Orientador: Kleber Roberto Pirota / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-20T23:05:11Z (GMT). No. of bitstreams: 1 Macedo_GleyguestoneLopesde_M.pdf: 4864713 bytes, checksum: a6eff7f69f1d64274cacac58dc118e5c (MD5) Previous issue date: 2012 / Resumo: Neste trabalho, seguindo uma nova rota de síntese, foram produzidas três amostras de nanopartículas do tipo dímero de prata com magnetita (Ag-Fe3O4), onde a única diferença entre elas é no valor da concentração de partículas de prata utilizadas na síntese. As amostras de tipo dímero possuem concentrações de prata iguais a 0,003 g/mL, 0,007 g/mL e 0,01 g/mL e foram chamadas, respectivamente, de AgFeO_1, AgFeO_2 e AgFeO_3. Sobre estes sistemas realizaram-se medidas da magnetização do tipo Zero Field cooling/Field cooling (ZFC-FC) onde se observou nos três sistemas um aumentou brusco da temperatura de irreversibilidade (Tirr) da magnetita quando unida a prata. Também se observou que somente na amostra com menor concentração de prata sofre um grande aumento em sua temperatura de bloqueio (T B), aproximadamente 130K, que pode ser devido a fatores como aumento do tamanho da partícula de magnetita contida no dímero, aglomerações e interações entre particulas. Porém, através de medidas de dicroísmo circular magnético de raios-X (XMCD) observou-se que com a união da prata a magnetita provoca nesta um aumento de seu momento orbital sendo mais intenso para a amostra com menor concentração de prata (AgFeO_1). Tal resultado pode explicar o aumento em Tirr e TB, já que o momento orbital é diretamente proporcional à anisotropia magnética. Por fim, gostaria de salientar que, em conjunto com meu orientador (Prof. Kleber Roberto Pirota) foi decidido optar por uma estrutura na qual inicio com descrição das bases teóricas de interesse, logo comento rapidamente sobre as técnicas experimentais utilizadas e, finalmente, anexo os trabalhos publicados. Porém, como alguns resultados obtidos neste trabalho ainda não foram publicados, decidi resumir-los no final da tese (capítulo 4) / Abstract: In this work, following a new synthesis route, three samples were produced nanoparticle type silver dimer with magnetite (Ag-Fe3O4), where the only difference between them is the value of the concentration of silver particles used in the synthesis. Samples of dimer type silver concentrations have equal 0,003 g/mL, 0,007 g/mL e 0,01 g/mL and were named, respectively AgFeO_1, and AgFeO_2 AgFeO_3. On these systems were expressed as the magnetization of the type Zero Field cooling/Field cooling (ZFC-FC) where it was observed in all three systems a sudden increase in temperature of irreversibility (T IRR) of magnetite attached to silver. It was also observed that the sample with only low silver concentration undergoes a sharp increase in its temperature block (TB), to approximately 130K, which may be due to factors such as increasing the particle size of magnetite contained in the dimer interactions and agglomerations. However, through measures of magnetic circular dichroism X-ray (XMCD) observed that with the union of silver magnetite causes this increased their orbital momentum being more intense for the sample with lower concentration of silver (AgFeO_1). This result may explain the increase in TB and TIRR, since the orbital momentum is directly proportional to the magnetic anisotropy. Finally, let me emphasize that, together with my advisor (Prof. Kleber Roberto Pirota) it was decided to opt for a structure in which beginning with a description of the theoretical bases of interest, just comment quickly on the experimental techniques used and eventually annex published works. However, as some results of this work have not yet been published, I decided to summarize them at the end of the thesis (Chapter 4) / Mestrado / Física / Mestre em Física

>Magister Scientiae - MSc / Crude extracts from Myrothamnus flabellifolius were fractionated through variouschromatography techniques in order to achieve satisfactory separations. Two compounds, arbutin and lupeol, were isolated from the butanol and ethyl acetate extracts, respectively. Structural elucidation of the compounds was carried out on the basis of 1H and 13C NMR spectroscopy. It was the first time that lupeol had been isolated from M. flabellifolius.The water extract was found to contain heterogeneous pectic polysaccharides. Three polysaccharide fractions were separated from the water extract, namely; MPS, MPS-I and MPS-II. The predominant fraction was found to be MPS, with a molecular weight distribution of 2 X 105 Da. The polysaccharides were made up the following monosaccharides; arabinose, rhamnose, xylose, mannose, galactose and glucose. Monosaccharide composition was determined through acid hydrolysis at high temperatures, followed by GC analysis. The linkage analysis was carried out by GC-MS, following partial methylation of the polysaccharides. The use of human serum albumin (HSA) following its anchoring on magnetic nanoparticles, in order to isolate targeted saponins from Sutherlandia frutescens led to successful isolation of four saponins, namely; sutherlandiosides A-D. The saponins showed great affinity to bind to the HSA.

In this dissertation, I present the results of a systematic study on novel multifunctional nanostructure systems for magnetic hyperthermia applications. All the samples have been synthesized, structurally/magnetically characterized, and tested for magnetic hyperthermia treatment at the Functional Materials Laboratory of the University South Florida. This work includes studies on four different systems: (i) Core/shell Fe/γ-Fe2O3 nanoparticles; (ii) Spherical and cubic exchange coupled FeO/Fe3O4 nanoparticles; (iii) Fe3O4 nano-octopods with different sizes; (iv) High aspect ratio FeCo nanowires and Fe3O4 nanorods. In particular, we demonstrated the enhancement of the heating efficiency of these nanostructures by creating monodisperse and highly crystalline nanoparticles, and tuning their magnetic properties, mainly their saturation magnetization (MS) and effective anisotropy, in controlled ways. In addition, we studied the influence of other parameters, such as the size and concentration of the nanoparticles, the magnitude of the applied AC magnetic field, or different media (agar vs. water), on the final heating efficiency of these nanoparticles. For the core/shell Fe/γ-Fe2O3 nanoparticles, a modest heating efficiency has been obtained, resulting mainly from the strong reduction in MS caused by the shrinkage of the core with time. However, for sizes above 14 nm, the shrinkage process is much slower and the obtained heating efficiency is better than the one exhibited by conventional solid nanoparticles of the same size. In the case of the exchange-coupled FeO/Fe3O4 nanoparticles, we successfully created two sets of comparable particles: spheres with 1.5 times larger MS than the cubes, and cubes with 1.5 times larger effective anisotropy than the spheres, while keeping the other parameters the same. Our results show that increasing the effective anisotropy of the nanoparticles gives rise to a greater heating efficiency than increasing their MS. The Fe3O4 nano-octopods, with enhanced surface anisotropy, present better heating efficiency than their spherical and cubic nanoparticles, especially in the high field region, and we have shown that by tuning their size and the effective anisotropy, we can optimize their heating response to the applied AC magnetic field. For magnetic fields, smaller than 300−400 Oe we found that the smallest nano-octopods give the best heating efficiency. Yet if we increase the AC field value, the bigger octopods show an increased heating efficiency and become more effective. Finally, the FeCo nanowires and Fe3O4 nanorods exhibit enhanced heating efficiency with increasing aspect ratio when aligned in the direction of the applied AC magnetic field, due to the combined effect of shape anisotropy and dipolar interactions. Of all the studied systems, these 1D high aspect ratio nanostructures have displayed the highest heating rates. All of these findings point toward an important fact that tuning the structural and magnetic parameters in general, and the effective anisotropy in particular, of the nanoparticles is a very promising approach for improving the heating efficiency of magnetic nanostructures for enhanced hyperthermia.

Lignin is one of the most common biopolymers in the world. Together with cellulose andhemicellulose it constitutes the fibers in the wood. It has a high molecular weight due to its complexstructure consisting of crossed-linked phenolic monomers and is concatenated with different types ofcarbon and ether bonds.In pulping processes, lignin is extracted in large quantities and used on site to produce energy for milloperations but is also removed as a waste product. This enables a product with high resources andaccessibility due to lignin's diverse properties. Therefore, lignin has the potential to be utilized inhigher value applications such as polymer materials, as well as a source of platform chemicals. Atpresent, the value applications of lignin are promising as additives for different kinds of productssuch as emulsifiers and especially as biofuel due to lignin's high carbon content.New technologies for development for utilization lignin are emerging for different kinds ofapplications due to lignin’s biocompatibility. The possibilities of lignin combined with existingresearch of nanotechnology gives opportunities to improve biomedical applications. By designinglignin derived nanoparticles with incorporated magnetic materials, the NPs obtainsuperparamagnetic properties which can be utilized for target drug delivery. This could be promisingagainst intractable cancer such as pancreatic cancer.This report presents a protocol for developing magnetic lignin nanoparticles from the lowestmolecular weight kraft lignin fractions of eucalyptus (hardwood) and spruce (softwood). By a methodof self-assembly, particles with a doughnut and core-shell morphology, as indicated by SEM and TEM,were yielded with a 10-50μL content of water-stabilized magnetite. The particle size distribution andzeta potential were determined by DLS and the possibility of the particles being suitable forbiomedical applications was discussed.

In this thesis I am presenting a detailed study to optimize the deposition of magnetic molecules and gold nanoparticles in atomically flat surfaces by self-assembling them from solution. Epitaxially grown and atomically flat gold surface on mica is used as substrate for this study. These surfaces have roughness of the order one tenth of a nanometer and are perfect to image molecules and nanoparticles in the 1-10 nanometers range. The purpose of these studies is to find the suitable parameters and conditions necessary to deposit a monolayer of nano-substance on chips containing gold nanowires which will eventually be used to form single electron transistors by electromigration breaking of the nanowire. Maximization of the covered surface area is crucial to optimize the yield of finding a molecule/nanoparticle near the gap formed in the nanowire after electromigration breaking. Coverage of the surface by molecules/nanoparticles mainly depends on the deposition time and concentration of the solution used for the self-assembly. Deposition of the samples under study was done for different solution concentrations and deposition times until a self-assembly monolayer covering most of the surface area is obtained. Imaging of the surfaces after deposition was done by tapping-mode AFM. Analysis of the AFM images was performed and deposition parameters (i.e. coverage or molecule/particle size distribution) were obtained. The subjects of this investigation were a molecular polyoxometalate, a single-molecule magnet and functionalized gold nanoparticles. The obtained results agree with the structure of each of the studied systems. Using the optimized deposition parameters found in this investigation, single-electron transport measurements have been carried out. Preliminary results indicate the right choice of the deposition parameters.

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Nanoparticles can be used as building blocks of materials. Properties of such materials depend on the organization of the constituent particles. Thus, control over particle organization enables control over material properties. However, robust and scalable methods for arranging nanoparticles are still lacking. This dissertation explores the use of an externally applied magnetic field to organize magnetic nanoparticles into microstructures of desired shape. It extends to proofs of concept towards applications in material design and tissue engineering. First, external control over dipolar self-assembly of magnetic nanoparticles (MNPs) in a liquid dispersion is investigated experimentally. Scaling laws are derived to explain experimental observations, correlating process control variables to microstructure morphology. Implications of morphology on magnetic properties of such structures are then explored computationally. Specifically, a method is proposed wherein superparamangetic nanoparticles, having no residual magnetization, can be organized into anisotropic structures with remanence. Another application explores the use of magnetic forces in organizing human cells into three-dimensional (3D) structures of desired shape and size. When magnetized cells are held in place for several days, they are seen to form inter-cellular contacts and organize themselves into tight clusters. This provides a method for 3D tissue culture without the use of artificial scaffolding materials. Finally, a method to pattern heterogeneities in the stiffness of an elastomer is developed. This makes use of selective inhibition of the catalyst of crosslinking reactions by magnetite nanoparticles. The last chapter discusses future possibilities. / Ph. D.

Macromolecular complexes of anionic-nonionic block copolymers and cationic antibiotic aminoglycosides have been formed by electrostatic condensation. Amphiphilicity of the complexes was introduced into the shells by incorporating a hydrophobic poly(propylene oxide) segment into the block copolymer. The resulting particles have an average hydrodynamic diameter of ~ 200 nm and contain up to 30-40 % of the drug payload. In vitro efficacies of such nanostructures in reduction of intracellular pathogens like Salmonella, Listeria, and Brucella were demonstrated. Current effort focuses on translation of this nano-drug delivery concept to in vivo model of intracellular infectious diseases. Atom transfer radical polymerization (ATRP) was utilized to prepare well-defined polymeric dispersion stabilizers that readily adsorb onto metal oxide surfaces. Two unimolecular bis(phosphonate) ATRP initiators were designed and prepared in good yield. These special initiators were successfully used to initiate polymerization of poly(N-isopropylacrylamide) (PNIPAM) in a controlled manner yielding PNIPAM with a bis(phosphonate) moiety at one terminus. The polymers readily adsorbed onto magnetite nanoparticle surfaces, thus creating thermosensitive magnetic nanostructures that form nanosized clusters upon heating above the lower critical solution temperature of PNIPAM. It is envisioned that modularity of this approach, relying on the applicability of ATRP to polymerize a vast array of monomers, could be used to prepare a library of polymeric shells for magnetic iron oxide nanoparticles. Medical intervention in drug delivery that includes detectability of drug carriers is greatly desirable. A real-time assessment of disease prognosis could be highly beneficial for developing personalized treatment strategies. As an example of this conceptual innovation, block ionomer functionalized magnetite complexes were synthesized and investigated as carriers for delivery of aminoglycosides into phagocytic cells for treatment of intracellular bacterial infections. The ionic block of copolymer contains multiple carboxylates for binding onto the iron oxide surface. The remaining unbound carboxylate anions were used to complex with cationic gentamicin in nanoshells of these complexes. The iron oxide particle core provides an imaging modality and serves as a pseudo-crosslinking site to enhance stabilities of the polyelectrolyte complexes, thus preventing them from disintegrating in the physiological environment. Currently, these hybrid complexes are being investigated in possible pharmaceutical formulations to eradicate intracellular pathogens in animal models. / Ph. D.

Master of Science / Department of Electrical and Computer Engineering / Punit Prakash / Thermal therapies employing interstitial microwave applicators for hyperthermia or ablation are in clinical use for treatment of cancer and benign disease in various organs. However, treatment of targets in proximity to critical structures with currently available devices is risky due to unfocused deposition of energy into tissue. For successful treatment, complete thermal coverage of the tumor and margin of surrounding healthy tissue must be achieved, while precluding damage to critical structures. This thesis investigates two approaches to increase precision of microwave thermal therapy. Chapter 2 investigates a novel coaxial antenna design for microwave ablation (MWA) employing a hemi-cylinderical reflector to achieve a directional heating pattern. A proof of concept antenna with an S₁₁ of -29 dB at 2.45 GHz was used in ex vivo experiments to characterize the antennas’ heating pattern with varying input power and geometry of the reflector. Ablation zones up to 20 mm radially were observed in the forward direction, with minimal heating (less than 4 mm) behind the reflector. Chapter 3 investigates the use of magnetic nanoparticles (MNP) of varying size and geometry for enhancing microwave tissue heating. A conventional dipole, operating at 2.45 GHz and radiating 15 W, was inserted into a 20 mm radius sphere of distributed MNPs and heating measurements were taken 5 mm, 10 mm, and 15 mm radially away. A heating rate of 0.08°C/s was observed at 10 mm, an increase of 2-4 times that of the control measurement. These approaches provide strong potential for improving spatial control of tissue heating with interstitial and catheter-based microwave antennas.

Master of Science / Department of Anatomy and Physiology / Deryl L. Troyer / There is renewed interest in magnetic hyperthermia as a treatment modality for cancer, especially when it is combined with other more traditional therapeutic approaches, such as the co-delivery of anticancer drugs or photodynamic therapy. The influence of bimagnetic nanoparticles (MNPs) combined with short external alternating magnetic field (AMF) exposure on the growth of subcutaneous mouse melanomas (B16-F10) was evaluated. Bimagnetic Fe/Fe3O4 core/shell nanoparticles were designed for cancer targeting after intratumoral or intravenous administration. Their inorganic center was protected against rapid biocorrosion by organic dopamine-oligoethylene glycol ligands. TCPP (4-tetracarboxyphenyl porphyrin) units were attached to the dopamine-oligoethylene glycol ligands. The magnetic hyperthermia results obtained after intratumoral injection indicated that micromolar concentrations of iron given within the modified core-shell Fe/Fe3O4 nanoparticles caused a significant anti-tumor effect on murine B16-F10 melanoma with three short 10-minute AMF exposures. There is a decrease in tumor size after intravenous administration of the MNPs followed by three consecutive days of AMF exposure. These results indicate that intratumoral administration of surface-modified MNPs can attenuate mouse melanoma after AMF exposure. Moreover, intravenous administration of these MNPs followed by AMF exposure attenuates melanomas, indicating that adequate amounts of TCPP-labeled stealth Fe/Fe3O4 nanoparticles can accumulate in murine melanoma after systemic delivery to allow effective magnetic hyperthermic therapy in a rodent tumor mode.