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Made available in DSpace on 2014-10-09T12:23:06Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:09Z (GMT). No. of bitstreams: 1 00622.pdf: 2326364 bytes, checksum: 665ea383abf1ee58d4ae5e2198a0bebb (MD5) / Dissertacao (Mestrado) / IEA/D / Escola Politecnica, Universidade de Sao Paulo - POLI/USP

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Made available in DSpace on 2014-10-09T12:23:06Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:09Z (GMT). No. of bitstreams: 1 00622.pdf: 2326364 bytes, checksum: 665ea383abf1ee58d4ae5e2198a0bebb (MD5) / Dissertacao (Mestrado) / IEA/D / Escola Politecnica, Universidade de Sao Paulo - POLI/USP

Made available in DSpace on 2014-10-09T12:26:20Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:04:18Z (GMT). No. of bitstreams: 0 / Um estudo das propriedades ópticas do cromóforo hipocrelina B (HB) e de seus complexos com os íons lantânio (La3+), európio (Eu3+) e térbio (Tb3+) em soluções em etanol foi realizado. Tal pigmento enquadra-se como um promissor fotossensibilizador de segunda geração dadas suas ótimas propriedades, tais como rápido metabolismo in vivo e principalmente elevado rendimento quântico de geração de oxigênio singleto (FD). O presente trabalho foi desenvolvido em duas etapas: a primeira consistiu do estudo espectroscópico dos complexos de hipocrelina B (HB) com os íons lantanídeos (Ln3+), e a segunda, de testes de PDT in vitro em cultura do fungo Candida albicans. Na primeira etapa do trabalho, a melhor razão molar entre HB e Ln3+ foi verificada através do monitoramento do pico de absorção em maior comprimento de onda de cada um dos complexos. O maior deslocamento do pico de absorção da HB (de 589 nm para 614 nm) foi notado para os complexos com razão de 1 mol de HB para 2 mols de íon lantanídeo. Observou-se que a emissão da HB e de seus complexos ocorre desde cerca de 600 nm até 750 nm. Foi possível, com base nos espectros de absorção e de emissão, calcular os valores de níveis de energia da molécula e de seus complexos. Todos os fotossensibilizadores apresentaram como menor nível de energia valor superior a 0,98 eV, o que é um indício de sua capacidade de geração de oxigênio singleto. Foram determinadas as constantes de dimerização das amostras, de maneira a identificar sua tendência à formação de dímeros ou agregados de ordem superior, e os valores obtidos para a HB e seus complexos com lantânio, európio e térbio foram, respectivamente, de 4,7.104, 3,6.105, 2,1.105 e 1,0.105 M-1. Todas as amostras mostraram-se estáveis perante a ação de luz de 532 nm de até 400 mW/cm2 de intensidade pelo período de uma hora de irradiação. As capacidades de geração de oxigênio singleto das amostras foram determinadas tanto através do método espectroscópico direto (detecção da emissão do oxigênio singleto em torno de 1270 nm) quanto do método químico indireto (variações na absorção em 440 nm do composto RNO). Notou-se que para a HB o método direto indicou haver geração de oxigênio singleto, e o método químico revelou que esta espécie é gerada à taxa de 2,8.10-4 s-1; para HB:La3+ (1:1) obteve-se aumento de 32% na geração de oxigênio singleto em relação à HB, e para HB:La3+ (1:2), determinou-se taxa de 3,0.10-4 s-1 pelo método indireto. Com base nos dados experimentais obtidos, verificou-se que o melhor dentre os complexos estudados foi o HB:La3+ (1:2), sendo este e seu precursor HB então aplicados em testes de PDT antimicrobiana in vitro, constituindo a segunda etapa do trabalho. A concentração de HB ideal para trabalho obtida foi de 10 M. Notou-se eliminação total de microorganismos com apenas 30 segundos de irradiação com LED de 460 nm e intensidade de 333 mW/cm2 tanto para o complexo como para o seu precursor. Porém, com excitação em 660 nm com esta mesma intensidade, apenas HB:La3+ (1:2) se mostrou efetivo, chegando ao efeito fotodinâmico total após 6 minutos de irradiação; a redução causada pela HB no mesmo intervalo de tempo foi bem menos pronunciada, o que comprova a eficiência do fotossensibilizador produzido. / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

The previously unknown chemical and physical properties of the ternary rare-earth inter­metallic compounds, RETGe (RE=Sc, Y, La–Lu; T=Ag, Au), are investigated using a variety of experimental techniques. The RETGe are found to crystallise in three basic different crystal structure types (CaIn2-, Fe2P-, and CeCu2-type derivatives).

In this work we report on physical properties of Nd2RhIn8 and Nd2IrIn8 rare-earth intermetallic compounds from the RmTnX{2n+3m} compound family. The compounds crystallize in the P4/mmm space group. Both compounds are anti-ferromagnetic with Néel temperatures TN of 10.8 K, 12.5 K respectively and their magnetization curves show characterisic step-like transitions at low temperatures. The measured M(T) and/or M(H) magnetization curves were used to determine magnetic phase diagrams for field along the c-axis. The specific heat of Nd2IrIn8 was analyzed at temperatures T<TN with respect to the dimensionality of the magnetic excitations. In the T>TN region the Schottky specific heat and susceptibility were compared to calculations based on the crystal field scheme in Nd2IrIn8 obtained by ab-initio methods. Powered by TCPDF (www.tcpdf.org)

Masters of Science / Rare-earth (RE) compounds have been an attractive subject, based on the unique electronic structures of the rare-earth elements. In particular, the RETX (RE = rare-earth, T = 3d/4d/5d, transition metals, and X = p – block elements) series is a large family of intermetallic compounds which crystallizes in different crystal structure depending on the constituents. Most of these compounds crystalize in the hexagonal, orthorhombic, and tetragonal crystal structure. On the other hand, the family of compounds RET2X2 adopted the tetragonal crystal structure of the ThCr2Si2 or the CaBe2Be2 with different space groups. Owing to the different crystal structure, these compounds show versatile magnetic and electrical properties such as Kondo effect, complex magnetic behaviour, valence fluctuation, unconventional and conventional superconductivity, heavy fermion behaviour, Fermi and non – Fermi liquid behaviour, metamagnetism, spin – glass, memory effect, crystal electric field (CEF), magnetoresistance and magnetocaloric effect. The history of magnetism reveals that it is closely related to practical applications and magnetic materials from the most vital components in many applications. These are memory devices, permanent magnets, transformer cores, magneto-mechanical devices and magneto-electronic devices. Recent additions to this list include magnetic refrigeration through the studies of magnetocaloric effect as well as spintronics. Magnetic refrigeration (MR) is an emerging technology and shows real potential to enter conventional markets and the principles of MR obeys the magnetocaloric effect (MCE), which is based on the effect caused by a magnetic field on the materials that accept the property of varying the magnetic entropy, as well as its temperature when varying the magnetic field. In this thesis, we report giant magnetocaloric effect and magnetic properties of NdPd2Al2 and RECuGa (RE = Nd, Dy, and Ho) compounds. These investigations were done through measurements of X – ray diffraction (XRD), magnetic susceptibility, ((T)), magnetization, (M(H)), isothermal magnetization, (M(H, T)), heat capacity, (Cp(T)) and electrical resistivity, ((T)). MCE has been studied from the isothermal magnetization and heat capacity measurements.The first chapter of the thesis describes the theoretical background from which the experimental results have been analyzed and interpreted. This is followed by the chapter which presents experimental details and methodology carried out in this thesis. Chapter three presents the results and discussion of the transport, magnetic and magnetocaloric properties of NdPd2Al2 compounds. XRD studies confirm the tetragonal CaBe2Ge2 – type structure with space group P4/nmm (No. 129). The results of (T), (T) and Cp(T) indicate a putative antiferromagnetic (AFM) phase transition at low temperature at, TN = 3 K. On the other hand, (T) data at high temperatures follow the Curie – Weiss relationship giving an effective magnetic moment close to that expected for the trivalent Nd3+ ion. The magnetization results indicate metamagnetic – like transition at a low field that bears a first-order character which corroborates with the Below – Arrott plots. Giant MCE was obtained for the NdPd2Al2 compound similar to those reported for potential magnetic refrigerant materials. Chapter four discusses the magnetic and thermodynamic properties of the series of compounds RECuGa where RE = Nd, Dy, and Ho. XRD studies indicate the orthorhombic CeCu2 – type crystal structure with space group Imma (No. 74) for all three compounds. Magnetic measurements indicate a putative AFM phase transition below 𝑇𝑁 = 7.1, 8.5, and 3.7 K for Nd, Dy, and Ho compounds, respectively. The high-temperature (T) data for all three compounds follow the Curie – Weiss relationship giving an effective magnetic moment close to that expected for the trivalent rare-earth ion. Again, large MCE were obtained for all three compounds similar to those reported for materials that can be used as magnetic refrigerant materials.

Up-conversion (UC) in rare-earth co-doped fluorides to convert diode laser light in the near infrared to red, green and blue visible light is applied to make possible high performance emissive displays. The infrared-to-visible UC in the materials we study is a sequential form of non-linear two photon absorption in which a strong absorbing constituent absorbs two low energy photons and transfers this energy to another constituent which emits visible light. Some of the UC emitters' most appealing characteristics for displays are: a wide color gamut with very saturated colors, very high brightness operation without damage to the emitters, long lifetimes and efficiencies comparable to those of existing technologies. Other advantages include simplicity of fabrication, versatility of operating modes, and the potential for greatly reduced display weight and depth. Thanks to recent advances in material science and diode laser technology at the excitation wavelength, UC selected materials can be very efficient visible emitters. However, optimal UC efficiencies strongly depend on chosing proper operating conditions. In this thesis, we studied the conditions required for optimization. We demonstrated that high efficiency UC depends on high pump irradiance, low temperature and low scattering. With this understanding we can predict how to optimally use UC emitters in a wide range of applications. In particular, we showed how our very efficient UC emitters can be applied to make full color displays and very efficient white light sources.