Aseptic loosening of artificial joints is caused by an osteolytic reaction to wear debris mediated by macrophages and other cells. Imaging these wear particles within cells can be a key process in understanding particle-cell interactions. However, the compounds used in surgical implants are not easily visualised as no tagging molecule can be added without altering the properties of the material. We were interested in using a label free optical technique known as coherent anti-Stokes Raman scattering spectroscopy (CARS) to image these particles in cells. In this thesis we studied how to use CARS to image physiologically relevant wear particles within cells. We characterised the responses from our CARS system and found them to be in good agreement to the Raman spectra we obtained for the same materials. We showed that the forward scattered CARS signal was consistently larger than the backwards scattered signal for the same size particles, and also generated a larger contrast, especially between sub-micron sized particles and the non-resonant background. Wear particles of polyethylene isolated from a pin-on-plate wear simulator were shown to be in a similar size range to those retrieved from revision tissue. When incubated in our model macrophage cells we were able to image areas of CARS signal that indicated the location of these particles in the cell. Furthermore, using multiple CARS images taken at different Raman resonances we were able to distinguish between three different polymeric compounds added to cells, showing the specificity of the technique. The inherent 3D sectioning capabilities of multiphoton microscopy were used to generate projected images of the cells and contents, as well as estimating the particle loads within cells. These results show that CARS could be an important tool in imaging intra-cellular polyethylene and characterising the interactions of wear particles with cells and the surrounding tissue.

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Made available in DSpace on 2014-10-09T12:28:19Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:45Z (GMT). No. of bitstreams: 0 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP / FAPESP:08/01954-0

Made available in DSpace on 2014-10-09T12:35:56Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:34Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:28:19Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:45Z (GMT). No. of bitstreams: 0 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / O estudo desenvolvido nessa dissertação foi dividido em dois momentos. Na primeira parte foi apresentado a realização de uma calibração independente do sistema LIDAR Raman de vapor d\'água instalado no CLA seguindo uma metodologia desenvolvida na Howard University, baseada em uma análise cuidadosa da eficiência óptica dos componentes do sistema tendo como objetivo determinar essa eficiência e apresentar a resposta espectral do sistema. Após esse estudo, que permitiu obter um melhor entendimento da área instrumental do sistema, é apresentado, na segunda parte, uma análise preliminar das propriedades ópticas dos aerossóis na troposfera por meio da avaliação de alguns parâmetros como, por exemplo, os perfis verticais de extinção desses aerossóis, a LR e a SR, utilizando um sistema LIDAR Raman móvel desenvolvido pela Raymetrics Lidar Systems durante campanhas realizadas em alguns institutos de pesquisa no Estado de São Paulo. / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP / FAPESP:08/01954-0

Made available in DSpace on 2014-10-09T12:35:56Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:34Z (GMT). No. of bitstreams: 0 / Lasers operando nas regiões espectrais do azul e do amarelo-laranja foram recentemente requisitados pelo mercado de aplicações quer para melhorar as tecnologias já conhecidas ou para possibilitar a criação de novas. Isso é devido às propriedades destas regiões espectrais, com o azul trazendo características tais como fótons de alta energia e feixes limitados por difração menores, enquanto a faixa do amarelo-laranja é ainda uma região espectral difícil de se atingir e não foi totalmente acessada ou nem mesmo acessada por fontes de luz laser eficientes. Aplicações dos lasers azuis são encontradas em tecnologias de alta densidade de armazenamento, displays a laser, sistemas LIDAR, pinças ópticas e uma longa série de aplicações que exigem alta precisão. Os lasers amarelo-laranja também têm aplicações importantes, destacando-se aplicações em cirurgia oftalmológica a laser, em displays de cores reais e como estrela guia (excitando linhas de sódio na atmosfera). A investigação de lasers de quase três níveis e laser Raman de Nd:YLF foi realizada neste trabalho. A finalidade é de propor fontes laser de alta potência e eficientes emitindo no azul e no amarelo para suprir as aplicações. Eficiência e potências de saída da ordem de Watt foram demonstradas para um laser de Nd:YLF emitindo em 908 nm assim como no segundo harmônico em 454 nm. Além disso, lasers Raman de Nd:YLF/BaWO4 e Nd:YLF/KGW foram demonstrados atingindo alguns Watts de potência de saída em regime quasi-CW e CW, com boas qualidades de feixe (M2 2) e em oito comprimentos de onda diferentes: 1147 nm, 1163 nm, 1167 nm , 549 nm, 552 nm, 573 nm, 581 nm e nm 583. Por fim, uma luminescência azul originada em alguns cristais Raman, durante a oscilação Stokes, teve sua origem e seus efeitos colaterais para lasers (perdas e calor adicionais) minuciosamente caracterizados. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Hydroxycalciomicrolite, Ca1.5Ta2O6(OH) is a new microlite-group mineral found in the Volta Grande pegmatite, Nazareno, Minas Gerais, Brazil. It occurs as isolated octahedral and as a combination of octahedral and rhombic dodecahedral crystals, up to 1.5 mm in size. The crystals are yellow and translucent, with a white streak and vitreous to resinous lustre. The mineral is brittle, with a Mohs hardness of 56. Cleavage is not observed and fracture is conchoidal. The calculated density is 6.176 g cm(3). Hydroxycalciomicrolite is isotropic, n(calc). = 2.010. The infrared and Raman spectra exhibit bands due to OH stretching vibrations. The chemical composition determined from electron microprobe analysis (n = 13) is (wt.%): Na2O 0.36(8), CaO 15.64(13), SnO2 0.26(3), Nb2O5 2.82(30), Ta2O5 78.39(22), MnO 0.12(2), F 0.72(12) and H2O 1.30 (from the crystal structure data), O = F -0.30, total 99.31(32), yielding an empirical formula, (Ca1.48Na0.06Mn0.01)(Sigma 1.55)(Ta1.88Nb0.11Sn0.01)S2.00O6.00[(OH)(0.76)F0.20O0.04]. Hydroxycalciomicrolite is cubic, with unit-cell parameters a = 10.4205(1) angstrom, V = 1131.53(2) angstrom(3) and Z = 8. It represents a pyrochlore supergroup, microlite-group mineral exhibiting P4(3)32 symmetry, instead of Fd (3) over barm. The reduction in symmetry is due to long-range ordering of Ca and vacancies on the A sites. This is the first example of such ordering in a natural pyrochlore, although it is known from synthetic compounds. This result is promising because it suggests that other species with P4(3)32 or lower-symmetry space group can be discovered and characterized.

We present X-ray diffraction and Raman spectroscopy investigations of a (100)-oriented (AlxGa1–x)2O3 thin film on MgO (100) and bulk-like ceramics in dependence on their composition. The thin film grown by pulsed laser deposition has a continuous lateral composition spread allowing to determine precisely the dependence of the phonon mode properties and lattice parameters on the chemical composition. For x<0.4, we observe the single-phase b-modification. Its lattice parameters and phonon energies depend linearly on the composition. We determined the slopes of these dependencies for the individual lattice parameters and for nine Raman lines, respectively. While the lattice parameters of the ceramics follow Vegard’s rule, deviations are observed for the thin film. This deviation has only a small effect on the phonon energies, which show a reasonably good agreement between thin film and ceramics.

Coral reefs are an important element of marine ecosystem that are critical to maintain a healthy environment. Unfortunately, in recent years coral reefs are doing poorly and many in parts of the ocean are simply dying. Therefore, study of coral’s structural response to external loads could answer what will happen with their structures, while they exhibit different types of loading. Therefore, the proposition of using in-situ micro-Raman spectroscopy to study skeletons of Acropora cervicornis was used. Coral skeleton samples I subjected to mechanical loading studied their vibrational properties by exciting the material with 532nm visible light. A uniaxial compressive load I applied using a MTS universal testing machine and then using the Raman Spectroscopy to study the vibrational response of coral skeletons. Indentations used Vickers Hardness tester and performed 2D mapping of the coral structure around the indentation. If it’s expected that as a result of the proposed research the better understanding of structural stability of the Acropora Cervicornis coral skeletons will be achieved.

Functional data analysis (FDA) studies data in the form of measurements over a domain as whole entities. Our first focus is on the post-hoc analysis with pairwise and contrast comparisons of the popular functional ANOVA model comparing groups of functional data. Existing contrast tests assume independent functional observations within group. In reality, this assumption may not be satisfactory since functional data are often collected continually overtime on a subject. In this work, we introduce a new linear contrast test that accounts for time dependency among functional group members. For a significant contrast test, it can be beneficial to identify the region of significant difference. In the second part, we propose a non-parametric regression procedure to obtain a locally sparse estimate of functional contrast. Our work is motivated by a biomedical study using Raman spectroscopy to monitor hemodialysis treatment near real-time. With contrast test and sparse estimation, practitioners can monitor the progress of the hemodialysis within session and identify important chemicals for dialysis adequacy monitoring. In the third part, we propose a functional data model for degradation analysis of functional data. Motivated by degradation analysis application of rechargeable Li-ion batteries, we combine state-of-the-art functional linear models to produce fully functional prediction for curves on heterogenous domains. Simulation studies and data analysis demonstrate the advantage of the proposed method in predicting degradation measure than existing method using aggregation method. / Doctor of Philosophy / Functional data analysis (FDA) studies complex data structure in the form of curves and shapes. Our work is motivated by two applications concerning data from Raman spectroscopy and battery degradation study. Raman spectra of a liquid sample are curves with measurements over a domain of wavelengths that can identify chemical composition and whose values signify the constituent concentrations in the sample. We first propose a statistical procedure to test the significance of a functional contrast formed by spectra collected at beginning and at later time points during a dialysis session. Then a follow-up procedure is developed to produce a sparse representation of the contrast functional contrast with clearly identified zero and nonzero regions. The use of this method on contrast formed by Raman spectra of used dialysate collected at different time points during hemodialysis sessions can be adapted for evaluating the treatment efficacy in real time. In a third project, we apply state-of-the-art methodologies from FDA to a degradation study of rechargeable Li-ion batteries. Our proposed methods produce fully functional prediction of voltage discharge curves allowing flexibility in monitoring battery health.