Application of thermogravimetric analysis to the renewable energy sources is a novel study and it has been becoming attractive by the researchers in recent years. In this thesis, thermal and kinetic properties of biodiesel as new energy source, diesel and canola oil have been analyzed by using very popular thermogravimetric analysis methods which are / Differential Scanning Calorimetry (DSC) and Thermogravimetry (TGA/DTG). The main aim of the study is to observe the combustion and pyrolysis behaviour of methanol route biodiesel and diesel blends at different blending rates. Additionally, combustion and pyrolysis behaviour of canola oil, the origin of biodiesel have been analysed to observe the transesterification reaction effect on biodiesel. Therefore, biodiesel, diesel, canola oil and blends of diesel and biodiesel at different percentages are exposed to isothermal heating under nitrogen and air atmosphere with a constant heating rate of 5, 10 and 15

Bacteria employ survival strategies to protect themselves against foreign invaders, including bacteriophages. The ‘immune system’ of bacteria relies mostly on restriction-modification (R-M) systems. The primary role of R-M systems is to protect the host from invading foreign DNA molecules. Three major types of R–M system are found in bacteria, viz.Types I, II and III. Type II R–M systems comprise a separate restriction endonuclease (REase) and a methyltransferase (MTase) that act independently of each other. Type II REases generally recognize palindromic sequences in DNA and cleave within or near their recognition sequences and produce DNA fragments of defined sizes. They have become indispensable tools in molecular biology and have been widely exploited for studying site-specific protein–DNA interactions. Surprisingly, these enzymes share little or no sequence homology among them, though the three-dimensional structures determined to date reveal a common-core motif (‘PD...D/EXK’ motif) with a central β-sheet that is flanked by α-helices on both sides. In the motif, two acidic residues (D and D/E) are important for the metal ion binding and catalysis. The work presented in this thesis deals with the determination of active site, elucidation of kinetic mechanism and study of evolution of sequence specificity using the well known, R.KpnI, from Klebsiella pneumoniae. The enzyme is a homodimer, which recognizes a palindromic double stranded DNA sequence, GGTAC↓C, and cleaves as shown. Unlike other REases, R.KpnI shows prolific promiscuous DNA cleavage in presence of Mg2+. Surprisingly, Ca2+ completely suppresses the Mg2+ mediated promiscuous activity and induces high fidelity cleavage at the recognition sequence. These unusual properties of R.KpnI led to the characterization of the active site of the enzyme. This thesis is divided into five chapters. Chapter 1 is a general introduction of R-M systems and an overview of the literature on active sites of Type II REases. It deals with discovery, nomenclature and classification followed by description of the enzymes diversity and general features of Type II REases. The different active site folds of the REases have been discussed in detail. The features of sequence specificity and the efforts undertaken to engineer the new specificity in the REases have been dealt at the end of the chapter. Chapter 2 describes identification and characterization of the R.KpnI active site by bioinformatics analyses, homology modeling and mutational studies. Bioinformatics analyses reveal that R.KpnI contains a ββα-Me-finger fold, which is a characteristic of many HNH-superfamily endonucleases. According to the homology model of R.KpnI, the putative active site residues correspond to the conserved residues present in HNH nucleases. Substitutions of these conserved residues in R.KpnI resulted in loss of the DNA cleavage activity, confirming their importance. This study provides the first experimental evidence for a Type IIP REase that is a member of the HNH superfamily and does not belong to the PD...D/EXK superfamily of nucleases. In Chapter 3 DNA binding and kinetic analysis of R.KpnI is presented. The metal ions which exhibit disparate pattern of DNA cleavage have no role in DNA recognition. The enzyme binds to both canonical and non-canonical DNA with comparable affinity irrespective of the metal ions used. Further, it was shown that Ca2+-imparted exquisite specificity of the enzyme is at the level of DNA cleavage and not at the binding step. The kinetic constants were obtained through steady-state kinetic analysis of R.KpnI in presence of different metal ions. With the canonical oligonucleotides, the cleavage rate of the enzyme was comparable for both Mg2+- and Mn2+-mediated reactions and was about three times slower with Ca2+. The enzyme discriminates non-canonical sequences poorly from the canonical sequence in Mg2+-mediated reactions unlike any other Type II REases, accounting for its promiscuous behavior. These studies suggest that R.KpnI displays properties akin to that of typical Type II REases and also endonucleases with degenerate specificity for DNA recognition and cleavage. In chapter 4, two uncommon roles for Zn2+ in R.KpnI are described. Examination of the sequence revealed the presence of a zinc finger (CCCH) motif rarely found in proteins of prokaryotic origin. Biophysical experiments and subsequent mutational analysis showed that the zinc binding motif tightly coordinates zinc to provide a rigid structural framework for the enzyme needed for its function. In addition to this structural scaffold, another atom of zinc binds to the active site to induce high fidelity cleavage and suppress the Mg2+- and Mn2+-mediated promiscuous behavior of the enzyme. This is the first demonstration of distinct structural and catalytic roles for zinc in a REase. Chapter 5 describes generation of highly sequence specific R.KpnI. Towards this end, site-directed mutants were generated at the putative secondary metal binding site. The DNA binding and cleavage analyses of the mutants at putative secondary metal binding site revealed that the secondary site is not important for primary catalysis and have a role in sequence specificity. A single amino acid change at the D163 position abolished the promiscuous activity of the wt enzyme in the presence of Mg2+ and Mn2+. Thus, a single point mutation converts the promiscuous endonuclease to a high fidelity REase. In conclusion, the work described in the thesis reveals new information on the REases in general and R.KpnI in particular. Many of the properties of R.KpnI elucidated in this thesis represent hitherto unknown features amongst REases. The presence of an HNH catalytic motif in the enzyme indicates the diversity of active site fold in REases and their distinct origin. Similarly, the high degree of promiscuity exhibited by the enzyme may hint at the evolutionary link between non-specific and highly sequence specific nucleases. The present studies also provide an example for the role of mutations in the evolution of sequence specificity. The utilization of different metal ions for DNA cleavage and the architectural role for Zn2+ in maintaining the structural integrity are other unusual properties of the enzyme.

O objetivo da pesquisa foi avaliar os efeitos da terapia de ondas de choque extracorpórea em pacientes com osteoartrose coxofemoral secundária a displasia. Foram analisados 30 cães (Grupo I) com auxílio da plataforma de baropodometria, portadores de osteoartrose bilateral da articulação coxofemoral, que receberam como tratamento ondas de choque radiais somente em uma das articulações acometidas de modo aleatório que foi comparado ao membro contralateral com o acompanhamento de 3 meses, 18 animais (Grupo II) com displasia coxofemoral e osteoartrose bilateral medicados com condroprotetor e também comparado ao banco de 20 animais hígidos (Grupo III). O protocolo de tratamento envolveu três sessões de 2000 pulsos cada com frequência de 10 Hz de 2-3,4 bars, com intervalo de 7 dias, e a aplicação realizada sob sedação e curta anestesia. A avaliação mensal quantitativa do apoio dos membros e da eficácia do tratamento foi realizada com análise cinética utilizando sistema de baropodometria, mensurando-se o pico de força vertical (PFV) e o impulso vertical (IV).O grupo I e II tiveram em média valores do PFV e IV inferiores ao grupo III. No grupo I, observou-se um aumento em média de 10,6% do PFV e de 10,4% do IV do membro tratado, assim como uma melhora na simetria. O grupo II apresentou um aumento em média do membro pélvico esquerdo de 9% do IV, porém houve piora de 11% na simetria deste mesmo parâmetro. Os dados da análise cinética no membro tratado do grupo I atingiram em média valores próximos, mas ainda inferiores, ao grupo III de animais hígidos. Estas avaliações verificaram a eficácia das ondas de choque como tratamento conservativo de cães portadores de osteoartrose secundária a displasia, sugerindo efeitos benéficos de forma quantitativa para uma melhor locomoção. / The objective of this research was evaluate the extracorporeal shockwave therapy (ESWT) effects in patients with hip osteoarthritis secondary to hip dysplasia. Thirty dogs (Group I) with bilateral hip osteoarthritis were evaluated trough pressure walkway system. They had received unilateral radial shockwaves for treatment in random selection. The treated limb was compared with contra lateral limb during a follow up of 3 months. A comparison with the treated group with eighteen dogs under conservative treatment (Group II) and twenty healthy dogs (Group III) was also performed. Protocol treatment included three sessions of 2000 pulses each in a frequency of 10Hz with a pressure between 2 and 3.4 bar performed weekly using chemical restraint and short general anesthesia. Monthly assessment with kinetic analysis had done it with pressure walkway system. The peak of vertical force (PVF) and vertical impulse (VI) were measured. Group III kinetic analysis mean values were higher than groups I and II. Our results of group I suggest 10.6% of improvement in the treated limb in the PVF and 10.4% in the VI. In this group was also detected an improvement in the symmetry. The group II showed an improvement of 9% of VI only in the left pelvic limb but the symmetry decreased in 11% in this parameter. The kinetic analysis data of group I reached mean values of the treated limb close to healthy dogs of group III but remains slightly lower. These evaluations verified the efficacy of ESWT suggesting benefic quantitative effects in dog\'s locomotion.

Prussian blue (PB) and Prussian blue analogues (PBAs) are compounds with potential applications in a large variety of fields such as gas storage, poison antidotes, electrochromism, electrochemistry and molecular magnets. The compounds are easy to synthesize, cheap, environmentally friendly and have been pursued for both fundamental research and industrial purposes. Despite the multifunctionality of PB and PBAs, they have complicated compositions, which are largely dependent on the synthesis methods and storage conditions. Thus, performing investigations on such compounds with defined composition, stoichiometry and crystal structure is essential. This thesis has focused on synthesis and detailed structure characterization of copper hexacyanoferrate (CuHCF) via X-ray powder diffraction (XRPD), neutron powder diffraction (NPD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), inductively coupled plasma-optical emission spectroscopy (ICP-OES), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), Mössbauer spectroscopy, extended X-ray absorption fine structure (EXAFS), infrared (IR) and Raman techniques. In addition, kinetics of thermal dehydration process, CO2 adsorption and CO2 adsorption kinetics were investigated. Moreover, in operando synchrotron X-ray diffraction experiments were performed to gain insight into the structure-electrochemistry relationships in an aqueous CuHCF/Zn battery during operation. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 4: Manuscript. Paper 5: Manuscript.</p>

A new detection reagent that could possibly augment or replace antibodies research and diagnosis methods are aptamers. Aptamers are ssDNA, RNA or polypeptide constructs that function like active antibodies. Antibodies and aptamers both specifically bind to selected target molecules, and as such they enable the detection or targeting of the presence or absence of a specific antigen. In order to ensure that ssDNA aptamers perform similarly to antibodies, anti-VEGF-A polyclonal antibody and anti-VEGF-A ssDNA aptamer were evaluated against vascular endothelial growth factor A (VEGF-A) using Surface Plasmon Resonance (SPR). It was hypothesized that the anti-VEGF-A aptamer had the same, if not better, binding kinetics than the anti-VEGF-A polyclonal antibody, and as such offers an ideal replacement for use in in field, real-time testing assays. SPR revealed that both the polyclonal antibody and ssDNA aptamer bound the target antigen, VEGF-A. Additionally, from the SPR kinetic analysis, the anti-VEGF-A aptamer had KD values of 20-28 nM and the anti-VEGF-A antibody had KD values of 16-127 uM. The binding efficacy of the aptamer was several orders of magnitude better than that of the antibody. The aptamer was also stable in solution for a longer amount of time than the antibody, which denatured in solution after two weeks.

O objetivo do trabalho é investigar como as condições biomecânicas de portadores de Osteoartrite (OA) de joelho afetam a capacidade de realizar atividades de vida diária. Participaram desse estudo 39 indivíduos, sendo 18 indivíduos com OA de joelho bilateral grau 3, na escala Kellgren Lawrence, e 21 indivíduos saudáveis. Foram utilizadas duas plataformas de força (AMTI) para registrar a Força de Reação do Solo, cinco câmeras (Sistema Vicon) para registrar as variações angulares das articulações do quadril, joelho e tornozelo, nos planos sagital e frontal, e cinco sensores de eletromiografia wireless (Sistema Noraxon) para registrar as atividades dos músculos reto femoris (RF), vastus lateralis (VL), biceps femoris (BF), tibialis anterior (TA) e gastrocnemius lateralis (GL) no segmento dominante (segmento D) dos sujeitos do grupo controle e no segmento com maior gravidade de lesão nos indivíduos com OA (segmento OA). Também foram calculados por meio de dinâmica inversa os momentos articulares nos planos sagital e frontal. Três atividades de vida diária foram investigadas, a marcha, o levantar e sentar em uma cadeira e o descer de um degrau de 20cm. Nos resultados, foi observada uma menor variação angular de forma geral nas articulações do quadril e joelho. Não foi observada diferença nas cargas mecânicas aplicadas ao aparelho locomotor. Nas três atividades cotidianas, os indivíduos com OA apresentaram adução no quadril e abdução no joelho, que denota um alinhamento em valgo durante a execução das tarefas. Poucas diferenças foram observadas nos momentos articulares flexores e extensores, nas três atividades de vida diária investigadas. No levantar e sentar menores momentos extensores foram observados no joelho durante as duas fases do movimento. Nos momentos adutores, poucas diferenças foram observadas na marcha. No levantar e sentar, o segmento OA não apresentou momentos adutores de joelho maiores que nos outros segmentos. No descer degrau, o segmento CL apresentou maior momento adutor que o segmento OA e D. De forma geral, as diferenças na ativação muscular indicam maior intensidade de ativação no grupo controle. O músculo VL nas três atividades apresentou intensidade de ativação menor nos indivíduos com OA. Observou-se maior co-ativação na marcha e no descer degrau, mas não no levantar e sentar. Na marcha a maior co-ativação ocorreu nas três articulações. No descer degrau, ocorreu no quadril e no joelho. Nas três atividades, maior co-contração foi observada e principalmente no joelho. Conclui-se que as alterações na técnica de movimento mostram-se tarefa dependente. As alterações na execução do movimento no plano sagital não foram suficientes para afetar o controle das cargas mecânicas, na marcha e no descer degrau. Apenas na tarefa de levantar e sentar surgiu algum indicio de que a eficiência seria pior. O alinhamento no joelho e os momentos adutores não sugerem maior magnitude de força no compartimento medial do joelho. Aparentemente, as características temporais sejam mais sensíveis à presença da OA no joelho do que a intensidade de ativação / The aim of this study is to investigate the biomechanical characteristics of patients with knee osteoarthritis (OA) and hoe it affects the ability to perform daily living activities. Thirty nine subjects participated in this study, 18 subjects with bilateral knee OA grade 3 Kellgren Lawrence scale) and 21 healthy individuals. Two force platforms (AMTI) were used to register the Grourd Reaction Force (GRF). Five cameras (System Vicon) were used to register the angular variations of the hip, knee and ankle in the sagittal and frontal planes. Five electromyographic electrodes (Noraxon System) were used to record the activities of the rectus femoris (RF), vastus lateralis (VL), biceps femoris (BF), tibialis anterior (TA) and gastrocnemius lateralis (GL) in the dominant segment (D segment) on control group and the segment with greater severity of injury in individuals with OA (OA segment). Inverse dynamics was used to calculate joint moments sagittal and frontal planes. Three daily living activities were investigated, the gait, the Sit-to stand and Stand-to-sit and Stepping down from a 20cm height step. In results, there was a smaller angular variation in hip and knee joints. No difference was observed in the mechanical loads applied to the locomotor system. In the three daily activities, people with knee OA showed hip adduction and knee abduction, in the three daily activities, which suggests an alignment valgus in the knee. Few differences were observed in joint moments in the three daily living activities. In sit-to-stand and stand-to-sit lower peak extensor moments were observed in the knee. Few differences were observed in adductor moments in gait. In sit-to-stand and stand-to-sit, no difference was observed in knee adductor moments. In stepping down, the CL segment showed greater adductor moment than OA segment and D. In general, differences in muscle activation indicate greater activation intensity in the control group. The VL muscle showed lower activation intensity in individuals with OA in all three activities. A higher co-activation was observed in gait and in stepping down, but not in sit-to-stand and stand-to-sit. In gait the higher co-activation occurred subjects with knee OA in the three joints. In stepping down, higher co-activation occurred in the hip and knee. In the three activities, greater co-contraction was observed and especially in the knee. It can be concluded that changes in movement technique appears to be task dependent. Changes in movement technique in the sagittal plane were not enough to affect the control of the mechanical loads on gait and stepping down movements. Only in sit-to-stand and stand-to-sit some indication of worse efficiency to perform the task was observed. Knee alignment and knee adductor moments do not suggest greater magnitude of force in the medial compartment of the knee. Apparently, the temporal characteristics of muscle activity are more sensitive to the presence of knee OA than the intensity of activation

Os efeitos catalíticos de Mo(VI) e Fe(III) na oxidação de iodeto por peróxido de hidrogênio foram explorados visando à determinação simultânea destes. Diferenças nas taxas de reação foram alcançadas através do estabelecimento de duas zonas reacionais distintas para alteração das cinéticas reacionais. Para isto, foi projetado um sistema de análises por injeção em fluxo que permite a inserção de duas alíquotas de amostra, sendo adicionado ácido sulfúrico em uma destas com formação de uma zona de amostra complexa. Cada elemento de fluido desta zona é caracterizado por composição química, tempo de residência e taxa de reação específicas. Os principais parâmetros que afetam a taxa reacional, tais como concentração dos reagentes, comprimento do reator e vazão total, dentre outros, foram avaliados buscando melhoria na sensibilidade e discriminação cinética entre os analitos. Os comprimentos das alças de amostragem e da bobina separadora foram avaliados construindo-se modelos matemáticos visando máxima discriminação nas previsões para os analitos. Os modelos foram construídos a partir da ferramenta quimiométrica PLS (Partial Least Squares) utilizando os dados gerados por medidas de máximos e mínimos ao longo da zona de amostra. O conjunto de calibração era composto por misturas de Mo(VI) e Fe(III) na faixa de concentrações 6,2 - 50,0 ?g L-1 e 0,5 - 7,0 mg L-1, respectivamente. O modelo selecionado apresenta boa habilidade de previsão com valores de RMSEP estimados como 0,67 ?g L-1 para Mo(VI) e 0,21 mg L-1 para Fe(III). Recuperações entre 85 e 114% foram obtidas para amostras de águas naturais. O sistema proposto apresenta estabilidade física, boa repetibilidade entre as leituras (d. p. r. < 2 %), velocidade analítica de 31 h-1 e consumo de 54 mg de iodeto de potássio e 0,30 mg de peróxido de hidrogênio por amostra / The catalytic effects of Mo(VI) and Fe(III) in the oxidation of iodide by hydrogen peroxide were exploited aiming at their simultaneous determination. Differences in reaction rates were achieved by establishing of two distinct reactions zones to modify the reaction kinetics involved. To this end, a flow injection system allowing insertion of two sample aliquots was designed, and sulfuric acid was added to one of the aliquots. A complex sample zone was then established. Each fluid element of this zone was characterized by a given chemical composition, residence time and reaction rate. The main parameters affecting the reaction rate, such as reagent concentrations, analytical path length and total flow rate, among others, were evaluated for improving sensitivity and analyte kinetic discrimination. Influences of sampling loop lengths and distance between initial plugs were studied, and mathematical models were constructed aiming at improved discrimination in prediction of analytes. The models were constructed from the PLS (Partial Least Squares) chemometric tool using data generated by measurements performed on sample zone regions with maximum and minimum local concentrations. The calibration set consisted of Mo(VI) and Fe(III) mixtures in concentration ranges of 6.2 - 50.0 ?g L-1 and 0.5 - 7.0 mg L-1, respectively. The selected model is characterized by good prediction ability prediction, as RMSEP values were estimated as 0.67 ?g L-1 for Mo(VI) and 0.21 mg L-1 for Fe(III), respectively. Recoveries within the 85 - 114% range were obtained for natural waters. The proposed system presents physical stability and favorable characteristics of measurement repeatability (r.s.d.<2%), sampling rate (31 h-1) and reagent consumption (54 mg of KI and 0.30 mg H2O2 per sample)

Os efeitos catalíticos de Mo(VI) e Fe(III) na oxidação de iodeto por peróxido de hidrogênio foram explorados visando à determinação simultânea destes. Diferenças nas taxas de reação foram alcançadas através do estabelecimento de duas zonas reacionais distintas para alteração das cinéticas reacionais. Para isto, foi projetado um sistema de análises por injeção em fluxo que permite a inserção de duas alíquotas de amostra, sendo adicionado ácido sulfúrico em uma destas com formação de uma zona de amostra complexa. Cada elemento de fluido desta zona é caracterizado por composição química, tempo de residência e taxa de reação específicas. Os principais parâmetros que afetam a taxa reacional, tais como concentração dos reagentes, comprimento do reator e vazão total, dentre outros, foram avaliados buscando melhoria na sensibilidade e discriminação cinética entre os analitos. Os comprimentos das alças de amostragem e da bobina separadora foram avaliados construindo-se modelos matemáticos visando máxima discriminação nas previsões para os analitos. Os modelos foram construídos a partir da ferramenta quimiométrica PLS (Partial Least Squares) utilizando os dados gerados por medidas de máximos e mínimos ao longo da zona de amostra. O conjunto de calibração era composto por misturas de Mo(VI) e Fe(III) na faixa de concentrações 6,2 - 50,0 ?g L-1 e 0,5 - 7,0 mg L-1, respectivamente. O modelo selecionado apresenta boa habilidade de previsão com valores de RMSEP estimados como 0,67 ?g L-1 para Mo(VI) e 0,21 mg L-1 para Fe(III). Recuperações entre 85 e 114% foram obtidas para amostras de águas naturais. O sistema proposto apresenta estabilidade física, boa repetibilidade entre as leituras (d. p. r. < 2 %), velocidade analítica de 31 h-1 e consumo de 54 mg de iodeto de potássio e 0,30 mg de peróxido de hidrogênio por amostra / The catalytic effects of Mo(VI) and Fe(III) in the oxidation of iodide by hydrogen peroxide were exploited aiming at their simultaneous determination. Differences in reaction rates were achieved by establishing of two distinct reactions zones to modify the reaction kinetics involved. To this end, a flow injection system allowing insertion of two sample aliquots was designed, and sulfuric acid was added to one of the aliquots. A complex sample zone was then established. Each fluid element of this zone was characterized by a given chemical composition, residence time and reaction rate. The main parameters affecting the reaction rate, such as reagent concentrations, analytical path length and total flow rate, among others, were evaluated for improving sensitivity and analyte kinetic discrimination. Influences of sampling loop lengths and distance between initial plugs were studied, and mathematical models were constructed aiming at improved discrimination in prediction of analytes. The models were constructed from the PLS (Partial Least Squares) chemometric tool using data generated by measurements performed on sample zone regions with maximum and minimum local concentrations. The calibration set consisted of Mo(VI) and Fe(III) mixtures in concentration ranges of 6.2 - 50.0 ?g L-1 and 0.5 - 7.0 mg L-1, respectively. The selected model is characterized by good prediction ability prediction, as RMSEP values were estimated as 0.67 ?g L-1 for Mo(VI) and 0.21 mg L-1 for Fe(III), respectively. Recoveries within the 85 - 114% range were obtained for natural waters. The proposed system presents physical stability and favorable characteristics of measurement repeatability (r.s.d.<2%), sampling rate (31 h-1) and reagent consumption (54 mg of KI and 0.30 mg H2O2 per sample)

Filtration of grape juice was investigated. Effects of process parameters of filtration were examined. The usage of precoating material and filter aid were found to be necessary to prolong the filter life. Filter cake was found to be incompressible with the effect of increasing pressure. Increase in temperature caused increase in flow rate due to the reduction in viscosity. The influences of depectinization and clarification on filtration process were also examined. Depectinization and clarification decreased the resistance and increased the flow rate. Improvement in the quality of the grape juice was observed when these pretreatments were employed. The effects of temperature and soluble solid concentration on physical properties of clarified fruit juices were investigated. High temperature and soluble solid content dependencies of density, viscosity and heat capacity were detected. Experimental data were fitted as a function of temperature and soluble solid content. Models being valid for studied clarified fruit juices were achieved for density and viscosity with the regression coefficients (R2) higher than 0.90. Optimization of the solid-liquid extraction conditions for trans-resveratrol, trans-&amp / #949 / -viniferin, ferulic acid, and total phenolics from milled grape canes has been investigated. Temperature and ethanol concentration were found to be major process variables for all responses. Maximum yields of trans-resveratrol, trans-&amp / #949 / -viniferin, ferulic acid, and total phenolics were predicted as 4.25 mg/g dw, 2.03 mg/g dw, 1.05 mg/g dw, and 9.28 mg/g dw, respectively. Optimization of extraction conditions for antioxidant activity of grape cane extracts measured by the Trolox equivalent antioxidant capacity (TEAC) and the oxygen radical absorbance capacity (ORACFL) assays was carried out using solid-liquid extraction and response surface methodology. Ethanol concentration and temperature employed for the extraction of antioxidant agents from grape cane samples were found to be statistically significant process variables affecting antioxidant activity measured by the TEAC and ORAC methods. trans-Resveratrol and trans-&amp / #949 / -viniferin were extracted from milled grape canes using pressurized low polarity water (PLPW). The extraction temperature was significant for both compounds: extraction at 160oC resulted in a 40% loss of trans-resveratrol compared to 95oC while reduction of trans-&amp / #949 / -viniferin at both temperatures remained at 30%. Increasing ethanol concentration from 0 to 25% increased the extraction of total phenolics and trans-&amp / #949 / -viniferin by 44% and 489%, respectively. Solvent flow rate also influenced trans-&amp / #949 / -viniferin extraction. Effective diffusivities of trans-resveratrol increased by three times with increasing temperature. The modified Gompertz equation satisfactorily explained the extraction of the stilbenes investigated.

Cette thèse a pour l’objectif d’élaborer, à partir de technologie additive 3D (extrusion de gel), des structures conductrices (électriquement) et résistantes (mécaniquement) en utilisant exclusivement des matériaux lignocellulosiques. Les matériaux sélectionnés sont des microfibrilles de cellulose (MFC), du lignosulfonate de sodium (LS ou NaLS) et de la cellulose en poudre (CP). Ces trois constituants peuvent être utilisés pour élaborer des hydrogels aqueux compatibles avec l’impression 3D (extrusion). De plus, ce procédé d’impression permet la mise en forme avec une excellente définition de structures à base de précurseurs de carbone dont les géométries peuvent être adaptées aux différentes techniques de caractérisation selectionnées. / In the present work, electrically conductive and mechanically resistant carbon structures were elaborated by 3D printing and subsequent pyrolysis using microfibrillated cellulose/lignosulfonate/cellulose powder (labeled as MFC/LS/CP) blends. The processability of MFC/LS/CP slurries by 3D printing was examined by rheological tests in both steady flow and thixotropic modes. The printed MFC/LS/CP pastes were self-standing, provided a high printing definition and were proved to be morphologically stable to air drying and the subsequent pyrolysis. Pyrolysis at a slow rate (0.2°C/min) to a final temperature in the range of 400-1200°C was used to manufacture MFC/LS/CP carbons. The TGA/DTG was applied to monitor the thermal degradation of MFC/LS/CP materials in blends as well as in a separated form. The resulting carbons were further characterized in terms of morphology, microstructure and physical properties (such as density, electrical conductivity and mechanical strength). At 900°C, MFC/LS/CP carbons displayed a high electrical conductivity of 47.8 S/cm together with a low density of 0.74 g/cm3 as well as an important porosity of 0.58. They also achieved an elastic modulus maximum of 6.62 GPa. Such interesting electrical and mechanical properties would lead to a promising application of MFC/LS/CP- derived biocarbons in energy storage devices as electrode materials in close future.