size distribution and monodispersity of the synthesized materials. These novel Fe3O4@calix-Eu(TTA) and Fe3O4@calix-Tb(ACAC) as well as Fe3O4@SiO2-TTA-Eu(L) and Fe3O4@SiO2-TTA-Tb(AB or AMB) magnetic luminescent nanomaterials show interesting superparamagnetic and photonic properties. The magnetic properties (M-H and ZFC/FC measurements) at temperatures of 2, 5 and 300 K were explored in order to investigate the extent of coating and crystalinity effect on the saturation magnetization and blocking temperatures. The influence of the RE3+ ions on the magnetization of the optical and magnetic nanomaterials was also studied. Even though magnetite is a strong luminescence quencher, the coating of the Fe3O4 nanoparticles with synthetically modified calixarene ligand (calix) and silica shell have overcome this difficulty. Moreover, the intramolecular energy transfer from the T1 excited triplet states of TTA and ACAC ligands to the emitting levels of Eu3+ and Tb3+ in the Fe3O4@calix-Eu(TTA) and Fe3O4@calix-Tb(ACAC) nanomaterials are discussed. The emission quantum efficiencies (η) for the Fe3O4@calix-Eu(TTA) and Fe3O4@SiO2-TTA-Eu(L) nanomaterials are also calculated and discussed, as well as the structural features based on the energy levels and experimental intensity parameters, in the case of the Eu3+ ion. These novel nanomaterials may act as the emitting layer for the red and green light for magnetic and light converting molecular devices (MLCMDs).

Magnetite (Fe3O4) is a commonly found in the environment and can form via several pathways, including biotic and abiotic reduction of Fe3+ oxides and the oxidation of Fe2+ and Fe0. Despite extensive research, the redox behavior of magnetite is poorly understood. In previous work, the extent and kinetics of contaminant reduction by magnetite varied by several orders of magnitude between studies, two fundamentally different models are used to explain magnetite oxidation (i.e., core-shell diffusion and redox-driven), and reported reduction potentials vary by almost 1 V. In other fields of science (e.g., physics), magnetite stoichiometry (x = Fe2+/Fe3+) is a commonly measured property, however, in environmental studies, the stoichiometry is rarely measured. The stoichiometry of magnetite can range from 0.5 (stoichiometric) to 0 (completely oxidized), with intermediate values (0 < x < 0.5) referred to as nonstoichiometric or partially oxidized magnetite. To determine the relationship between magnetite stoichiometry and contaminant fate, the reduction rates of three substituted nitrobenzenes (ArNO2) were measured. The kinetic rates varied over five orders of magnitude as the particle stoichiometry increased from x = 0.31 to 0.50. Apparent 15N kinetic isotope effects (15N-AKIE) values for ArNO2 were greater than unity for all magnetite stoichiometries investigated, and indicated that mass transfer processes are not controlling the reaction rate. To determine if the reaction kinetics were redox-driven, magnetite open circuit potentials (EOCP) were measured. EOCP values were linearly related to the stoichiometry, with more stoichiometric magnetite having a lower potential, in good agreement with redox-driven models. The reaction of aqueous Fe2+ and magnetite was investigated. Similar to previous findings for other Fe3+ oxides, the formation of a stable sorbed Fe2+ species was not observed; instead, the sorbed Fe2+ underwent interfacial electron transfer to form a partially oxidized magnetite phase, which was accompanied by reduction of the underlying magnetite. The lack of a stable sorbed Fe2+ species on magnetite indicated that the traditional surface complexation model was incorrect; instead, the uptake of Fe2+ by magnetite appeared to be limited by the whole particle (i.e., the sorbed and underlying phases combined) reaching a stoichiometry of 0.5.