The constant growth in population worldwide over the past decades continues to put forward the need to provide access to safe, clean water to meet human needs. There is a need for cost-effective technologies for water and wastewater treatment that can meet the global demands and the rigorous water quality standards and at the same maximizing pollutant efficiency removal. Current remediation technologies have failed in keeping up with these factors without becoming cost-prohibitive. Nanotechnology has recently been sought as a promising option to achieve these goals. The use of iron oxide magnetic nanoparticles as nanoadsorbents has led to a new class of magnetic separation strategies for water treatment. We have developed magnetic nanocomposite systems able to capture polychlorinated biphenyls (PCBs), as model organic pollutants, in aqueous solution, providing a cost-effective water remediation technique. Two distinct methods were employed to develop these polyphenolic nanocomposite materials. The polyphenolic moieties were incorporated to create high affinity binding sites for organic pollutants within the nanocomposites. The first method utilized a surface initiated polymerization of polyphenolic-based crosslinkers and co-monomers on the surface of iron oxide magnetic nanoparticles to create a core-shell nanocomposite. The second method utilized a bulk polymerization method to create macroscale films composed of iron oxide nanoparticles incorporated into a polyphenolic-based polymer matrix, which were then processed into microparticles. Both methods produce nanocomposite materials that can bind chlorinated organics, can rapidly separate bound organics from contaminated water sources using magnetic decantation, and can use thermal destabilization of the polymer matrix for contaminant release and material regeneration. The polyphenol functionalities used to bind organic pollutants were quercetin multiacrylate (QMA) and curcumin multiacrylate (CMA), which are acrylated forms of the nutrient polyphenols quercetin (found in berries) and curcumin (found in turmeric), both with expected affinity for chlorinated organics. The affinity of these novel materials for PCB 126 was evaluated at equilibrium conditions using a gas chromatography coupled to electron capture detection (GC-ECD) for quantification purposes, and the data was fitted to the nonlinear Langmuir model to determine binding affinity (KD) and maximum biding capacity (Bmax). The KD values obtained demonstrated that the presence of the polyphenolic-based moieties, CMA and QMA, as crosslinkers enhanced the binding affinity for PCB 126, expected to be a result of their aromatic rich nature which provides sites for π – π stacking interactions between the nanoparticle surface and the PCBs in solution. These values are lower that the reported affinity coefficients for activated carbon, which is the gold standard for capture/binding of organic contaminants in water and waste water treatment. Furthermore, upon exposure to an alternating magnetic field (AMF) for a period of 5 minutes, over 90% of the bound PCB on these materials was released, offering a low-cost regeneration method for the nanocomposites. Additionally, this novel regeneration strategy does not require the use of large volumes of harsh organic solvents that oftentimes become harmful byproducts. Overall, we have provided strong evidence that these novel nanocomposites have a promising application as nanoadsorbents for specific organic contaminants in contaminated water sources providing high binding affinities, a low-cost regeneration technique and are capable of withstanding use under environmental conditions offering a cost effective alternative to current remediation approaches.

We present a systematic methodology to functionalize magnetic nanoparticles through surface-initiated atom-transfer radical polymerization (ATRP). The magnetite nanoparticles are prepared according to the method proposed by Sun et al. (2004), which leads to a monodisperse population of ~ 6 nm particles stabilized by oleic acid. The functionalization of the nanoparticles has been performed by transforming particles into macro-initiators for the ATRP, and to achieve this two different routes have been explored. The first one is the ligand-exchange method, which consists of replacing some oleic acid molecules adsorbed on the particle surface with molecules that act as an initiator for ATRP. The second method consists in using the addition reaction of bromine to the oleic acid double bond, which turns the oleic acid itself into an initiator for the ATRP. We have then grown polymer brushes of a variety of acrylic polymers on the particles, including polyisopropylacrylamide and polyacrylic acid. The nanoparticles so functionalized are water soluble and show responsive behavior: either temperature responsive behavior when polyisopropylacrylamide is grown from the surface or PH responsive in the case of polyacrylic acid. This methodology has potential applications in the control of clustering of magnetic nanoparticles. / Singapore-MIT Alliance (SMA)

Magnetic nanoparticles attract increasing attention because of their current and potential biomedical applications, such as, magnetically targeted and controlled drug delivery, magnetic hyperthermia and magnetic extraction. Increased magnetization can lead to improved performance in targeting and retention in drug delivery and a higher efficiency in biomaterials extraction. We reported an approach to synthesize iron contained magnetic nanoparticles with high magnetization and good oxidation resistibility by pyrolysis of iron pentacarbonyl (Fe(CO)[subscript 5]) in methane (CH[subscript 4]). Using the high reactivity of Fe nanoparticles, decomposition of CH[subscript 4] on the Fe nanoparticles leads to the formation of nanocrystalline iron carbides at a temperature below 260°C. Structural investigation indicated that the as-synthesized nanoparticles contained crystalline bcc Fe, iron carbides and spinel iron oxide. The Mössbauer and DSC results testified that the as-synthesized nanoparticle contained three crystalline iron carbide phases, which converted to Fe[subscript 3]C after a heat treatment. Surface analysis suggested that the as-synthesized and subsequently heated iron-iron carbide particles were coated by iron oxide, which originated from oxidization of surface Fe atoms. The heat-treated nanoparticles exhibited a magnetization of 160 emu/g, which is two times of that of currently used spinel iron oxide nanoparticles. After heating in an acidic solution with a pH value of 5 at 60°C for 20 h, the nanoparticles retained 90 percentage of the magnetization. / Singapore-MIT Alliance (SMA)

One of the main issues with the use of nickel titanium alloy (NiTi) implants in cardiovascular implants (stents) is that these devices must be of very high quality in order to avoid subsequent operations due to failing stents. For small stents with diameters below ca. 2 mm, however, stent characterization is not straightforward. One of the main problems is that there are virtually no methods to characterize the interior of the NiTi tubes used for fabrication of these tiny stents. The current paper reports on a robust hybrid actuator for the characterization of NiTi tubes prior to stent fabrication. The method is based on a polymer/hydrogel/magnetic nanoparticle hybrid material and allows for the determination of the inner diameter at virtually all places in the raw NiTi tubes. Knowledge of the inner structure of the raw NiTi tubes is crucial to avoid regions that are not hollow or regions that are likely to fail due to defects inside the raw tube. The actuator enables close contact of a magnetic polymer film with the inner NiTi tube surface. The magnetic signal can be detected from outside and be used for a direct mapping of the tube interior. As a result, it is possible to detect critical regions prior to expensive and slow stent fabrication processes.

Surface Biological Modification and Cellular Interactions of Magnetic Spinel Nanoparticles Eva Liang-Huang Heintz 191 Pages Directed by Dr. Z. John Zhang The interest in magnetic nanoparticles is multi-dimensional. Fundamentally, it is important to be able to control their magnetic properties and to correlate to specific applications. In biology, magnetic nanoparticles offer promising potential as magnetic carriers or chaperones for magnetic localization and manipulation of therapeutic reagents. The synthesis of superparamagnetic CoFe2-xSmxO4 nanoparticles and the tunability of their magnetic properties by size and composition variations are discussed. An increase in size of CoSm0.19Fe1.81O4 nanoparticles produced an increase in blocking temperature and saturation magnetization, but a non-linear coercitivity response was observed with change in size. By varying the composition, the saturation magnetization of CoFe2-xSmxO4 decreased dramatically while the coercitivity increased when compared to native cobalt spinel ferrite (CoFe2O4) nanoparticles. These results demonstrate how the magnetic properties of cobalt spinel ferrite nanoparticles can be tailored to specific applications. Surface modifications of cobalt spinel ferrite nanoparticles facilitated the conjugation of oligonucleotides. Using a transfection reagent, CoFe2O4 ??igonucleotide conjugates were delivered into mammalian cells. Post transfection, synchronized movement of cells in response to an external magnetic field was observed. This demonstrated the possibility of magnetic manipulation and localization of therapeutic reagents coupled to CoFe2O4 magnetic nanoparticles. Results from this thesis demonstrate the potential role of magnetic spinel nanoparticles in cell biology and will facilitate the progress towards in vivo testing.

ANDRADE NETO, Davino Machado. Magnetic ressonance imaging contrast agents obtained by fast sonochemistry approach. 2016. 84 f. Dissertação (Mestrado em Química)-Universidade Federal do Ceará, Fortaleza, 2016. / Submitted by Aline Mendes (alinemendes.ufc@gmail.com) on 2017-01-25T19:35:32Z No. of bitstreams: 1 2016_dis_dmandradeneto.pdf: 4658452 bytes, checksum: 4d05fbe6bccc67518a89306c468793a6 (MD5) / Approved for entry into archive by Jairo Viana (jairo@ufc.br) on 2017-01-26T20:28:31Z (GMT) No. of bitstreams: 1 2016_dis_dmandradeneto.pdf: 4658452 bytes, checksum: 4d05fbe6bccc67518a89306c468793a6 (MD5) / Made available in DSpace on 2017-01-26T20:28:31Z (GMT). No. of bitstreams: 1 2016_dis_dmandradeneto.pdf: 4658452 bytes, checksum: 4d05fbe6bccc67518a89306c468793a6 (MD5) Previous issue date: 2016 / Functionalized Fe3O4 nanoparticles (NPs) have emerged as a promising contrast agent for magnetic resonance imaging (MRI). Their synthesis and functionalization methodology strongly affects their performance in vivo. Although thermal decomposition is the most commonly used growth methodology reported in the literature, it has proven to be time-consuming, expensive, and laborious. Therefore, this work describes a rapid and facile sonochemical methodology to synthesize and functionalize Fe3O4 NPs with excellent physico-chemical properties for MRI. In this work, a sonochemistry approach was used to produce, in 12 min, Fe3O4 NPs functionalized with polysodium acrylate (PAANa), trisodium citrate (CIT), branched polyethylenimine (BPEI), and sodium oleate. X-ray diffraction and transmission electron microscopy demonstrated that the NPs were composed of a single inverse spinel phase with an average diameter of 9–11 nm and a narrow size distribution. It was confirmed by Mössbauer spectroscopy and magnetic measurements that the obtained NPs were transitioning to the superparamagnetic regime and possessed excellent magnetization saturation values (59–77 emu/g). Fourier transform infrared spectroscopy proved that the sonochemistry approach provided conditions that induced a strong interaction between Fe3O4 and the capping agents. Furthermore, dynamic light scattering experiments evidenced that samples coated with PAANa, CIT, and BPEI possess colloidal stability in aqueous solvents. Emphasis must be placed on PAANa-coated NPs, which also presented remarkable colloidal stability under simulated physiological conditions. Finally, the obtained NPs exhibited great potential to be applied as an MRI contrast agent. The transverse relaxativity values of the NPs synthesized in this work (277–439 mM-1s-1) were greater than those of commercial NPs and those prepared using other methodologies. Therefore, this work represents significant progress in the preparation of Fe3O4 NPs, providing a method to prepare high-quality materials in a rapid, cost-effective, and facile manner. / Nanopartículas (NPs) funcionalizadas emergiram como promissores candidatos para serem aplicadas como agente de contraste para imagem por ressonância magnética nuclear e sua metodologia de síntese e funcionalização afetam fortemente sua performance in vivo. A metodologia mais utilizada para a produção dessas NPs funcionalizadas é a decomposição térmica, a qual tem provado ser financeiramente desfavorável, laboriosa além de requisitar longos tempos de execução. Portanto, este trabalho tem como objetivo descrever uma metodologia fácil e rápida, através do método sonoquímico, para a síntese e funcionalização de NPs de Fe3O4 com excelentes propriedades físico-químicas com objetivo de serem aplicadas como agente de contraste para imagem por ressonância magnética nuclear. Neste trabalho, o método sonoquímico foi usado para produzir, em 12 min, NPs de Fe3O4 funcionalizadas com policrilato de sódio, citrato de sódio, polietilenamina ramificada e oleato de sódio. Difração de raios-X e microscopia eletrônica de transmissão demonstraram que as NPs produzidas são compostas de uma única fase de espinélio inverso de 9-11 nm de diâmetro e uma distribuição de tamanho estreita. Foi confirmado por meio da espectroscopia Mössbauer e medidas magnéticas que as NPs sintetizadas estão em transição para o regime superparamagnético e que possuem excelente valor de magnetização de saturação (59-77 emu/g) para aplicações biomédicas. Espectroscopia de infravermelho por transformada de Fourier provou que a radiação sonoquímica forneceu condições adequadas para que acontecesse uma interação forte entre o núcleo magnéticos e os agentes fucionalizantes. Além disso, experimentos de espalhamento dinâmico de luz confirmaras que as amostras recobertas com moléculas orgânicas hidrofílicas possuem estabilidade coloidal em solventes aquosos. Destaque deve ser dado a nanopartícula magnética recoberta com poliacrilato de sódio, que demonstrou excelente estabilidade coloidal em condições fisiológicas simuladas. Finalmente, as NPs obtidas se mostraram serem promissores candidatos a agentes de contraste. Uma vez que seus valores de relaxatividade transversal foram maiores que os agentes de contraste comerciais e daqueles preparados por outras metodologias sintéticas. Portanto, este trabalho trás um grande avanço no que se refere a preparação de NPs de Fe3O4 funcionalizadas para aplicações biológicas, uma vez que materiais de alta qualidade foram preparados de forma rápida e fácil.

Submitted by CAROLINE OLIVEIRA DA ROCHA null (carolnine@hotmail.com) on 2016-04-07T01:01:26Z No. of bitstreams: 1 Dissertação CAROL _final.pdf: 2850056 bytes, checksum: faa1d75413b1d7af499fafe8cb5e9700 (MD5) / Approved for entry into archive by Ana Paula Grisoto (grisotoana@reitoria.unesp.br) on 2016-04-07T16:24:41Z (GMT) No. of bitstreams: 1 rocha_co_me_araiq.pdf: 2850056 bytes, checksum: faa1d75413b1d7af499fafe8cb5e9700 (MD5) / Made available in DSpace on 2016-04-07T16:24:41Z (GMT). No. of bitstreams: 1 rocha_co_me_araiq.pdf: 2850056 bytes, checksum: faa1d75413b1d7af499fafe8cb5e9700 (MD5) Previous issue date: 2016-03-14 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / As enzimas são catalisadores de alto custo, sendo necessário a imobilização para que haja a recuperação e a reutilização tornando o processo viável economicamente. Além disso, a utilização de enzimas imobilizadas permite simplificar o modelo de reatores e o controle da reação. Assim, a imobilização é geralmente um requisito para a utilização de enzimas como biocatalisadores industriais. A escolha do suporte para imobilização depende das propriedades da enzima a ser imobilizada. Suportes sólidos podem interagir com a enzima por diferentes vias: por adsorção, ligação covalente ou encapsulamento. Um importante fator para imobilizar a enzima é que o suporte deve ser inerte e biocompatível ao ambiente, ou seja, não deve interferir na estrutura nativa da proteína e nem comprometer sua atividade biológica. Dentre as principais enzimas, as lipases hidrolisam triglicerídeos (TAG) em glicerol e ácidos graxos e por este motivo estão na classe das hidrolases. Uma proposta de imobilização destas enzimas consiste na utilização de nanoestruturas magnéticas como biocatalisadores da reação de transesterificação para a produção de biodiesel, devido à facilidade e a rápida separação das enzimas imobilizadas, a partir da mistura reacional, usando um campo magnético externo. As vantagens das enzimas imobilizadas em relação às enzimas livres surgem da sua maior estabilidade e facilidade de separação, o que acarreta economia significativa no custo global do processo, desde que o procedimento de imobilização não seja muito caro, haja boa recuperação da atividade enzimática e que a estabilidade operacional da enzima imobilizada seja suficientemente longa. O uso de enzimas imobilizadas permite a retenção do biocatalisador no reator; elevada concentração de catalisador no reator permitindo intensificar o processo; controle do microambiente da enzima; facilidade de recuperação e reutilização do catalisador, o que reduz os custos das enzimas; possibilidade de ser utilizado em sistemas contínuos. Utilizando a técnica de difração de raios X foi possível confirmar a fase magnetita nas sínteses propostas: método de coprecipitação e em meio orgânico. A funcionalização da superfície da NP e SP com APTS, foi comprovado por espectroscopia na região de infravermelho, apresentando bandas de –NH2. A técnica de DLS comprovou a funcionalização, pelo aumento dos diâmetros hidrodinâmicos das amostras NP-APTS e SP-APTS comparada a NP e SP. O ponto isoelétrico das amostras SP e SP-APTS apresentou aumento de 2,33 para 6,44. O derivado imobilizado apresentou bandas típicas de amidas. As lipases imobilizadas apresentaram diâmetros hidrodinâmicos maiores que NP-APTS e SP-APTS. Os resultados da atividade hidrolítica das enzimas suportadas foram satisfatórios, sendo que SP-APTS-LPP apresentou maior atividade. Pela análise termogravimétrica comprovou-se rendimento de imobilização de 22,86%. Determinou-se o pH ótimo da lipase imobilizada que mostrou maior atividade em pH 8 enquanto a LPP livre em pH 6,5. As medidas de temperatura ótima demostrou que o derivado imobilizado possui maior atividade que a LPP livre a 50 °C, favorecendo a utilização deste suporte em processos industriais de biodiesel que opera em altas temperaturas. Neste contexto, a síntese de suportes magnéticos porosos e a imobilização de lipases com este suporte, apresentou excelentes resultados para a aplicação em biocatálise na reação de transesterificação para a síntese de biodiesel. / Enzymes are expensive catalysts, immobilization is necessary for recovery and reuse making the process economically viable. Furthermore, use of immobilized enzymes can simplify model reactor and control reaction. Thus, immobilization is generally a requirement for use of the enzyme as an industrial biocatalyst. The choice of support for biocatalysts immobilization depends on properties of enzyme to be immobilized. Solid supports can interact with enzyme in different ways: by adsorption, covalent bonding or encapsulation. An important factor to immobilize the enzyme is that support must be inert and biocompatible to environment; it should not interfere in native structure of protein and not compromising their biological activity. The main enzymes, lipases hydrolyze triglycerides (TAG) to glycerol and fatty acids and for this reason; they are in the class of hydrolases. These enzymes are carboxylesterases that catalyze hydrolysis in glycerides synthesis. A proposal for immobilization of these enzymes is use of magnetic nanostructures in biocatalysts transesterification reaction for producing biodiesel due to ease and rapid separation of immobilized enzyme, from a mixture reaction using an external magnetic field. The benefits of immobilized enzymes compared to free enzymes arise from their greater stability and ease of separation, which leads to significant savings in the overall cost of the process, provided that immobilization procedure is not very expensive, there is good recovery of enzyme activity, and operational stability of immobilized enzyme is sufficiently long. The use of immobilized enzymes allow retention of biocatalyst in reactor; high concentration of catalyst in reactor to intensify the process; control of microenvironment of enzyme; ease of recovery and reuse of catalyst, which reduces the costs of enzymes; possibility of being used in continuous systems. Using the technique of X-ray diffraction was confirmed magnetite phase in syntheses proposed: co-precipitation method and organic solvent. The functionalization of surface NP and SP with APTS confirmed by spectroscopy in infrared region, with bands of -NH2. The DLS technique proved the functionalization, the increase of hydrodynamic diameters NP-APTS samples and SP-APTS compared to NP and SP. The isoelectric point of SP and SP-APTS samples increased by 2.33 to 6.44. The immobilized derivative showed typical bands of amides. Immobilized lipases showed higher hydrodynamic diameters NP-APTS and SP-APTS. The results of hydrolytic activity of supported enzymes were satisfactory and SP-APTS-LPP showed higher activity. By thermogravimetric analysis, it was shown immobilization yield 22.86%. It was determined the pH optimum of immobilized lipase showed highest activity at pH 8 while the LPP free at pH 6.5. The optimum temperature measurements demonstrated that immobilized derivative is more active than free LPP at 50 ° C, favoring the use of support in industrial processes of biodiesel, which operates at high temperatures. In this context, the synthesis of porous magnetic support and immobilization of lipases showed excellent results for use in biocatalysis in transesterification reaction for biodiesel synthesis.

Made available in DSpace on 2014-06-11T19:25:34Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-10-29Bitstream added on 2014-06-13T20:53:38Z : No. of bitstreams: 1 souza_at_me_sjrp_parcial.pdf: 48305 bytes, checksum: 2ab2a37aa6e511084d3705cb0e675c4c (MD5) Bitstreams deleted on 2014-10-03T16:24:37Z: souza_at_me_sjrp_parcial.pdf,Bitstream added on 2014-10-03T16:27:36Z : No. of bitstreams: 2 souza_at_me_sjrp_parcial.pdf.txt: 18111 bytes, checksum: c5bd29ac564839820b6ca688b23abec8 (MD5) 000680523.pdf: 1511132 bytes, checksum: c20e5a6a65edf2cba90d4de2b5073a08 (MD5) Bitstreams deleted on 2014-10-03T16:33:13Z: 000680523.pdf,Bitstream added on 2014-10-03T16:43:27Z : No. of bitstreams: 2 souza_at_me_sjrp_parcial.pdf.txt: 18111 bytes, checksum: c5bd29ac564839820b6ca688b23abec8 (MD5) 000680523.pdf: 1511132 bytes, checksum: c20e5a6a65edf2cba90d4de2b5073a08 (MD5) Bitstreams deleted on 2014-10-03T16:48:53Z: 000680523.pdf,Bitstream added on 2014-10-03T16:49:45Z : No. of bitstreams: 1 000680523.pdf: 1511132 bytes, checksum: c20e5a6a65edf2cba90d4de2b5073a08 (MD5) Bitstreams deleted on 2014-10-27T11:47:06Z: 000680523.pdf,Bitstream added on 2014-10-27T11:48:03Z : No. of bitstreams: 1 000680523.pdf: 1511132 bytes, checksum: c20e5a6a65edf2cba90d4de2b5073a08 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Nanopartículas magnéticas (NPMs) têm sido alvo de inúmeras investigações por seu grande potencial de aplicação nos mais diferentes campos tecnológicos. Dentre tantos, elas destacam-se na área biomédica, seja no diagnóstico ou tratamento de diversas doenças. Neste trabalho foram sintetizadas nanopartículas magnéticas (NPMs) de óxido de ferro (magnetita) pelo método de coprecipitação de íons Fe2+ e Fe3+ em meio alcalino. O objetivo central foi estudar as características morfológicas, estruturais, magnéticas e o comportamento biológico desses compostos em células cancerígenas, visando futuras aplicações biomédicas. Inicialmente as nanopartículas magnéticas foram avaliadas em função dos parâmetros físico-químicos que influenciam diretamente as características finais do produto (pH, molaridade, temperatura e tipo de base) para se observar as melhores condições de síntese e a influência de cada um nas características do produto. As nanopartículas foram caracterizadas por difratometria de raios-X, microscopia eletrônica de varredura, potencial zeta e magnetometria. Desse primeiro estudo concluiu-se que a coprecipitação produz partículas com polidispersão de tamanhos alta e que os parâmetros de síntese influenciam drasticamente as propriedades dos materiais, no entanto, todas as amostras exibiam características magnéticas. Depois de estabelecida esta etapa, as NPMs foram submetidas à transfecção em cultura celular de carcinoma cervical humano (células HeLa) e a testes biológicos como coloração com Azul da Prússia e hematoxilina-eosina, ensaio de MTT e ensaio de apoptose para averiguação da citotoxidade. A principal observação vinda desses resultados foi que as nanopartículas magnéticas sintetizadas, salvo algumas adaptações de síntese... / Magnetic nanoparticles (MNPs) have been the subject of numerous investigations because of its great potential application in many different fields of technology. Among many, they stand out in the biomedical area, either in diagnosis or treatment of various diseases. In this work were synthesized magnetic nanoparticles (MNPs) of iron oxide (magnetite) by the coprecipitation method of Fe2+ and Fe3+ in an alkaline medium. The main objective was to study the morphological, structural, magnetic and biological behavior of these compounds in cancer cells, in order to future biomedical applications. Initially the magnetic nanoparticles were evaluated against the physical and chemical parameters that directly influence the final characteristics of product (pH, molarity, temperature and type of base) to observe the best synthesis conditions and influence of each characteristics. The nanoparticles were characterized by X-ray diffraction, sccaning electron microscopy, zeta potential and magnetometry. In this first study showed that coprecipitation produces particles with high polydispersity of sizes and that the synthesis parameters dramatically influence the properties of materials, however all samples exhibited magnetic characteristics. After you make this step, the MNP were subjected to transfection in cell culture of human cervical carcinoma (HeLa) and biological tests such as staining with Prussian blue and hematoxylin-eosin, MTT assay and apoptosis assay to investigate cytotoxicity. The main observation was that these results coming magnetic nanoparticles synthesized, except for some adjustments in short, constitute a class of nanocomposites with enormous potential for therapeutic and / or diagnosis. The work brings together information ranging from the synthesis of nanoparticles to their behavior inside the cells, emphasizing the best conditions for each procedure

Orientador: José Geraldo Nery / Banca: Paula Rahal / Banca: Maria Cristina Nonato Costa / Resumo: Nanopartículas magnéticas (NPMs) têm sido alvo de inúmeras investigações por seu grande potencial de aplicação nos mais diferentes campos tecnológicos. Dentre tantos, elas destacam-se na área biomédica, seja no diagnóstico ou tratamento de diversas doenças. Neste trabalho foram sintetizadas nanopartículas magnéticas (NPMs) de óxido de ferro (magnetita) pelo método de coprecipitação de íons Fe2+ e Fe3+ em meio alcalino. O objetivo central foi estudar as características morfológicas, estruturais, magnéticas e o comportamento biológico desses compostos em células cancerígenas, visando futuras aplicações biomédicas. Inicialmente as nanopartículas magnéticas foram avaliadas em função dos parâmetros físico-químicos que influenciam diretamente as características finais do produto (pH, molaridade, temperatura e tipo de base) para se observar as melhores condições de síntese e a influência de cada um nas características do produto. As nanopartículas foram caracterizadas por difratometria de raios-X, microscopia eletrônica de varredura, potencial zeta e magnetometria. Desse primeiro estudo concluiu-se que a coprecipitação produz partículas com polidispersão de tamanhos alta e que os parâmetros de síntese influenciam drasticamente as propriedades dos materiais, no entanto, todas as amostras exibiam características magnéticas. Depois de estabelecida esta etapa, as NPMs foram submetidas à transfecção em cultura celular de carcinoma cervical humano (células HeLa) e a testes biológicos como coloração com Azul da Prússia e hematoxilina-eosina, ensaio de MTT e ensaio de apoptose para averiguação da citotoxidade. A principal observação vinda desses resultados foi que as nanopartículas magnéticas sintetizadas, salvo algumas adaptações de síntese... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Magnetic nanoparticles (MNPs) have been the subject of numerous investigations because of its great potential application in many different fields of technology. Among many, they stand out in the biomedical area, either in diagnosis or treatment of various diseases. In this work were synthesized magnetic nanoparticles (MNPs) of iron oxide (magnetite) by the coprecipitation method of Fe2+ and Fe3+ in an alkaline medium. The main objective was to study the morphological, structural, magnetic and biological behavior of these compounds in cancer cells, in order to future biomedical applications. Initially the magnetic nanoparticles were evaluated against the physical and chemical parameters that directly influence the final characteristics of product (pH, molarity, temperature and type of base) to observe the best synthesis conditions and influence of each characteristics. The nanoparticles were characterized by X-ray diffraction, sccaning electron microscopy, zeta potential and magnetometry. In this first study showed that coprecipitation produces particles with high polydispersity of sizes and that the synthesis parameters dramatically influence the properties of materials, however all samples exhibited magnetic characteristics. After you make this step, the MNP were subjected to transfection in cell culture of human cervical carcinoma (HeLa) and biological tests such as staining with Prussian blue and hematoxylin-eosin, MTT assay and apoptosis assay to investigate cytotoxicity. The main observation was that these results coming magnetic nanoparticles synthesized, except for some adjustments in short, constitute a class of nanocomposites with enormous potential for therapeutic and / or diagnosis. The work brings together information ranging from the synthesis of nanoparticles to their behavior inside the cells, emphasizing the best conditions for each procedure / Mestre

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / No presente trabalho, nanopartÃculas de M0,5Zn0,5Fe2O4 (M= Ni ou Mn) foram preparadas por sÃntese hidrotÃrmica sob condiÃÃes brandas sem qualquer procedimento de calcinaÃÃo. Amostras de composiÃÃo MFe2O4 (M = Zn, Ni ou Mn) tambÃm foram sintetizadas para fins de comparaÃÃo. As propriedades estruturais e magnÃticas das amostras foram investigadas por DifraÃÃo de Raios-X (DRX), Espectroscopia na RegiÃo do Infravermelho com Transformada de Fourier (FTIR), Espectroscopia Raman, Espectroscopia MÃssbauer, MagnetÃmetro de Amostra Vibrante (VSM) e Microscopia EletrÃnica de TransmissÃo (TEM). As anÃlises de DRX exibiram picos caracterÃsticos da fase de espinÃlio em todas as amostras sintetizadas. O tamanho mÃdio de partÃcula foi obtido por DRX, VSM e TEM e apresentou valor em torno de 10 nm para o M0,5Zn0,5Fe2O4. As imagens de TEM exibiram nanopartÃculas de morfologia cÃbica. Os parÃmetros magnÃticos observados por MÃssbauer e VSM mostraram comportamento superparamagnÃtico para todas as amostras contendo Zn, alÃm de altos valores de magnetizaÃÃo de saturaÃÃo (~55 meu/g) para a amostra Ni0,5Zn0,5Fe2O4. Devido a isto, este nÃcleo magnÃtico foi escolhido para a formulaÃÃo do nanocarreador. Desta forma, este foi inicialmente modificado com Ãcido olÃico. As anÃlises de TG e FTIR evidenciaram a presenÃa de molÃculas de oleato na superfÃcie da nanopartÃcula. AlÃm disso, o coeficiente de revestimento do processo realizado foi 3,7 oleato / nm2. Um estudo de adsorÃÃo da piplartina na nanopartÃcula modificada (NiZn-AO) foi realizado e observou-se relaÃÃo (NiZn-AO : Piplartina) Ãtima de 1 : 2 (m/m). ApÃs o processo adsortivo, o sistema contendo NiZn-AO e piplartina foi revestido com matriz polimÃrica constituÃda de P123 e F127 para conferir biocompatibilidade ao sistema, e formar o nanocarreador. Testes preliminares de hipertermia foram realizados na nanopartÃcula e observou-se que um campo de 126 Oe conduz a geraÃÃo de calor para alcanÃar uma temperatura de 42ÂC, dentro da faixa de hipertermia moderada. Portanto, o nanocarreador formulado apresenta potencial para aplicaÃÃes biomÃdicas. / In this work, nanoparticles of the M0,5Zn0,5Fe2O4 (M = Ni ou Mn) have been prepared by hydrothermal synthesis in mild conditions without any calcinations process. MFe2O4 (M = Zn, Ni or Mn) nanoparticles were also prepared for comparison. The structural and magnetic properties of the ferrites were investigated by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, MÃssbauer spectroscopy, vibrating sample magnetometer (VSM) and Transmission electron microscopy (TEM). XRD analysis showed peaks of the spinel phase for all samples. The average particle size was obtained by XRD, TEM and VSM and values around 10 nm were found for M0,5Zn0,5Fe2O4. TEM images showed particles of cubic morphology. The magnetic parameters observed by MÃssbauer and VSM shown superparamagnetic behavior for the samples containing Zn and high saturation magnetization values (~55 emu/g) for Ni0,5Zn0,5Fe2O4. Due to this, it was chosen for formulating the nanocarrier. Thus, it was first modified with oleic acid. The TG and FTIR analysis revealed the presence of oleate molecules on the surface of the nanoparticle. Furthermore, the coating coefficient of the process carried was 3.7 oleate / nm2. A study of piplartine adsorption on the modified nanoparticle (NiZn-AO) was performed and the optimum relationship (NiZn-AO: piplartine) was 1 : 2 (w / w). After the adsorptive process, the system containing NiZn-AO and piplartine was coated with polymeric matrix consisting of F127 and P123 to confer biocompatibility to the system and form the nanocarrier. Hyperthermia tests were performed in nanoparticles and it was observed that a field of 126 Oe leads to heat generation to attain a temperature of 42ÂC within the range of moderate hyperthermia. Therefore, the fabricated nanocarrier had potential for biomedical applications.