Magnetic nanoparticles are of great interest for a wide range of applications. This work has focused on three primary forms of iron based nanoparticles and combinations thereof: α-iron, iron oxide, and iron carbide or cementite. The synthesis of several core-shell particles including cementite-iron oxide, α-iron-cementite, and α-iron-iron oxide was accomplished through reverse micelle routes and high temperature decomposition of iron pentacarbonyl in various media. Structural analysis to confirm the structures was performed using extended x-ray absorption fine structure (EXAFS) techniques. A rapid characterization technique was developed utilizing a correlation between Fourier transform infrared spectroscopy and EXAFS to determine the full metal cation distribution between the octahedral and tetrahedral sites in manganese zinc ferrite (MZFO). This method was then used to show that the initial Fe3+ to Fe2+ ratio in MZFO synthesis could be used to design a desired cation distribution and affected the zinc incorporation levels into the resultant ferrite. Functionalization of nanoparticles for aqueous dispersions and ferrofluids has varying degrees of importance, depending on the application. In applications such as magnetic resonance imaging (MRI) where the targets are biological systems, it was important to produce solutions that will not aggregate in the high magnetic field of the MRI. It was also vital to characterize decomposition mechanisms and products that would be presented to the body after use as a contrast agent. This work has provided insight into both the preparation of magnetic samples for MRI applications and implications of the biocompatibility of reactive and decomposition products. Three successful methods of forming dispersions that would not aggregate in the high magnetic field of the MRI were comprised of cysteine/polyethylene glycol (PEG), PEG based ferrofluids, and dopamine/PEG. The dopamine functionalization however showed reactivity with the iron/iron oxide nanoparticles and led to the formation of the cytotoxic dopamine quinone and resulted in the destruction of the nanoparticles. Using all three types of dispersions to compare the iron based nanomaterials, the MRI measurements concluded with the iron oxide ferrofluid yielding the highest R2 enhancement.

Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.

Les gliomes sont des tumeurs agressives de mauvais pronostic, très angiogéniques et infiltrantes ce qui rend leur exérèse particulièrement difficile. Vu les limites des techniques actuelles d’imagerie, nous avons proposé la spectro-imagerie Infrarouge à Transformée de Fourier (IRTF), d’une résolution spatiale de 6 µm, pour apporter une information moléculaire à l’examen histologique actuel des gliomes. Nos travaux ont été fondés sur la recherche de paramètres moléculaires des vaisseaux sanguins, notamment sur la base des contenus de leur membrane basale. Celle-ci subit des altérations dûes au stress angiogénique tumoral. Nous avons mis en évidence des altérations de la structure secondaire des protéines (tels les collagènes) des vaisseaux sanguins au cours de la croissance de la tumeur. Nous avons aussi évalué les modifications des chaines d’acides gras des phospholipides membranaires, qui révélent un degré d’insaturation plus important pour les vaisseaux tumoraux. Ensuite, sur un modèle de gliome murin, nous avons établi une méthode efficace de classification des capillaires sanguins sur la base d’absorptions de leurs contenus glucidiques et lipidiques, permettant de discriminer totalement les capillaires sains et tumoraux. La combinaison de ces paramètres a été mise à profit pour assurer une histopathologie moléculaire des gliomes humains. Nos résultats ont démontré qu’il est possible de différencier entre la vasculature saine et tumorale sur ces gliomes humains, ce qui permet une bonne délimitation des zones tissulaires correspondantes. Cette technique pourrait devenir un outil analytique fiable, rapide d’une durée compatible avec la chirurgie et donc très utile pour les neurochirurgiens. / Malignant gliomas are very aggressive tumors with poor prognosis, highly angiogenic and invasive into the surrounding brain parenchyma, making their resection very difficult. Regarding the limits of current imaging techniques, we have proposed Fourier Transform Infrared (FTIR) spectro-imaging, with a spatial resolution of 6 µm, to provide molecular information for the histological examination of gliomas. Our work was based on the research of molecular parameters of blood vessels, notably on the basis of the contents of their basement membrane, which undergoes changes due to tumor angiogenic stress. We have identified alterations of the secondary structure of proteins (such as collagen) in blood vessels during tumor growth. We have also assessed the changes in fatty acyl chains of membrane phospholipids, which revealed a higher unsaturation level in tumor vessels. Then, on a murine glioma model, we have established an efficient method of blood vessels classification based on their carbohydrates and fats contents, allowing the differentiation between healthy and tumor blood vessels. The combination of these parameters was used to provide a molecular histopathology for the study of human gliomas. Our results have demonstrated the feasibility of differentiating between healthy and tumor vasculature in these human gliomas, which help delimitating areas of corresponding tissue. This technique could become a reliable and fast analytical tool, with duration compatible with the surgery and thus very useful for neurosurgeons.

Les contaminations par les moisissures représentent un problème majeur au sein de l'industrie agroalimentaire, pharmaceutique, cosmétique, et dans le secteur médical. Actuellement, l'identification des champignons filamenteux est basée sur l'analyse des caractéristiques phénotypiques, nécessitant une expertise et pouvant manquer de précision, ou sur les méthodes moléculaires, coûteuses et fastidieuses. Dans ce contexte, l'objectif de cette étude a consisté à développer un protocole simple et standardisé à l'aide de la spectroscopie infrarouge à transformée de Fourier (IRTF) combinée à une méthode d'analyse chimiométrique, proposant une méthode alternative pour l'identification rapide des moisissures. Au total, 498 souches de champignons filamenteux (45 genres et 140 espèces) ont été analysées à l'aide d'un spectromètre IRTF à haut débit. L'analyse discriminante des moindres carrés partiels (PLS -DA), méthode chimiométrique supervisée, a été appliquée à chaque spectre dans les gammes spectrales 3200-2800 et 1800-800 cm-1. Différents modèles de calibration ont été construits à partir de 288 souches, ceci en cascade de la sous-division jusqu'à l'espèce en se basant sur la taxonomie actuelle. La prédiction des spectres en aveugle, obtenus à partir de 105 souches, au niveau du genre et de l'espèce est respectivement de 99,17 % et 92,3 %. La mise en place d'un score de prédiction et d'un seuil a permis de valider 80,22 % des résultats. L'implémentation d'une fonction de standardisation (SF) a permis d'augmenter le pourcentage de spectres bien prédits, acquis sur un autre instrument, de 72,15 % (sans fonction) à 89,13 %, validant la transférabilité de la méthode. Puisqu'une biomasse mycélienne suffisante peut être obtenue après 48h de culture et que la préparation des échantillons implique l'utilisation d'un protocole simple, la spectroscopie IRTF combinée à la PLS-DA apparaît comme une méthode rapide et peu coûteuse, ce qui la rend particulièrement attractive pour l'identification des champignons filamenteux au niveau industriel. Les résultats obtenus placent la spectroscopie IRTF parmi les méthodes analytiques prometteuses et avant-gardistes, possédant un haut pouvoir discriminant et une forte capacité d'identification, en comparaison avec les techniques conventionnelles. / Mold contaminants represent a major problem in various areas such as food and agriculture, pharmaceutics, cosmetics and health. Currently, molds identification is based either on phenotypic characteristics, requiring an expertise and can lack accuracy, or on molecular methods, which are quite expensive and fastidious. In this context, the objective was to develop a simple and standardized protocol using Fourier transform infrared (FTIR) spectroscopy combined with a chemometric analysis, allowing to implement an alternative method for rapid identification of molds. In total, 498 fungal strains (45 genera and 140 species) were analyzed using a high-throughput FTIR spectrometer. Partial Least Squares Discriminant Analysis (PLS-DA), a supervised chemometrics method, was applied to each spectrum in the spectral ranges 3200-2800 and 1800-800 cm-1 for the identification process. Using 288 strains, different calibration models were constructed in cascade and following the current taxonomy, from the subphylum to the species level. Blind prediction of spectra from 105 strains at the genus and species levels was achieved at 99.17 % and 92.3% respectively. The establishment of a prediction score and a threshold permitted to validate 80.22% of the obtained results. The implementation of a standardization function (SF) permitted to increase the percentage of well predicted spectra from strains analyzed using another instrument from 72.15% (without SF) to 89.13% and permitted to verify the transferability of the method. Since sufficient mycelial biomass can be obtained at 48h culture and sample preparation involved a simple protocol, FTIR spectroscopy combined with PLS-DA is a very rapid and cost effective method, which could be particularly attractive for the identification of moulds at the industrial level. The results obtained places FTIR spectroscopy among the avant-garde promising analytical approaches, with high discriminant power and identification capacity, compared to conventional techniques.

<p>Dioxins and poly-chlorinated biphenyl (PCB) compounds are high priority organic pollutants which are similar in structure and well known for their toxicity, bioaccumulation and persistence in the environment. Dioxins and PCBs have a high affinity for certain types of clay minerals. However, the molecular mechanism for the observed high affinity of these compounds to clay minerals is not well understood and has been the main focus of this research work. The mechanisms that govern dioxin-clay and PCB-clay interactions were investigated from two perspectives. First, the influence of selected properties clay minerals on dioxin sorption was investigated via in-situ spectroscopic techniques (ATR-FTIRand Raman) structural (XRD) and macroscopic batch sorption methods using dibenzo-p-dioxin (DD) as a model solute. Second, the influence of solute properties, especially position and degree of chlorination and molecular planarity, on sorption was investigated.</p> <p> Smectites, especially, Cs-saponite effectively adsorbs dibenzo-p-dioxin (DD) from water with values reaching 10,000 mg kg^-1, or one weight percent which greatly exceeds that by other naturally occurring sorbents such as soil organic matter. Adsorption was promoted by clay interlayer exchangeable cations with low hydration energies, and by smectites in which negative charge in the smectite originate from the tetrahedral siloxane sheets. IR-active bands of DD sorbed to saponite in the 1280 to 1500 cm^-1region were perturbed compared to the ‘reference’ IR spectra. Combined batch sorption, XRD and spectroscopic data confirm that the intercalation of DD occurred in the clay interlayer and site specific interactions occur between DD molecule and Cs⁺ cation. </p> <p> Sorption of 1-chloro-dibenzo-p-dioxin (1-ClDD) and 2-chloro-dibenzo-p-dioxin (2-ClDD) on homoionic (Na⁺, K⁺, Rb⁺, and Cs⁺) smectites was evaluated to explore the effect of chlorine substitution position (and steric hindrance) of dioxin on sorption mechanisms. Similar to DD, adsorption was influenced by the hydration energy of exchangeable cations and the origin of negative charge in the smectite. XRD measurements revealed that 1-ClDD molecules were oriented nearly parallel to the siloxane surface of the clay while 2-ClDD adopted a tilted orientation, similar to DD. The location of the chlorine constituent in 1-ClDD prevents the molecule from its apparent energetically more favorable orientation. In-situ ATR-FTIR spectra revealed that sorption of 1-ClDD to Cs-saponite resulted in the loss of interfacial H₂O and suggested that the sorption 1-ClDD displaces interlayer H₂O and 2-ClDD is less sterically restricted in the clay interlayer. </p> <p> Sorption of three dioxins (DD, 1-ClDD and 2-ClDD) was compared to three PCBs (PCB-1, PCB-4, and PCB47) with similar octanol-partition coefficients (log K_ow) but varying molecular planarity and degree of chlorination onto Cs-saponite, which was shown to be representative of other smectites, revealed that despite having similar structure and hydrophobicity, dioxins have higher affinity for smectites than PCBs. Sorption studies also showed that sorption of PCBs is influenced by molecular planarity and hydrophobicity. Polarizability and dipole-moment were identified as important solute properties that affect the sorption behavior of dioxins and PCBSs. Linear relationships between these properties and log K_f’(subcooled liquid solubility normalized Freundlich sorption coefficient) values suggest that high sorption affinity of planar dioxins could be due to a combination of <i>Van der Waals</i> interactions with the siloxane surface, steric effects, and site-specific interactions between dioxin and exchangeable cations. In contrast, the sorption of PCBs was highly influenced by their molecular orientation.</p>

Este trabalho apresenta a preparação e caracterização de materiais compósitos baseados na mistura (blenda) de poli (ácido lático) PLA e poli (adipato co-tereftalato de butileno) PBAT reforçados com bio-hidroxiapatita \"HAp\", obtida a partir de cascas de ovos brancos de galinha. A obtenção de HAp foi realizada por via úmida, reação ácido-base. Primeiramente, foi obtido o bio-carbonato de cálcio a partir das cascas de ovos brancos de galinha, seguido de um ciclo térmico de aquecimento a 800 °C para a conversão em óxido de cálcio, o qual posteriormente foi sinterizado a 900 °C para a obtenção da HAp. Os materiais compósitos de PLA/PBAT reforçados com 1, 3 e 5 %, em massa, de HAp em pó, com tamanho de partículas iguais ou menor que 10 &mu;m, foram preparadas pelo processo de extrusão utilizando-se uma extrusora de dupla-rosca. Após o processo de extrusão, os materiais foram alimentados ao funil de alimentação de uma injetora de laboratório para a obtenção dos corpos de prova para os ensaios de caracterização. Parte dos corpos de prova foram submetidos à esterilização por radiação gama (radioesterilização), utilizando-se feixe de elétrons de alta energia, gerados em um acelerador de elétrons industrial, de 1,5 MeV, à temperatura ambiente e na presença de ar, com dose de radiação de 25 kGy. As amostras de HAp foram caracterizadas por meio dos ensaios de difração de raios X (DRX), espectroscopia vibracional de absorção no infravermelho com transformada de Fourier (FTIR), termogravimetria (TG) e microscopia eletrônica de varredura com fonte de emissão de campo (MEV-FEG). O PLA/PBAT puro e seus compósitos não irradiados e irradiados foram caracterizados por meio dos ensaios de DRX, TG, MEV-FEG, calorimetria exploratória diferencial (DSC), temperatura de distorção térmica (HDT), ponto de amolecimento Vicat, resistência à tração, à flexão e ao impacto Izod, validação do processo de esterilização (teste de carga microbiana (Biocarga ou Bioburden) e ensaios de esterilidade) e citotoxicidade \"in vitro\" pelo método de incorporação do vermelho neutro para avaliação da biocompatibilidade das amostras. As análises de DRX da HAp mostraram os picos característicos presentes na fase amorfa da HAp; os picos e bandas largas pertencentes aos grupos moleculares da HAp foram identificados por meio da análise por FTIR; a estabilidade térmica da HAp obtida foi confirmada por termogravimetria, a qual mostrou uma pequena perda de massa com o aumento da temperatura, devido à queima do solvente, evaporação de água e queima de materiais orgânicos presentes na amostra de HAp, as imagens obtidas por MEV-FEG mostraram estruturas irregulares características da HAp. A incorporação de HAp na blenda de PLA/PBAT promoveu ganhos superiores a 10 % na temperatura de distorção térmica e no ponto de amolecimento Vicat original da blenda, aumento superior a 15 % nas propriedades mecânicas de resistência à tração e à flexão, e aumento superior a 10 % a resistência ao impacto Izod, melhorando suas propriedades de forma significativa quando comparado a blenda de PLA/PBAT. Os testes de carga microbiana e esterilidade mostraram que a dose de radiação de 25 kGy aplicada foi eficaz para a esterilização das amostras dos materiais. Todas as amostras apresentaram-se biocompatíveis em ambiente celular pelo teste de citotoxicidade \"in vitro\", apresentando potencial para estudo \"in vivo\". / This work presents the preparation and characterization of composites based on blends of poly (lactic acid) - PLA and poly (adipate co-terephthalate of butylene) - PBAT reinforced with bio-hydroxyapatite \"HAp\", obtained from avian eggshells waste of white color. The HAp was obtained by the wet chemical method from the acid-base reaction. Firstly, the bio-calcium carbonate (bio-CaCO3) was obtained from the avian eggshells waste. The bio-CaCO3 was submitted to a heating cycle at 800 °C in order to convert bio-CaCO3 in the bio-calcium oxide, which was then sintered at 900 °C and the bio-HAp was obtained. PLA/PBAT reinforced with 1, 3 and 5 % in weight of HAp, particle size &le; 10 &mu;m, were prepared by the extrusion process using a twin-screw extruder. After the extrusion process, the PLA/PBAT blend and its composites were fed into a laboratory injection molding machine and the specimens test were obtained for the characterization tests. Part of the specimens was submitted to sterilization by gamma radiation (radio-sterilization) with electron-beam using an industrial electron accelerator of 1.5 MeV, at the radiation dose of 25 kGy, room temperature and in the presence of air. HAp was characterized by X ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetry (TG) and scanning electron microscopy with field emission source (FE-SEM) analysis. The blends and composites (non-irradiated and irradiated samples) were characterized by XRD; TG; FE-SEM and differential scanning calorimetry (DSC) analysis. The thermal distortion temperature (HDT), Vicat softening temperature, tensile, flexural, and impact Izod tests were also carried out. The validation of materials sterilization process (Bioburden tests) and cytotoxicity test \"in vitro\" to evaluating the biocompatibility of the material composites were also made. XRD analyzes results showed a characteristic peak in the amorphous phase of HAp. FTIR analysis identified broad peaks and bands belonging to the molecular groups of HAp. The thermal stability of the HAp was confirmed by the TG analysis, which showed a small loss of mass with the increase of temperature due to the burning of solvents, water evaporation and burning of organic materials present in the sample of HAp. The FE-SEM images showed irregular structures characteristic of HAp. Regarding the PLA/PBAT/HAP composites, it can be observed increases up to 10 % in thermal distortion temperature and Vicat softening temperature, higher than 15 % in the tensile and flexural strength, and higher than 10 % in the Izod impact when compared with neat PLA/PBAT blend. The bioburden tests showed that radiation dose of 25 kGy was effective for sterilization of the materials. The results of the cytotoxicity test \"in vitro\" showed that all samples are biocompatible in the cellular environment, and therefore, presents a potential for \"in vivo\" study.

Com as descobertas das inúmeras aplicações potenciais da biomassa de microalgas é necessário o desenvolvimento de ferramentas que visem auxiliar o aumento da produtividade dos cultivos. A espectrometria por infravermelho com transformada de Fourier (FTIR) é uma técnica versátil e rápida utilizada na identificação, caracterização e quantificação de diversos compostos moleculares. Sua aplicação está definida de acordo com a região espectral a ser analisada. O objetivo deste trabalho é desenvolver uma metodologia que torne possível a utilização da espectroscopia FTIR na região do infravermelho médio (MIR) para quantificar os teores de lipídeos, proteínas, carboidratos e células de Scenedesmus sp. Para tanto, a biomassa de Scenedesmus sp. foi analisada diariamente por métodos tradicionais e através do espectro FTIR. Posteriormente os dados foram correlacionados com as bandas de absorção características de cada composto. O modelo gerado para lipídeos na região entre 3000-2800 cm-1 obteve o maior coeficiente de correlação (R2) de 0,8265. Para os carboidratos, a banda de absorção que melhor representou as ligações características foi entre 1200-950cm-1, com R2=0,8023. Já para proteínas, a escolha do método tradicional não mostrou boa relação com os resultados do FTIR. Quando a concentração celular foi correlacionada com a área total foi obtido R2=0,7900. Por fim, realizaram-se experimentos para validar os modelos preditos, obtendo bons resultados para a quantificação de lipídeos e carboidratos. O FTIR mostra ser uma ferramenta eficiente para estimar os conteúdos de lipídeos e carboidratos de Scenedesmus sp. Além disso, o FTIR permite análise simultânea de múltiplos metabolitos que permitirá o monitoramento mais detalhado do cultivo em um tempo de análise muito mais curto e com alta reprodutibilidade dos resultados. / With the discoveries of the numerous potential applications of microalgal biomass, it is necessary to develop tools to help increase the productivity of cultivation. Infrared spectrometry with Fourier transform (FTIR) is a versatile and fast technique used in the identification, characterization and quantification of several molecular compounds. Its application is defined according to the spectral region to be analyzed. The objective of this work is to develop a methodology that makes possible the use of FTIR spectroscopy in the medium infrared region (MIR) to quantify lipid, protein, carbohydrate and cells contents of Scenedesmus sp. For this, the Scenedesmus sp. biomass was analyzed daily by traditional methods and through the FTIR spectrum. Subsequently the data were correlated with the absorption bands characteristic of each compound. The model generated for lipids in the region between 3000-2800 cm-1 obtained the highest coefficient of correlation (R2) of 0.8265. For carbohydrates, the absorption band that best represented the characteristic bonds was between 1200-950cm-1, with R2=0.8023. For proteins, the choice of the traditional method did not show a good relation with the FTIR results. When the cell concentration was correlated whit the total area an R2=0.7900. Finally, experiments were carried out to validate the predicted models, obtaining good results for the quantification of lipids and carbohydrates. The FTIR shows to be an efficient tool to estimate lipid and carbohydrate contents of Scenedesmus sp. In addition, the FTIR allows simultaneous analysis of multiple metabolites that will enable more detailed monitoring of the cultivation in a much shorter analysis time and with high reproducibility of the results.

Este trabalho apresenta a preparação e caracterização de materiais compósitos baseados na mistura (blenda) de poli (ácido lático) PLA e poli (adipato co-tereftalato de butileno) PBAT reforçados com bio-hidroxiapatita \"HAp\", obtida a partir de cascas de ovos brancos de galinha. A obtenção de HAp foi realizada por via úmida, reação ácido-base. Primeiramente, foi obtido o bio-carbonato de cálcio a partir das cascas de ovos brancos de galinha, seguido de um ciclo térmico de aquecimento a 800 °C para a conversão em óxido de cálcio, o qual posteriormente foi sinterizado a 900 °C para a obtenção da HAp. Os materiais compósitos de PLA/PBAT reforçados com 1, 3 e 5 %, em massa, de HAp em pó, com tamanho de partículas iguais ou menor que 10 &mu;m, foram preparadas pelo processo de extrusão utilizando-se uma extrusora de dupla-rosca. Após o processo de extrusão, os materiais foram alimentados ao funil de alimentação de uma injetora de laboratório para a obtenção dos corpos de prova para os ensaios de caracterização. Parte dos corpos de prova foram submetidos à esterilização por radiação gama (radioesterilização), utilizando-se feixe de elétrons de alta energia, gerados em um acelerador de elétrons industrial, de 1,5 MeV, à temperatura ambiente e na presença de ar, com dose de radiação de 25 kGy. As amostras de HAp foram caracterizadas por meio dos ensaios de difração de raios X (DRX), espectroscopia vibracional de absorção no infravermelho com transformada de Fourier (FTIR), termogravimetria (TG) e microscopia eletrônica de varredura com fonte de emissão de campo (MEV-FEG). O PLA/PBAT puro e seus compósitos não irradiados e irradiados foram caracterizados por meio dos ensaios de DRX, TG, MEV-FEG, calorimetria exploratória diferencial (DSC), temperatura de distorção térmica (HDT), ponto de amolecimento Vicat, resistência à tração, à flexão e ao impacto Izod, validação do processo de esterilização (teste de carga microbiana (Biocarga ou Bioburden) e ensaios de esterilidade) e citotoxicidade \"in vitro\" pelo método de incorporação do vermelho neutro para avaliação da biocompatibilidade das amostras. As análises de DRX da HAp mostraram os picos característicos presentes na fase amorfa da HAp; os picos e bandas largas pertencentes aos grupos moleculares da HAp foram identificados por meio da análise por FTIR; a estabilidade térmica da HAp obtida foi confirmada por termogravimetria, a qual mostrou uma pequena perda de massa com o aumento da temperatura, devido à queima do solvente, evaporação de água e queima de materiais orgânicos presentes na amostra de HAp, as imagens obtidas por MEV-FEG mostraram estruturas irregulares características da HAp. A incorporação de HAp na blenda de PLA/PBAT promoveu ganhos superiores a 10 % na temperatura de distorção térmica e no ponto de amolecimento Vicat original da blenda, aumento superior a 15 % nas propriedades mecânicas de resistência à tração e à flexão, e aumento superior a 10 % a resistência ao impacto Izod, melhorando suas propriedades de forma significativa quando comparado a blenda de PLA/PBAT. Os testes de carga microbiana e esterilidade mostraram que a dose de radiação de 25 kGy aplicada foi eficaz para a esterilização das amostras dos materiais. Todas as amostras apresentaram-se biocompatíveis em ambiente celular pelo teste de citotoxicidade \"in vitro\", apresentando potencial para estudo \"in vivo\". / This work presents the preparation and characterization of composites based on blends of poly (lactic acid) - PLA and poly (adipate co-terephthalate of butylene) - PBAT reinforced with bio-hydroxyapatite \"HAp\", obtained from avian eggshells waste of white color. The HAp was obtained by the wet chemical method from the acid-base reaction. Firstly, the bio-calcium carbonate (bio-CaCO3) was obtained from the avian eggshells waste. The bio-CaCO3 was submitted to a heating cycle at 800 °C in order to convert bio-CaCO3 in the bio-calcium oxide, which was then sintered at 900 °C and the bio-HAp was obtained. PLA/PBAT reinforced with 1, 3 and 5 % in weight of HAp, particle size &le; 10 &mu;m, were prepared by the extrusion process using a twin-screw extruder. After the extrusion process, the PLA/PBAT blend and its composites were fed into a laboratory injection molding machine and the specimens test were obtained for the characterization tests. Part of the specimens was submitted to sterilization by gamma radiation (radio-sterilization) with electron-beam using an industrial electron accelerator of 1.5 MeV, at the radiation dose of 25 kGy, room temperature and in the presence of air. HAp was characterized by X ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetry (TG) and scanning electron microscopy with field emission source (FE-SEM) analysis. The blends and composites (non-irradiated and irradiated samples) were characterized by XRD; TG; FE-SEM and differential scanning calorimetry (DSC) analysis. The thermal distortion temperature (HDT), Vicat softening temperature, tensile, flexural, and impact Izod tests were also carried out. The validation of materials sterilization process (Bioburden tests) and cytotoxicity test \"in vitro\" to evaluating the biocompatibility of the material composites were also made. XRD analyzes results showed a characteristic peak in the amorphous phase of HAp. FTIR analysis identified broad peaks and bands belonging to the molecular groups of HAp. The thermal stability of the HAp was confirmed by the TG analysis, which showed a small loss of mass with the increase of temperature due to the burning of solvents, water evaporation and burning of organic materials present in the sample of HAp. The FE-SEM images showed irregular structures characteristic of HAp. Regarding the PLA/PBAT/HAP composites, it can be observed increases up to 10 % in thermal distortion temperature and Vicat softening temperature, higher than 15 % in the tensile and flexural strength, and higher than 10 % in the Izod impact when compared with neat PLA/PBAT blend. The bioburden tests showed that radiation dose of 25 kGy was effective for sterilization of the materials. The results of the cytotoxicity test \"in vitro\" showed that all samples are biocompatible in the cellular environment, and therefore, presents a potential for \"in vivo\" study.

The surface and structural change of human hair fibre have been analysed to determine the oxidation effects for bleached hairs. Three types of bleached hairs (6% H2O2 bleach, 9% H2O2 commercial bleach and commercial persulphate bleach (contains 9% H2O2)) as well as virgin hair were evaluated with the increasing treatment time using Scanning Electron Microscopy (SEM), Reflective Spectrophotometry, Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared (FTIR) Spectroscopy. It is obvious that longer treatment times result in the greater surface and structural damage. However, commercial persulphate bleach causes less surface damage for the cuticle. 6% H202 bleach has overall moderate damage effects on both cuticle and cortex over the treatment time. 9% H2O2 commercial bleach indicates two different damage stages. The first 1.5h bleached hairs show mild oxidation to the surface, whereas the damage becomes heavy after 2h. This phenomenon results in that 9% H2O2 commercial bleach has a more intensive oxidation damage in the cortex than the commercial persulphate bleach. This is in line with DSC investigation which shows that the intermediate filament of 9% H2O2 commercial bleach is heavily damaged after the extensive oxidation time (greater than or equal to2h). Although commercial persulphate bleach contains the stronger oxidising agent, it has a less surface damage than 9% H2O2 commercial bleached hair in FTIR-ATR measurement, and a similar oxidation effect on the matrix as 6% H202 bleached hair in FTIR transmission investigation. In addition, it has been verified by colour measurements that bleached hairs have an overall lighter, yellowish and reddish colour. Consequently, commercial persulphate bleached hair is much lighter and more yellow than 9% H2O2 commercial bleached hair and 6% H202 bleached hair. DSC investigations reveal that the three bleaches have a homogenous oxidation effect on IFs and IFAPs. The deconvolution results using three Gaussian distributions confirm this observation. The stronger bleach results in a homogenous structural damage on both para- and ortho-cortex with increasing bleaching time. Commercial persulphate bleach and 9% H2O2 commercial bleach have a progressive damage effect on the ortho- and para- cortex than 6% H202 bleach. Kinetics analysis is conducted for the virgin and bleached hairs by using various heating rates according to ASTM-E698. The activation energies of 260 kJ/mol for the virgin hair and 295 kJ/mol for the commercial persulphate bleached hair (2h) are determined from the slope of the regression line of peak temperature, TD (as 1/TD) and heating rate, β (as lnβ) on the basis of the Arrhenius-equation. The predominant structural damage for various heating rates only occurs in the IF. It is shown that a linear increase in DeltaHD occurs for lower heating rates, while it is constant for higher heating rates. This can be ascribed to the hypothesis that a lower heating rate favours a crystal transformation change (alpha-β transformation), while a higher rate favours a crystalline-amorphous transformation. SEM examines the morphological changes of hair samples after DSC. The cortex has been dissolved at the lower heating rate. The commercial persulphate bleached hairs (2h) show an overall shrunk cuticle surface and fewer and smaller hydrolysed protein granules, due to the previous damage of the alpha-helix in the cortical cell.

Live cell imaging with FTIR spectroscopy offers a high throughput, non-damage and lab-free method to study the cells in vivo which has significant advantages in the field of cancer diagnosis and drug screening. However, due to the strong absorbance of water, using infrared spectroscopy in such field remains to be an underdeveloped topic. This project demonstrates a novel method to perform IR imaging of cells in solution. A novel water correction method, which avoids the using of water combination band, is proposed. A buffer reference and a cell reference spectra were introduced to fitting the contribution based on protein bands. This method was implemented on three types of IR spectrometers, namely conventional FTIR spectrometer, synchrotron-based FTIR spectrometer and quantum cascade laser (QCL) microscope. To date, most of the live cell imaging carried out with IR sources utilise synchrotron radiation. Recently, a new bench top system, QCL microscope, has been developed. It incorporates four tunable QCL laser sources covering the wavenumber range 900-1800 cm-1 which are many orders of magnitude brighter than conventional sources. The proposed water correction method is, therefore, capable of processing the data recorded by all three types of IR spectrometers. Three prostate cancer cell lines were employed to evaluate the water correction method and the performance of three spectrometers on imaging of cell in solution. The obtained spectra was analysed with multivariate analysis, PCA and PC-LDA which shows good separation between cell lines. The data was also examined with Random Forest algorithm to establish a classifier and the diagnostic capability of the water corrected spectra was proven.