Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Interaction processes of the anionic dyes, remazol yellow (AMR), remazol blue (AZR) and remazol red (VMR) with scales of the fish Piau (Leporinus elongatus) have been evaluated by kinetic and thermodynamic studies. Raw scales and containing the adsorbed dyes were characterized by thermogravimetric analysis, infrared spectroscopy and X- ray diffraction. The point of zero charge (PCZ) of the scale was determined and the found value of 6,98 indicated that the surface of the scales is protonated in acidic medium. Kinetic studies were carried out in order to evaluate the influence of the structures of the dyes, pH and temperature. It was observed that the material presented a higher affinity for anionic dyes, whose adsorbed amounts decreased with increasing temperature, suggesting exothermic processes. The obtained data fitted to the model of pseudo-second-order. In order to obtain thermodynamic parameters, the processes of interaction of the anionic dyes AZR, AMR, VMR with the scales were evaluated by isothermal calorimetry, using the membrane breaking technique. The data were applied to the linear regression model of Langmuir. From this model, values of enthalpy change in the formation of monolayer, ΔmonH, change of the Gibbs free energy of formation of the monolayer, ΔmonG, and entropy change of the formation of the monolayer, ΔmonS, were determined. The obtained values of ΔmonH, ΔmonG and ΔmonS were, respectively, -83,28 kJ mol-1, -17,92 kJ mol-1; -219,22 JK-1mol-1 for the AZR dye, -199,68 kJ mol-1, -20,97 kJ mol-1; -599,40 JK-1mol-1 for AMR dye and -120,87 kJ mol-1, -22,48 kJ mol-1, -330, 00 JK-1mol-1 for the VMR dye. / Processos de interação dos corantes aniônicos, amarelo de remazol (AMR), azul de remazol (AZR) e vermelho de remazol (VMR) com escamas do peixe Piau (Leporinus elongatus) foram avaliados através de estudo cinético e termodinâmico. Escamas puras e contendo os corantes adsorvidos foram caracterizadas por análise termogravimétrica, espectroscopia de absorção na região do infravermelho e difração de raios-X. Também foram realizadas medidas para determinar o ponto de carga zero (PCZ), cujo valor encontrado de 6,98 indicou que a superfície das escamas está protonada em meio ácido. Estudos cinéticos foram realizados com o intuito de avaliar a influência das estruturas dos corantes, do pH e da temperatura nos processos de interação. Observou-se que as escamas apresentaram maiores afinidades por corantes aniônicos, cujas quantidades adsorvidas diminuíram com o aumento da temperatura, sugerindo processos exotérmicos. Os dados cinéticos obtidos ajustaram-se ao modelo de pseudo-segunda-ordem. A fim de se obter parâmetros termodinâmicos, os processos de interação dos corantes aniônicos AZR, AMR, VMR com as escamas foram avaliados por calorimetria isotérmica, utilizando o sistema de quebra de membrana. Os dados obtidos foram aplicados ao modelo da regressão linear de Langmuir. A partir desse modelo, foram determinados os valores de variação de entalpia na formação da monocamada, ΔmonH, variação da energia livre de Gibbs na formação da monocamada, ΔmonG, e variação de entropia na formação da monocamada, ΔmonS. Os valores de ΔmonH, ΔmonG e ΔmonS obtidos foram, respectivamente, -83,28 kJ mol-1; -17,92 kJ mol-1; -219,22 JK-1mol-1, para o corante AZR, -199,68 kJ mol-1; -20,97 kJ mol-1; -599,40 JK-1mol-1, para o corante AMR e -120,87 kJ mol-1 ; -22,48 kJ mol-1; -330,00 JK-1mol-1, para o corante VMR.

C'est dans un contexte marqué par une demande croissante en énergie primaire, une diminution des ressources et dans un souci de protection de l'environnement que le biocarburant de 2ème génération est développé. Cependant, ce biocarburant est non viable économiquement. L’optimisation, le contrôle et la connaissance des cinétiques régissant les procédés de fabrication de ce bioéthanol sont donc des éléments capitaux. Dans cette étude, le potentiel de la calorimétrie isotherme pour surveiller les réactions d'hydrolyse et de fermentation est testé.Les résultats montrent que cette méthode est efficace. En effet, celle-ci a permis de mettre en évidence l'importance du ratio enzyme/substrat pour maximiser le rendement et de déterminer un meilleur cocktail composé de cellulases + cellobiose déshydrogénase (CDH) qui permet la production d'une certaine quantité d'acide gluconique, qui pourrait améliorer l'attractivité de ce biocarburant. Ces mêmes essais ont également permis de déterminer la chaleur de l'hydrolyse de la paille de blé, qui est 32,18 ± 3,18 J.g-1 (gramme de sucres produits).Les mesures obtenues ont été utilisées pour déterminer les constantes cinétiques des cellulases + CDH sur la paille de blé et les résultats montrent que ce cocktail enzymatique est plus rapide à 45 °C dans la gamme de températures testée (40-55°C) avec une vitesse de 7,36 ± 0,62 mmol/L.min.Par ailleurs, les essais avec un calorimètre à échelle laboratoire ont montré que même si celui-ci ne mesure pas avec précision les chaleurs engendrées par les réactions d'hydrolyse et de fermentation, celui-ci donne de bonnes indications sur le déroulement et l'avancement de ces réactions. / Second generation biofuel is developed in a context marked by an increasing demand for primary energy, a decrease in resources and in environmental protection concernsHowever, this biofuel is not economically viable. Optimization, control and knowledge of the kinetics governing this bioethanol production processes are crucial elements.In this study the potential of isothermal calorimetry to monitor hydrolysis and fermentation reactions is tested.The results show that the isothermal calorimetry is an effective method. Indeed this method allowed determining that the substrate/enzyme ratio is an important parameter of the hydrolysis yield.Furthermore it has determined a better enzyme cocktail consisting of Cellulases + Cellobiose Dehydrogenase (CDH) which allows the production of a certain amount of gluconic acid, which could improve the attractiveness of these second-generation biofuels. These same tests also determined the hydrolysis heat of wheat straw which is 32.18 ± 3.18 J.g-1 (gram reducing sugars product).The measurements obtained were used to determine kinetic constants cellulases + CDH on wheat straw and the results show that this enzyme cocktail is faster at 45 ° C in the range of temperatures tested (40 - 55°C) with a speed of 7.36 ± 0.62 mmol/L.min.In addition, testing with a laboratory-scale calorimeter showed that even if this tool does not accurately measure the heat generated by the hydrolysis reaction and fermentation, it gives a good indication of the development and advancement of these reactions.

<p>Superabsorbent polymer (SAP) hydrogel particles have been used as internal curing agents in concrete mixes as they are capable of absorbing and subsequently releasing large amounts of water. This reduces autogenous shrinkage during early stages of hydration. The size, shape, and composition of the hydrogel particles can be controlled during the synthesis, hence providing the opportunity to custom synthesize these internal curing agents to elicit desired structure-property relationships. Utilization of optimized dosage and formulation of SAP has the potential to improve the microstructure, durability, and strength of internally cured concrete. </p> <p>The first study focuses on the synthesis and application of novel composite hydrogel particles as internal curing agents in cementitious mixes. Composite polyacrylamide hydrogel particles containing two different amorphous silica–either nanosilica or silica fume–were used to investigate whether the internal curing performance of hydrogel particles could be enhanced. The dosage and type of silica, crosslinker amount were varied to identify the composite polyacrylamide hydrogel particle composition that provides optimum benefits to internally cured cementitious systems. The synthesized hydrogels were characterized by means of absorption capacity tests, compositional and size analysis. The beneficial impacts of the addition of composite hydrogels on cement paste microstructure are highlighted, including the preferential formation of cement hydration products (such as portlandite) within the hydrogel-induced voids that appeared to be influenced by the composition of the hydrogel particles. The interrelationship between extent of hydration, size of hydrogel voids, and void-filling with hydration products was found to strongly influence mechanical strength and is thus an important structure-property relationship to consider when selecting hydrogels for internal curing purposes. This study informs the design of composite hydrogel particles to optimize performance in cementitious mixes. Additionally, it provides a novel means of incorporating other commonly used admixtures in concrete without facing common challenges related to dispersion and health hazards.</p> <p>The second study focuses on the utilization of two retarding admixture-citric acid and sucrose-to custom synthesize composite polyacrylamides to investigate whether the composite hydrogels could delay hydration of cement paste. Isothermal calorimetry analysis results showed that composite sucrose-containing polyacrylamide hydrogel particles were successfully able to retard main hydration peak of cement paste, beyond the retardation capabilities of the pure polyacrylamide hydrogels. Thus, this study provides avenues of exploring the utilization of common admixtures to formulate novel composite hydrogels that imparts specific properties to cementitious systems.</p> <p>In another study, SAP formulated by admixture industries were used to investigate the feasibility of internal curing of bridge decks and pavement patches with SAP particles. The microstructure and early age hydration properties of SAP-cured cementitious systems were studied. Mitigation of microcracks in the matrix, along with portlandite growth in SAP voids, were observed in SAP-cured mortars. Presence of SAP also mitigated autogenous shrinkage and improved early age hydration as observed by isothermal calorimetry analysis. This thesis highlights some of the beneficial impacts of SAP-cured cementitious systems, and the potential to harness those benefits in large-scale applications of SAP-cured concrete.</p> <br>

Self-heating in storage facilities of biomass pellet can lead to spontaneous combustion. This has resulted in many fires over the years, causing both financial and environmental losses. In order to assess the risk for spontaneous combustion of biomass pellets during storage, it is important to know how prone the fuel is to self-heating, i.e. to determine its reactivity. This thesis presents experimental work performed to develop a sensitive screening test procedure for biomass pellets, using isothermal calorimetry for direct measurement of the heat production rate. This method can be used to compare the reactivity of different biomass pellets. This could be useful for e.g. facility owners to gain better knowledge of their fuels propensity for self-heating and thereby facilitate safer storage. The screening test procedure can also be used for research purposes. Experiments have been performed with 31 different biomass pellet batches to investigate how the pellet composition, origin, etc. influence the reactivity of the pellets. The results from these experiments clearly show a significant difference in reactivity between different types of pellets. The results indicate that pine/spruce mix pellets are significantly more reactive than all other types of pellets tested, and that pellets consisting of 100 % pine are more reactive than pellets consisting of 100 % spruce. Pellets produced from winery wastes, straw, or eucalyptus, have low reactivity compared to pellets consisting of pine and/or spruce. The reactivity of the pellets was shown to be reduced by either introducing certain types of anti-oxidants into the pellets or by extracting lipids from the raw material of pellets. The screening test procedure is already being used today by some facility owners for assessing their fuels propensity for self-heating. The procedure is also one of the suggested test methods in “ISO/CD 20049 Solid biofuels — Determination of self-heating of pelletized biofuels”. / This thesis presents experimental work performed to develop a sensitive screening test procedure for biomass pellets, using isothermal calorimetry for direct measurement of the heat production rate. This method can be used to directly compare the reactivity, that is how prone the fuel is to self-heating, of different batches of biomass pellets. The results could be used for safety assessment by the industry or for research purposes to investigate how different factors influence the self-heating potential. Experiments were performed with 31 different biomass pellet batches to investigate how the pellet composition, origin, etc. influence the heat release rate. The results clearly show that there is a significant difference in reactivity between different types of pellets. Pine/spruce mix pellets are more reactive than the other types of pellets tested and pellets consisting of 100 % pine are more reactive than pellets consisting of 100 % spruce. Pellets produced from winery wastes, straw, or eucalyptus, have low reactivity compared to pellets consisting of pine and/or spruce. The results also show that the reactivity of the pellets can be reduced by either introducing certain types of anti-oxidants into the pellets or by extracting lipids from the raw material of pellets.

Cellulose Nanocrystals have been used in a wide range of applications including cement composites as a strength enhancer. This work analyses the use of CNC from several sources and production methods, and their effects on rheology and hydration of pastes made using different cement types with different compositions. Cement Types I/II and V were used to prepare pastes with different water to cement ratios (w/c) and measure the changes in rheology upon CNC addition. The presence of tricalcium aluminate (cement chemistry denotes as C3A) made a difference in the magnitude of CNC effects. At dosages under 0.5vol% to dry cement, CNC reduced the yield stress up to 50% the control value. Pastes with more C¡A reduced yield stress over a wider range of CNC dosages. CNC also increased yield stress of pastes with dosages above 0.5%, twice the control value for pastes with high C3A content at 1.5% CNC and up to 20 times for pastes without C3A at the same dosage.<br>All the CNCs used were characterized in length, aspect ratio, and zeta potential to identify a definitive factor that governs the effect in the rheology of cement pastes. However, no definitive evidence was found that any of these characteristics dominated the measured effects.<br>The CNC dosage at which the maximum yield stress reduction occurred increased with the amount of water used in the paste preparation, which provides evidence of the dominance of the water to cement ratio in the rheological impact of CNC.<br>14<br>Isothermal calorimetry showed that CNC cause concerning retardation effects in cement hydration. CNC slurries were then tested for sugars and other carbohydrates that could cause the aforementioned effect, then slurries were filtered, and impurities were detected in the filtrate, these impurities were quantified and characterized, however, the retardation appeared to be unaffected by the amount of the species detected, suggesting that the crystal chemistry, which is a consequence of the production method, is responsible of this retardation.<br>This work explores the benefits and drawbacks of the use of CNC in cement composites by individually approaching rheology and heat of hydration on a range of physical and chemical tests to build a better understanding of the observed effects.<br>Understanding the effect of CNCs on cement paste rheology can provide insights for future work of CNCs applications in cement composites.

Calmodulin (CaM) is a ubiquitous calcium-binding protein responsible for the binding and activation of a vast number of enzymes and signaling pathways. It contains two lobes that bind two calcium ions each, separated by a flexible central linker. This structural flexibility allows CaM to bind and regulate a large number of diverse protein targets within the cell in response to Ca2+ gradients. Voltage gated calcium channels (CaVs), as main sources of extracellular Ca2+, are crucial for a number of physiological processes, from muscle contraction to neurotransmission and endocrine function. These large transmembrane proteins open in response to membrane depolarization and allow gated entry of Ca2+ ions into the cytoplasm. Their regulation is currently the subject of intense investigation due to its pharmacological and scientific importance. CaM has been previously shown to pre-associate and act as a potent inhibitor of one class of high-voltage activated (HVA) channels called L-type channels via its interaction with their C-terminal cytoplasmic region. This interaction is primarily mediated by a conserved CaM-binding motif called the ‘IQ’ motif (for conserved isoleucine and glutamine residues), although the exact molecular details of its involvement in inactivation are currently unclear. Elucidation of these details was the primary objective of this dissertation. Recently, a novel sequence motif within this channel called ‘NSCaTE’ (N-terminal spatial calcium transforming element) has been described as an important contributor to calcium-dependent inactivation (CDI) of L-type channels. It was presumed to be unique to vertebrates, but we also show its conservation in a distantly related L-type channel homolog of Lymnaea stagnalis (pond snail). The interaction of CaM with a number of peptides representing the different regulatory motifs (IQ and NSCaTE) for both mammalian and snail isoforms was characterized in an attempt to better understand their role in CDI. Biophysical work with peptides as well as electrophysiology recordings with an N-terminal truncation mutant of Lymnaea CaV1 homolog were performed to expand our understanding of how the interplay between these channel elements might occur. In brief, the most striking feature of the interaction concerns the strong evidence for a CaM-mediated bridge between the N- and C-terminal elements of L-type channels. Further investigation of the CaM interaction with both IQ and NSCaTE peptides using Ca2+-deficient CaM mutants reveals a preference of both peptides for the Ca2+-C-lobe of CaM, and a much higher affinity of CaM for the IQ peptide, suggesting that the N-lobe of CaM is the main interaction responsible for the physiological effects of NSCaTE. These results are consistent with our electrophysiology findings that reveal a distinct buffer-sensitive CDI in wild type LCaV1 that can be abolished by the N-terminal truncation spanning the NSCaTE region. In addition to L-type channels, CaM has also been shown to have an indirect role in the regulation of low-voltage activated (LVA) or T-type channels (CaV3.x), via their phosphorylation by CaM-dependent protein kinase II (CaMKII). Using a primary sequence scanning algorithm, a CaM-binding site was predicted in a cytoplasmic region of these channels that was also previously shown to be important in channel gating. Biophysical experiments with synthetic peptides spanning this gating brake region from the three human and the single Lymnaea isoform strongly suggest that there is a novel, bona fide CaM interaction in this channel region, and also hint that this interaction may be a Ca2+-dependent switch of some sort. The results confirm a possible new role for CaM in the direct regulation of these channels, although the exact mechanism remains to be elucidated.

This thesis is focused at possibilities of preparation and characterization of XRD-amorphous delaminated and dehydroxylated talc phase – meta-talc, which can have its potential application and a starter material for a preparation of magnesium-silicate analogues of geopolymers. Changes in structure and morphology of talc ore were observed during this work. For the purposes of this research, two various talc ores – chloritic and dolomitic were examined. Whole process of meta-talc preparation was examined with whole scale of instrumental techniques such as X-ray diffraction, simultaneous thermogravimetric a differential thermal analysis, infrared spectroscopy, scanning electron microscopy or laser analysis of particle size. Meta-talc can be obtained via mechanochemical activation of talc ore with subsequent calcination. Mechanochemical treatment lead to destruction of original crystal structure and breaking of original bonds, i.e. the product of this treatment was almost amorphous and delaminated. Most of hydroxyl groups were converted to molecules of water which remained adsorbed or coordinated in ore structure. These molecules were removed during calcination step.

Concrete is the most widely used man-made material in the world. Its versatility, strength, and relative ease of construction allow it to be used in the majority of civil infrastructure. However, concrete production plays a significant role in greenhouse gas emissions, accounting for around 8% of CO2 emissions worldwide. This thesis aims to reduce the demand for cement in concrete construction, thus reducing the carbon footprint of the concrete, by focusing on classifying and determining the effectiveness of seven different quarry by-products as partial replacements of cement. Several methods were utilized in this study to characterize the quarry by-products: particle size distribution, helium pycnometry, X-Ray diffraction, X-Ray fluorescence, scanning electron microscopy, and a modified ASTM C1897 Method A that utilizes isothermal calorimetry and thermogravimetric analysis. These various methods allowed for the determination of the physical properties (e.g., gradation, specific gravity, and morphology) and the chemical properties (e.g., mineralogy and reactivity in a cementitious system). The quarry by-products were classified as four granites, two limestones, and one greenstone. These quarry by-products were found to be non-pozzolanic and non-hydraulic. However, there are indications that there may be reactions with the various clays and feldspars in the quarry by-products with calcium hydroxide, which suggests a degree of reactivity that is not necessarily pozzolanic or hydraulic. / Master of Science / Concrete is the most widely used man-made material in the world. Its versatility, strength, and relative ease of construction allow it to be used in the majority of civil infrastructure. However, concrete production plays a significant role in greenhouse gas emissions, accounting for around 8% of CO2 emissions worldwide. This thesis aims to reduce the demand for cement in concrete construction, thus reducing the carbon footprint of the concrete, by focusing on classifying and determining the effectiveness of seven different quarry by-products as partial replacements of cement. Several methods were utilized in this study to determine the physical properties (e.g., gradation, specific gravity, and morphology) and the chemical properties (e.g., mineralogy and reactivity in a cementitious solution) of the materials. The quarry by-products were classified as four granites, two limestones, and one greenstone. In general, these quarry by-products were not found to be reactive as a supplementary cementitious material, although the data may suggest some degree of reactivity between calcium hydroxide and the clays and/or feldspars in the quarry by-products.

At present, soils face great threats. Consequences of human activities, such as climate change, acidification and contamination result in decreased soil health. This is a threat to human health and well-being, since our society is dependent on soil ecosystem services. The soil ecosystems provide resources, such as food and fresh water, regulate the climate and play key parts in important life supporting biological processes, e.g. cycling of carbon and nutrients. Due to increased awareness of the threats that soils face, and its importance to humans, soil quality monitoring has recently received increased attention. Microorganisms run most biological processes in the soil, such as decomposition of organic material and nutrient cycling. Thus, microbial activity and diversity are considered useful biological indicators for soil quality monitoring. These biological properties can be examined using different methods. The aim of the project was to evaluate the potential of multiple substrate-induced respiration (MSIR), using the MicroRespTM system, and isothermal calorimetry for determining microbial activity and diversity in soils contaminated with copper (Cu) and polycyclic aromatic hydrocarbons (PAH). Thereby, the methods’ applicability in risk assessment of contaminated soil could be decided. MSIR is considered appropriate for determining microbial activity and functional diversity, while isothermal calorimetry has not been tested as much in this area. The calorespirometric ratio (produced heat per unit CO2) was calculated to evaluate potential relationships between heat and CO2 at different contamination levels. Although there was some variation between the methods, Cu had a clear effect on both microbial activity and functional diversity. Both methods were thus considered applicable in risk assessment of soil contaminated with Cu. The impact of PAH appeared to be more complex, the effects on microbial activity varied and PAH had little significant effect on functional diversity. Neither of the methods were therefore considered applicable for assessment of soil contaminated with PAH. The calorespirometric ratio did not provide useful results, and cannot be recommended for risk assessment purposes at present. / I dagsläget utsätts marken för stora hot. Följder av mänsklig aktivitet, så som klimatförändringar, försurning och förorening försämrar markens kvalitet. Detta är ett hot mot människors hälsa och välmående, eftersom vårt samhälle är beroende av markens ekosystemtjänster. Markens ekosystem förser oss med exempelvis mat och rent vatten, reglerar klimatet, och har nyckelroller i viktiga biologiska processer, exempelvis cirkulering av kol och näringsämnen. På grund av ökad medvetenhet om hoten mot marken samt dess betydelse för människan, har kontroll av markens kvalitet börjat få ökad uppmärksamhet. Mikroorganismer sköter de flesta biologiska processer som sker i marken, så som nedbrytning av organiskt material och cirkulering av näringsämnen. Därmed anses mikrobiell aktivitet och diversitet vara lämpliga biologiska indikatorer vid kontroll av markens kvalitet. Dessa biologiska egenskaper kan mätas med flera olika metoder. Syftet med projektet var att utvärdera potentialen i att använda multipla substrat-inducerad respiration (MSIR), genom att använda systemet MicroRespTM, samt isotermisk kalorimetri för att mäta mikrobiell aktivitet och funktionell diversitet i mark förorenad med koppar (Cu) och polycykliska aromatiska kolväten (PAH). Därmed kunde metodernas tillämplighet i riskbedömning av förorenad mark bestämmas. MSIR anses vara en lämplig metod i syfte att undersöka mikrobiell aktivitet och funktionell diversitet, medan isotermisk kalorimetri inte är lika beprövat. Kvoten mellan värmeproduktion och respirerad CO2, the calorespirometric ratio, beräknades för att utvärdera eventuella samband mellan värmeproduktion och respiration vid olika föroreningskoncentrationer. Trots att det förekom viss variation mellan metoderna, hade Cu en tydlig effekt på både mikrobiell aktivitet och funktionell diversitet. Båda metoder ansågs därför vara tillämpbara i riskbedömning av Cu-förorenad jord. PAH hade varierande effekt på mikrobiell aktivitet och liten signifikant effekt på funktionell diversitet. Ingen av metoderna ansågs därför tillämpbar i riskbedömning av jord förorenad med PAH. The calorespirometric ratio tillhandahöll ej användbara resultat, och kunde därmed inte rekommenderas i riskbedömningssyfte.

The concept of a self-incompatible solvent is introduced as a molecule composed of two parts (compound 1 and 2) with unfavourable interactions. A third compound will be readily dissolved in this solvent to diminish this unfavourable interaction by dilution. The more incompatible compounds 1 and 2 are, the stronger this behaviour is expected to be. In this work, ionic liquids comprising non-polar carbon chain and polar ionic group are chosen to serve as a model of self-incompatible solvent. The interactions parameters k of the ionic liquids with active ingredients are investigated to examine the effect of self-incompatibility of the ionic liquid molecule. On the other hand, phase separation between compounds 1 and 2 will reduce the positive effect of self-incompatibility. The tendency of phase separation is increasing with increasing size of the two compounds. Thus, if compounds 1 and 2 are blocks tied together into a block copolymer, one expects a decreasing ability of the block copolymer to dissolve an active ingredient with increasing block length. In this work the ability of polybutadiene-block-poly(2-vinylpyridine) (PB-b-P2VP) block copolymers to dissolve the model compound anthracene is investigated. As expected, the solubility indeed decreases with increasing block length.