Content: Acrylic resin (AR) is a most popular retanning agent due to its selective filling property and advantage of formaldehyde-free. The retanning performance of acrylic resin mainly depends on its penetration depth and filling parts in leather. Therefore, to improve the retanning performance, it is necessary to fully understand the factors affecting the mass transfer and the distribution of acrylic resin in leather. We have found that the structure and the charge of leather and the dosage of acrylic resin rather than the molecular weight of acrylic resin are important factors affecting the penetration rate of acrylic resin in crust leather by using fluorescent tracer technique. In this study, from the view of electrostatic interaction, effects of neutralizing pH and retanning auxiliaries such as phenol sulfonic acid condensation (PSAC) and sodium carboxymethylcellulose (CMC) on the penetration and the distribution of acrylic resin in crust leather were investigated. Higher neutralizing pH led to a faster transfer of acrylic resin in leather because of the decrease in the positive charges of chrome-tanned leather (isoelectric point 7.1) and the increase in the negative charges of acrylic resin. Employing PSAC and CMC enhanced acrylic resin transfer in crust leather due to the dramatic increase in the negative charges of acrylic resin. These results indicated that decreasing the electrostatic binding force between acrylic resin and crust leather is beneficial to the penetration of acrylic resin in leather, which could be achieved by adjusting the neutralizing pH or using acrylic resin together with proper retanning auxiliaries. Take-Away: 1. Using phenol sulfonic acid condensation and sodium carboxymethylcellulose enhanced acrylic resin transfer in crust leather. 2. Decreasing electrostatic binding force between acrylic resin and crust leather is beneficial to penetration of acrylic resin in leather. 3. Increasing neutralizing pH or using proper retanning auxiliaries can decrease the electrostatic interaction between acrylic resin and crust leather effectively.

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No / We investigated five different methods for evaluating the electrostatic interaction between atoms in force field calculations on organic solids. Atomic charges and multipoles were obtained by fitting them to the molecular electrostatic potential, calculated in vacuum with an ab initio quantum mechanical method. Multipole moments were derived using three schemes, differing in the order in which the monopoles, dipoles and quadrupoles were fitted. For comparison, Gasteiger charges were also calculated. Using these electrostatic models, the lattice parameters and the molecular geometry of 48 organic crystals were optimised with the DREIDING force field. During the optimisation, the atomic multipoles were rotated with their local environment to account for molecular flexibility. For comparative reasons, rigid-body optimisations were performed on a subset of structures. The results were analysed in terms of structural parameters of the lattice and the molecules, and, for the ten polymorphic systems present in the test set, in terms of relative stability. On average, the multipole methods were not superior to the point charge methods for the full optimisation. For rigid molecules, however, the multipole models gave a substantial improvement in lattice parameters. No evidence was found that parameters for van der Waals energies need to be refitted for a specific electrostatic model. Energy differences between polymorphs were less than 5 kcal mol¿1 in eight out of ten cases, independent of the electrostatic model used. The results show that our use of distributed multipoles to describe the intra-molecular as well as inter-molecular electrostatic interactions does lead to an improvement in accuracy for rigid molecules, but not for flexible molecules. The investigation shows that accurate descriptions of the intra-molecular as well as the inter-molecular energies are crucial for the successful optimisation of crystal structures of organic solids.

Orientador: Carlos Raimundo Ferreira Grosso / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-22T17:05:27Z (GMT). No. of bitstreams: 1 Nogueira_GislaineFerreira_M.pdf: 14331604 bytes, checksum: 0299d24569a9a146c6085746fe878fed (MD5) Previous issue date: 2013 / Resumo: O objetivo deste trabalho foi produzir micropartículas com multicamadas contendo alto teor de proteínas, capazes de serem estáveis a condições adversas do meio e resistentes ao ambiente gástrico. Na primeira parte deste estudo, interações eletrostáticas entre o alginato e proteínas do concentrado proteico do soro do leite (WPC) foram avaliadas em relação às condições de pH (3,5 e 3,75) e proporções de polissacarídeo e proteína. A formação de coacervados com os biopolímeros alginato e WPC foi caracterizada quanto à aparência, tamanho médio e carga superficial. Esta análise permitiu definir as condições em que a interação entre proteínas e partículas de alginato pudesse ocorrer. Assim, micropartículas de alginato produzidas por gelificação iônica foram posteriormente recobertas por interação eletrostática com proteínas, utilizando soluções de diferentes concentrações de concentrado proteico do soro do leite, em dois pHs. Foram testadas três concentrações de proteína em solução para cada pH de recobrimento, sendo 0,6, 3 e 4% para o pH 3,5 e 1,7, 3 e 4% para o pH 3,75. As partículas obtidas foram caracterizadas com relação ao teor total de proteína, conteúdo de umidade, tamanho e morfologia. As maiores adsorções proteicas foram obtidas com a maior concentração de proteína em solução (4%) em ambos pHs. A partir deste estudo preliminar, selecionou-se a amostra de micropartículas com o maior teor de proteína adsorvida para se construir multicamadas em sua superfície através da interação eletrostática. Na segunda parte do estudo, foram produzidas multicamadas de alginato e proteínas do concentrado proteico do soro do leite sobre a superfície da partícula de alginato. Essas partículas foram caracterizadas igualmente as anteriores. A proteína total adsorvida na partícula foi alta, variou de 51,20% a 64,91%, sendo 33,24% dessa proteína encontrada na primeira camada (AlgPart1). Na terceira camada (AlgPart3), também foram encontradas elevados teores proteicos, variando de 17,96% a 31,67%. Uma relação proporcional entre a concentração de alginato e WPC com o aumento da adsorção proteica nesta camada foi observada. A formação das multicamadas (AlgPart1 e AlgPart3) sobre a superfície das partículas provocou uma diminuição significativa no teor de umidade das partículas (AlgPart), ao contrário do que foi observado com o tamanho. Observações realizadas por MEV revelaram que as camadas produzidas com alginato tendem a ter superfícies mais lisas, e com WPC, tendem a ser rugosas. A amostra de micropartículas com multicamadas que apresentou a maior adsorção proteica foi avaliada quanto à estabilidade em temperatura de esterilização (121 ºC, por 15 minutos),pH (2, 4, 6 e 8), concentração de sal (0, 50, 100, 150 e 200 mM) e em condições gastrointestinais (in vitro). Além disso, foram caracterizadas em relação ao tamanho médio, solubilidade proteica e morfologia. Partículas multicamadas úmidas permaneceram íntegras à temperatura de esterilização, apresentaram uma diminuição significativa de tamanho e um acréscimo significativo na solubilidade da camada proteica para o meio em pH 2, e permaneceram estáveis em pHs 4, 6 e 8. A perda de proteína das multicamadas da partícula aumentou significativamente com o aumento da força iônica do meio. As partículas com multicamadas se mostraram parcialmente resistentes às condições gástricas, com uma liberação de 30,5% da proteína presente na partícula e, foram sensíveis à atividade proteolítica em ambiente intestinal simulado promovendo a desintegração das multicamadas e a liberação de praticamente toda proteína da partícula. Considerando os resultados obtidos, conclui-se que é possível a formação de multicamadas de alginato e WPC sobre a superfície de partículas de gelificação iônica com alta adsorção proteica, capazes de serem estáveis em condições adversas do meio e parcialmente resistente às condições gástricas / Abstract: The objective of this work was to produce microparticles with multilayer containing high protein content, capable of being stable to harsh conditions of the environment and resistant to the gastric environment. In the first part of this study, the electrostatic interaction between the alginate and protein of concentrate whey protein (WPC) was evaluated in relation to pH conditions (3.5 and 3.75) and ratio of polysaccharide: protein. The formation of coacervates between the alginate and WPC was characterized as the visual appearance, medium size and surface charge. This analysis allowed us to define the conditions in which the interaction between proteins and alginate particles could occur. Thus alginate microparticles produced by ionic gelation were subsequently coated by electrostatic interaction with proteins, using solutions with different concentrations of whey protein at two pHs. Three concentrations were tested with respect to the protein concentration, being 0.6, 3 and 4% for pH 3.5 and 1.7, 3 and 4% for pH 3.75. The particles were characterized with respect to the total protein content, moisture content, size and morphology. The highest protein adsorption were obtained with the higher concentration of protein solution (4%) by both pH. From this preliminary study, we selected the particle with the highest level of protein adsorbed to construct multilayer using electrostatic interaction on its surface. In the second part of the study, were produced multilayers of alginate and WPC were produced on the surface of the particle of alginate. These particles were characterized in relation to protein adsorption, moisture content, medium size and morphology. The total protein adsorbed on the particle was high, varied from 51.20% to 64.91%, being 33.24% of this protein found in the first layer (AlgPart1). In the third layer (AlgPart3), were also found elevated protein levels, varying from 17.96% to 31.67%. A proportional relationship between the concentration of alginate and WPC with increased protein adsorption was observed in this layer. The formation of multilayers (AlgPart1 and AlgPart3) on the particle surface caused a significant decrease in moisture content of the particles (AlgPart), contrary to what was observed with the size. Observations made by SEM revealed that layers produced with alginate tend to have most smooth surfaces, and WPC tend to be rough. The particle multilayers that presented the highest protein adsorption was evaluated as to the stability at sterilization temperature (121 º C for 15 minutes), pH (2, 4, 6 and 8), salt concentration (0, 50, 100, 150 and 200 mM) and in gastrointestinal conditions. Furthermore were characterized with respect to medium size, protein solubility and morphology. Moist Multilayer particles have remained stable against the temperature of sterilization, showing a significant decrease in size and a significant increase in the solubility of the protein layer into the medium at pH 2, and remain stable at pH 4, 6 and 8. The loss of protein from multilayer particle increased as ionic strength increased. The particles with multilayer were partially resistant to gastric conditions, with a release of 30.49% of the protein in the particle, and were susceptible to proteolytic activity in simulated intestinal environment promoting the particle disintegration and the release of all protein recovering the particles. Considering the results obtained, it is concluded that it is possible the formation of multilayer alginate and WPC on the surface of particles obtained ionic gelation using high protein adsorption, capable of being stable in adverse conditions of the environment (temperature, pH, ionic strength) and resistant to gastric conditions / Mestrado / Consumo e Qualidade de Alimentos / Mestra em Alimentos e Nutrição

Orientador: Carlos Raimundo Ferreira Grosso / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-19T12:00:06Z (GMT). No. of bitstreams: 1 Rodrigues_JulianaBurger_M.pdf: 1839902 bytes, checksum: 0d3867db41bf2e89beac57f40237e09a (MD5) Previous issue date: 2012 / Resumo: Este estudo teve como objetivo produzir micropartículas por gelificação iônica associada à interação eletrostática, contendo constituintes nutricionalmente importantes para a alimentação de larvas de peixes. Na primeira parte deste estudo, foram desenvolvidas micropartículas por gelificação iônica, utilizando-se pectina e cloreto de cálcio para a formação das matrizes. O recheio das micropartículas era constituído de proteínas do soro de leite, na sua forma não-desnaturada ou desnaturada, e óleo de soja adicionado de oleoresina de páprica. Nas partículas em que o recheio era constituído somente de óleo, a proteína de soro de leite foi incluída por meio da interação eletrostática na superfície da micropartícula. Além disto, avaliou-se a influência do teor de cálcio e do grau de amidação da pectina na incorporação proteica, nos teores de umidade e na morfologia das micropartículas. As micropartículas produzidas por gelificação iônica, seguidas de recobrimento com proteínas do soro de leite (WPC) por interação eletrostática, foram as que apresentaram os melhores teores de umidade e proteína. Na segunda parte do estudo, partículas produzidas por gelificação iônica, utilizando pectina de baixo grau de esterificação amidada, foram recobertas com proteínas de soro de leite por interação eletrostática na tentativa de mimetizar a composição centesimal encontrada em náuplios de Artemia, alimento vivo comumente utilizado na criação intensiva de larvas de peixes. Após a produção, as partículas foram caracterizadas em relação à composição centesimal, tamanho médio e distribuição de tamanho, morfologia e comportamento de reidratação após secagem por liofilização. As matérias-primas utilizadas para a produção das partículas foram também caracterizadas quanto à composição centesimal e ao potencial zeta quando em solução. Adicionalmente, partículas otimizadas quanto à composição centesimal foram utilizadas em experimento de crescimento de larvas de pacu (Piaractus mesopotamicus). Lactobacillus acidophilus foram acrescentados a uma das dietas e seu efeito avaliado no experimento biológico. Os teores de proteína, lipídio e umidade das partículas foram semelhantes aos dos náuplios de Artemia, com valores médios de 50, 23 e 85%, respectivamente. Partículas apresentaram forma esférica quando úmidas ou reidratadas, com uma distribuição de tamanho de 75-619 µm e aglomeração após secagem. A reidratação das partículas secas foi instantânea, sem diferença de tamanho médio entre partículas úmidas ou reidratadas. O experimento biológico mostrou que as larvas alimentadas com as dietas experimentais não apresentaram crescimento quanto ao peso e tamanho, em relação aos resultados observados para as larvas alimentadas com os náuplios de Artemia ou para uma dieta comercial usada como controle. As dietas testadas, incluindo as experimentais, náuplios de Artemia e dieta microencapsulada comercial, apresentaram elevada taxa de ingestão (>90%). As taxas de sobrevivência obtidas foram de 83,6%, 43,6%, 30,7% e 34,5%, para larvas alimentadas com náuplios de Artemia, dieta microencapsulada comercial, dieta experimental contendo o probiótico e dieta experimental, respectivamente, após 28 dias de experimento. No teste de estresse provocado pela exposição ao ar, larvas que receberam a dieta contendo o probiótico por 21 dias apresentaram menor porcentagem de mortalidade quando comparado à dieta comercial, porém ainda superior à observada com larvas alimentadas com Artemia. A possível inadequação nutricional das dietas experimentais, a baixa quantidade mineral e vitamínica presentes nas dietas experimentais e a possível indisponibilidade de nutrientes devido à associação forte desses nutrientes com o polissacarídeo utilizado poderiam ter produzido as taxas de crescimento nulas obtidas, indicando a necessidade de novos experimentos / Abstract: The aim of this study was to produce microparticles by ionic gelation associated with electrostatic interaction containing important nutritionally constituents for fish larvae. In the first part of this study, microparticles were developed by pectin using ionic gelation and calcium chloride to form the matrices. The filling of the microparticles consisted of nondenatured or denatured whey proteins and soybean oil with paprika oleoresin. Filling particles consisting only of oil and whey protein was included through the electrostatic interaction on the surface of the microparticle. In addition, the influence of calcium and the amidation of pectin in the protein incorporation, moisture content and the morphology of the microparticles were evaluated. The microparticles produced by ionic gelation followed by coating with whey proteins (WPC) by electrostatic interaction were the ones that contained the best levels of moisture and protein. In the second part of the study, particles produced by ionic gelation using low methoxyl amidated pectin were coated with milk whey proteins by electrostatic interaction in an attempt to mimic the proximate composition found in Artemia, commonly used in the intensive rearing of fish larvae. The particles after production were characterized with respect to their chemical composition, average size and size distribution, morphology and rehydration behavior after freeze dried. The raw materials used for the production of particles were also characterized as its chemical composition and zeta potential in solution. Additionally, optimized particles as to chemical composition were used in an experiment of growth with larvae of Pacu (Piaractus mesopotamicus). Lactobacillus acidophilus has been added in one of the diets and its effect evaluated in this assay. The levels of protein, lipid and moisture of the particles were similar to those of Artemia, with mean values of 50, 23 and 85% respectively. Particles had spherical shape when wet or rehydrated with a size distribution from 75 to 619 mM and agglomeration after drying. Rehydration of the dry particles was instantaneous without difference in the average size between wet or rehydrated particles. The biological experiment showed that larvae fed the experimental diets showed no growth in weight and size, in relation to the results observed for larvae fed Artemia or with the commercial diet used as control. The diets tested, including the experimental diets, Artemia and the commercial diet showed a high rate of intake (> 90%). Survival rates were 83.6%, 43.6%, 30.7% and 34.5% for larvae fed with Artemia, commercial microencapsulated diet, experimental diet containing the probiotic and experimental diet, respectively, after 28 days of experiment. Larvae fed the diet containing the probiotic for 21 days showed a lower percentage of mortality in relation to the commercial diet, but still higher than that observed with larvae fed with Artemia. The possible nutritional inadequacy of the experimental diets, low ash content present in the experimental diets and possible lack of nutrients due to the strong association with the polysaccharide used in the diets may have produced low growth, indicating that more experiments are needed / Mestrado / Nutrição Experimental e Aplicada à Tecnologia de Alimentos / Mestre em Alimentos e Nutrição

Orientador: Carlos Raimundo Ferreira Grosso / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-19T20:01:52Z (GMT). No. of bitstreams: 1 Souza_FlaviaNoelide_M.pdf: 960857 bytes, checksum: 86bfea219b44c6fdc64e31d18b5491df (MD5) Previous issue date: 2012 / Resumo: O objetivo deste trabalho foi produzir micropartículas capazes de resistir ao ambiente gástrico e liberar o material encapsulado em ambiente intestinal. As partículas foram produzidas pela gelificação iônica da pectina de baixo teor de esterificação amidada com íons cálcio e posteriormente recobertas com proteínas utilizando soluções de diferentes concentrações de concentrado proteíco do soro do leite (WPC), submetidas ou não a tratamento térmico. A condição de adsorção das proteínas sobre a superfície das partículas de pectina foi definida a partir da análise da carga livre total das soluções de proteína e polissacarídeos e assim a definição de pH e a relação entre eles foi usada para produção das micropartículas. As micropartículas obtidas foram caracterizadas com relação a sua carga elétrica de forma a se obter as condições de pH e a relação de concentração de polissacarídeo : proteína em solução em que a interação eletrostática entre os biopolímeros fosse possível. Foram testados 5 níveis de proteína em soluções ( 2, 4, 6, 8 e 12%) associados a proteína sem tratamento térmico (STT) e tratada termicamente (TT), desnaturação a 80ºC por 15 minutos, sendo que as partículas obtidas foram caracterizadas com relação a morfologia, teor de proteína e conteúdo de umidade. A partir deste estudo preliminar foram selecionados dois tipos de partículas, uma partícula recoberta com proteína STT e outra partícula recoberta com proteína TT, utilizando como critério de seleção as soluções proteícas onde foram obtidas partículas com o maior teor de proteína adsorvida. As partículas selecionadas foram avaliadas com relação à resistência ao ambiente gástrico e capacidade de liberação do material encapsulado em ambiente intestinal, sendo que, para isso, as micropartículas foram submetidas a uma simulação das condições gastrointestinais in vitro, avaliando sua integridade nestas condições e quantificando-se o teor de proteína solubilizada em ambiente gástrico simulado. Também foi avaliada a estabilidade das partículas em diferentes pHs, tamanho médio, morfologia interna e externa e capacidade de reidratação pós liofilização. As concentrações de proteína em solução em que foram obtidos os mais altos valores de proteína adsorvida foram de 4 a 6%, com adsorção de 49,2 ± 1,0 % para partículas com WPC - STT e 27,6 ± 1,8% para solução de WPC - TT. Variações de tamanho das micropartículas após sua inserção em diferentes pHs assim como em suco gástrico artificial, foram de 224,8 µm a 342,9 µm. As partículas liofilizadas e reidratadas readquiriram forma e tamanho original após uma hora de inserção em água além de apresentarem estabilidade às variações de pH. As partículas permaneceram íntegras em ambiente gástrico e desintegraram-se em meio intestinal, entretanto durante a simulação das condições gástricas houve uma alta solubilização da proteína em suco gástrico quando o pH foi ajustado a 1,2 com a presença de pepsina, enquanto menor solubilização foi observada quando o pH do suco gástrico foi ajustado para 3, também em presença de pepsina / Abstract: The aim of this study was to produce microparticles able to resist the gastric environment and after releasing the encapsulated material in the gut environment. Particles were produced by ionic gellling using low methoxyl amidated pectin with calcium ions and coated with protein using solutions of different concentrations of whey protein concentrated (WPC), submitted or not submitted to thermal treatment. The condition of the protein adsorption on the surface of pectin particles was defined as the analysis of free charge total protein and polysaccharide solutions and thus defining the relationship between pH and ratio used for the production of particles. The particles obtained were characterized with to their electrical change so as to obtain conditions of pH and the concentration of polysaccharide to protein in solution in which the electrostatic interaction between the biopolymer possible. Five levels of protein in solution (2, 4, 6, 8 e 12%) associated with non-denatured (STT) and denatured (TT) protein in a water bath at 80°C for 15 minutes were tested, and the resulting particles were characterized with respect to their morphology, protein and moisture content. From this preliminary study were selected two types of particles, one particle with STT protein and another with TT protein, using as a standard the conditions of protein in solution which produced the highest level of protein adsorbed. The particles selected were evaluated with respect to resistance to the environment of the stomach and ability to release encapsulated material in intestinal environment, and for that, the microparticles were subjected to a simulated gastrointestinal conditions in vitro evaluating its integrity in these conditions and the protein solubilized in the simulated gastric environment quantified. The stability of the particles at different pHs, average size, internal and external morphology and capacity to rehydration after freeze drying were also evaluated. The concentration of protein in solution where the highest values of protein adsorbed was obtained was 4 ¿ 6%, with adsorption of 49.2 ± 1.0% for particles with WPC - STT and 27.6 ± 1.8 % for the solution contained WPC - TT. The size of the microparticles after their insertion at different pHs as well as in artificial gastric juice, ranging from 224,8 µm to 342,9. The microparticles freeze dried and rehydrated regained the shape and original size after one hour of insertion in water and were stable against changes in pH. The particles remained intact in the environment of the stomach and disintegrated at the intestinal environment, however during the simulation of gastric conditions the was a high concentration of protein in gastric juice while the pH was adjusted to 1.2 with the presence of pepsin while smaller solubilization was observed then the pH of gastric juice was adjusted to 3, also in the presence pepsin / Mestrado / Nutrição Experimental e Aplicada à Tecnologia de Alimentos / Mestre em Alimentos e Nutrição

Per- and polyfluoroalkyl substances (PFASs) have drawn great attention recently, due to their environmental persistence, potential toxicity and global distribution. PFAS is a large family of substances, characterized by a perflourinated carbon chain and a functional group. All PFASs are synthetic and have been widely used since the 1950s due to their unique properties of being both hydrophobic and oleophobic, making them useful for many industries. To be able to predict the fate of PFASs in the environment and to obtain detailed understanding of the transport processes, their partitioning behavior between soil particles and water depending on a range of parameters must be investigated. The aims of this study was to investigate the effects of pH, cation composition, functional group and perfluorocarbon chain length on sorption of PFASs to soil particles, by batch sorption experiment in laboratory scale. The laboratory-scale experiments were combined with modelling of the net charge to evaluate if net charge is a good predictor for sorption of PFASs to soil particles. 14 PFASs of varying length and functional groups were studied (PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUnDA, PFDoDA, PFTeDA, PFBS, PFHxS, PFOS and FOSA). The effect on sorption of Na+, Ca2+ (two different concentrations) and Al3+ were investigated at pH-range 3-6. Modelling of net charge was carried out in the geochemical model Visual MINTEQ. The soil had 45% organic carbon content. The adsorption of PFASs was strongly correlated with perfluorocarbon chain length, showing a stronger adsorption to particles with increasing perfluorocarbon chain length (i.e. more hydrophobic). The relation between sorption (represented by the distribution coefficient log Kd) and perfluorocarbon chain length was linear for all PFSAs and C3 to C10 PFCAs. The PFSAs (sulfonate functional group) sorbed stronger to soil particles than the PFCAs (carboxylic functional group), and FOSA (sulfonamide functional group) sorbed the strongest. For most PFCAs, (C5-C13) there was a trend of decreasing log Kd (i.e. decreased sorption) with increasing pH, due to pH-dependent changes of the soil particle surfaces. For short and intermediate perfluorocarbon chain length PFCAs (C5-C8) and for PFHxS among the PFSAs, cations had a clear effect on sorption. Aluminium ions (trivalent, Al(NO3)3) had the largest effect, followed by calcium (divalent, Ca(NO3)2) where higher concentration resulted in stronger sorption. Sodium (univalent, NaNO3) had the least influence on sorption. The net charge modelled with Visual MINTEQ takes into account many parameters (including pH) that affect the surface charge and sorption of PFASs to soil particles. When comparing log Kd for the different PFASs with pH and net negative charge, net charge was a better predictor of sorption of PFASs to soil particles than solution pH alone. / Per- och polyfluoroalkylsubstanser (PFAS:er) har dragit stor uppmärksamhet till sig på senare tid, på grund av deras persistenta egenskaper, potentiella toxicitet och globala utbredning. PFAS är en stor grupp ämnen, kännetecknad av en perflourinerad kolkedja och en funktionell grupp. Alla PFAS är syntetiska och har använts i stor utsträckning sedan 1950-talet på grund av deras unika egenskaper av att vara både vatten- och fettavstötande, vilket gör dem användbara för många industriella tillämpningar. För att kunna förutsäga var dessa föroreningars hamnar i miljön och få mer detaljerad förstående för transportprocesserna, måste deras fördelningbeteende mellan jordpartiklar och vattenundersökas för en rad olika parametrar. Syftet med denna studie var att undersöka effekterna av förändrat pH, katjonsammansättning, funktionell grupp och perfluorkolkedjelängd på sorption av PFAS:er till jordpartiklar. Detta gjordes med sorptionsexperiment i laboratorieskala. Laboratorieexperimentet kompletterades med modellering av nettoladdning, för att se huruvida detta väl kunde förklara sorptionen till jordpartiklar. 14 PFAS:er av varierande längd och med tre olika funktionella grupper studerades (PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUnDA, PFDoDA, PFTeDA, PFBS, PFHxS, PFOS och FOSA). Effekten på sorption av Na+, Ca2+ (två olika koncentrationer) och Al3+ undersöktes vid pH-intervallet 3-6. Modellering av nettoladdning utfördes i den geokemiska modellen Visual MINTEQ. Jorden som användes hade en halt av organiskt kol på 45%. Adsorptionen av PFAS:er var starkt positivt korrelerad med kedjelängden på de perfluorinerade kolkedjan. Ju längre kolkedja (dvs. mer hydrofob), desto starkare adsorption till partiklar. Relationen mellan sorptionen (här uttryckt som partitioneringskofficienten log Kd) och kedjelängd var linjär för alla PFSA och för C3 till C10 för PFCA. PFSA (sulfonat) adsorberade starkare än PFCA (karboxyl), och FOSA (sulfonamid) adsorberades starkast. För de flesta PFCA, (C5-C13) fanns en allmän trend där log Kd (dvs. sorption) minskade med ökande pH, på grund av pH-beroende förändringar på jordpartiklarna. För korta och medellånga PFCA (C5-C8) och för PFHxS hade katjonsammansättningen en tydlig effekt på sorptionen. Aluminiumjoner (trevärd, Al(NO3)3) hade den största effekten, följt av kalcium (tvåvärd, Ca(NO3)2) där den högre koncentrationen resulterade i starkare sorption. Natrium (envärd, NaNO3) hade minst påverkan på sorptionen till jordpartiklar. Visual MINTEQ tar hänsyn till många parametrar (inklusive pH), när nettoladdningen på jordpartiklarnas yta räknas ut. När log Kd för olika PFAS:er jämfördes med endera pH eller negativ nettoladdning, drogs slutsatsen att nettoladdning korrelerade bättre med sorption än pH.

Le présent travail est destiné à acquérir un ensemble de données expérimentales et quantitatives cohérentes sur le comportement physico-chimique d'un système constitué d'un polysaccharide linéaire, flexible et chimiquement fonctionnalisé en groupements carboxyliques, le carboxyméthyl-dextrane (CMD) et d'un milieu ionique comportant des cations d'affinité variée pour ces fonctions : Na+, Ca2+ et Cd2+. La densité de sites et leur constante de dissociation - complexation ont été déterminées par titrage potentiométrique avec des électrodes spécifiques (proton et cadmium). Les propriétés électro-hydrodynamiques et les transitions conformationnelles ont été étudiées en combinant la conductimétrie, l'électrophorèse, la diffusion dynamique de lumière et la viscosimétrie. Enfin, la stabilité colloïdale en relation avec les interactions intermoléculaires a été étudiée par turbidimétrie et diffusion dynamique de lumière. En présence d'ions monovalents, le comportement du CMD, typique d’une particule microgel molle, est déterminé par la force ionique et la concentration en polysaccharide. A basse force ionique, le CMD est en condition de bon solvant lorsqu'il est peu concentré tandis que le recouvrement des doubles-couches électriques autour des macromolécules détermine les propriétés électro-hydrodynamiques du CMD en régime concentré. A haute salinité, les interactions électrostatiques intramoléculaires et interparticulaires sont négligeables, et la macromolécule a un comportement caractéristique de polymère en mauvais solvant à haute fraction volumique. En présence de cations divalents, le calcium, et plus encore le cadmium, entrent en compétition avec le proton pour l’occupation des sites carboxyliques, ce qui s’accompagne par une réorganisation locale des chaînes polymères. A haute force ionique, la taille élevée des agrégats, la vitesse initiale d'agrégation élevée, ainsi que la persistance d'une forte turbidité au maximum d'effet, suggèrent que les agrégats sont formés en régime de type agrégation limitée par la diffusion des particules (DLA) / The present work focused on the acquisition of experimental and quantitative data on the physico-chemical properties of a linear, flexible and chemically functionalized polysaccharide by carboxymethyl grafting, yielding carboxymethyldextran macromolecules (CMD) and an aqueous electrolyte containing various ions Na+, Ca2+ et Cd2+ with different chemical affinity for these chemical functions. Charge density and complexation – dissociation constants have been evaluated using specific electrodes-based potentiometric titration. The electro-hydrodynamic properties and the conformational transitions were examined through electrical conductivity increment measurements, electrophoresis, dynamic light scattering and viscosimetry. Also, colloidal stability has been investigated by means of turbidimetry and dynamic light scattering. In the presence of monovalent ions, the behaviour of CMD, typically that of a soft microgel particle, is strongly depending on ionic strength and polysaccharide content. For low ionic strengths and in dilute regime, CMD is in situation of good solvent while in concentrated regime, overlapping double layers that develop around macromolecules governs the electro-hydrodynamic features of CMD. For sufficiently high ionic strengths, intermolecular and intramolecular electrostatic interactions are nearly suppressed, and CMD behaves as a polymer in bad solvent upon increase of its concentration in the medium. In the presence of divalent ions, calcium ions and cadmium ions are in competition with hydronium ions to occupy the carboxylic sites, and this situation is concomitantly accompanied by local reorganization of polymer chains. The large size of formed clusters, the high initial aggregation rate and the increased turbidity all suggest that aggregates are generated according to a diffusion limited aggregation (DLA) type of mechanism

Ce travail porte sur l’étude de mésophases lamellaires lyotropes qui contiennent des polymères hydrosolubles confinés dans les lamelles d’eau de l’empilement. L’effet du polymère confiné sur la stabilité de la structure lamellaire est en particulier étudié grâce à une mesure directe des interactions entre les membranes de tensioactif grâce la technique du Surface Force Apparatus (SFA). Les systèmes étudiés sont des fluides complexes et très visqueux ce qui a donné lieu au développement d’une nouvelle méthode pour analyser les données collectées. En l’absence de polymère dissous dans l’empilement lamellaire, la valeur du module de compressibilité élastique mesurée est remarquablement interprétée avec la théorie électrostatique corrigée des corrélations des contre-ions. En présence de polymère, au fur et à mesure que les macromolécules remplacent le contenu en eau, le module élastique de compressibilité de l’empilement lamellaire chute,signature d’une interaction attractive due à la présence des macromolécules. Néanmoins, les développements théoriques proposés ne parviennent pas à interpréter quantitativement cette décroissance. De plus, des comportements très intéressants et inattendus ont été mis en évidence lors de l’approche d’un point critique : la présence de dislocations de très grands vecteurs de Burgers à grande séparation ainsi que des phénomènes d’avalanches. En particulier, des énergies de nucléation de dislocation ont pu être extraites. / This work deals with lyotropic lamellar mesophases which contain confined hydrosoluble polymers in the water layers of the stack. In particular the effect of confined polymers on the stability of the lamellar structure is investigated through a direct measurement of the interactions between the surfactant membranes thanks to the Surface Force Apparatus (SFA) technique. The investigated systems are complex fluids and samples are extremely viscous, this is why a new procedure for analyzing the collected data has been developed. In the absence of dissolved polymer in the lamellar stack, the measured value of the elastic compressibility modulus is remarkably interpreted with the electrostatic interaction corrected from the counterions correlations. In the presence of polymer, as long as the macromolecules replace the water content the elastic compressibilitymodulus of the lamellar stack decreases, evidencing an attractive interaction due to the macromolecules. Nevertheless, the proposed theoretical developments fail to quantitatively interpret this drop. Moreover, very interesting and unexpected phenomena have been evidenced on the approach of one critical point: dislocations of large Burgers vectors at large separations and avalanche phenomena. In particular dislocation nucleation energies have been extracted.

Submitted by Daniel Lucas Zago Caetano (daniel.caetano@sjrp.unesp.br) on 2017-09-29T00:38:30Z No. of bitstreams: 1 caetano_dlz_dr_sjrp.pdf: 13957655 bytes, checksum: 5b96587e7372ab57b53df4f703a1de39 (MD5) / Approved for entry into archive by Monique Sasaki (sayumi_sasaki@hotmail.com) on 2017-09-29T18:31:12Z (GMT) No. of bitstreams: 1 caetano_dlz_dr_sjrp.pdf: 13957655 bytes, checksum: 5b96587e7372ab57b53df4f703a1de39 (MD5) / Made available in DSpace on 2017-09-29T18:31:12Z (GMT). No. of bitstreams: 1 caetano_dlz_dr_sjrp.pdf: 13957655 bytes, checksum: 5b96587e7372ab57b53df4f703a1de39 (MD5) Previous issue date: 2017-09-26 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Este trabalho tem por objetivo estudar, por meio de simulações computacionais baseadas no método de Monte Carlo, interações eletrostáticas em superfícies e macromoléculas. Na primeira parte deste estudo é abordada a interação entre polieletrólitos, mais especificamente, homopolímeros e copolímeros em bloco suscetíveis à variações de pH, e macromoléculas com distribuição helicoidal de carga compatível com a encontrada em polinucleotídeos. A macromolécula foi representada por um cilindro rígido infinito que simula a parte central do DNA/RNA, totalmente inacessível ao polieletrólito. Visando simular os sulcos do DNA, duas esferas completam o modelo: uma localizada na posição dos grupos fosfato (esfera externa) e outra localizada entre a esfera externa e o cilindro (esfera interna). A distribuição de carga da macromolécula é dada por um conjunto de cargas negativas monovalentes centradas nas esferas externas. O polieletrólito foi representado por uma cadeia de N esferas rígidas carregadas, conectadas por um potencial harmônico e com um valor de pKa específico. A solução eletrolítica foi tratada pela teoria de Debye-Hückel. Os efeitos do pH, da concentração de sal, da estrutura primária e da rigidez da cadeia polimérica e da distribuição de carga da macromolécula sobre as propriedades conformacionais e físico-químicas da cadeia adsorvida foram calculados. Verificou-se que a presença da macromolécula modifica as propriedades ácido/base do polieletrólito e que o efeito de regulação de carga afeta o processo de adsorção/dessorção. Além disso, constatou-se uma dependência entre as conformações adotadas pelo polieletrólito na superfície da macromolécula e a concentração de sal da solução. Na segunda parte deste trabalho é investigada a influência das interações de hidratação sobre a capacitância diferencial da dupla camada elétrica por meio de simulações de Monte Carlo e por modelos teóricos baseados na aproximação de Campo Médio. Um eletrodo plano e carregado foi inserido em uma solução eletrolítica constituída por íons monovalentes e com concentração próxima às condições fisiológicas. As interações de hidratação foram descritas por meio de potenciais de Yukawa, as quais foram adicionadas às interações de Coulomb e de volume excluído entre os íons e entre os íons e o eletrodo. O modelo de Campo Médio proposto não só inclui interações de hidratação aos pares ânion-ânion, ânion-cátion e cátion-cátion de intensidades arbitrárias, mas também leva em consideração o tamanho finito dos íons por meio de duas abordagens distintas: i) equação de estado de Carnahan-Starling; e ii) modelo de rede. A capacitância diferencial obtida não só pelas simulações de Monte Carlo, mas também pelas aproximações de Campo Médio, apresenta o característico pico duplo, usualmente denominado de camel-shape, no qual seu decaimento reflete o empacotamento dos contraíons nas proximidades do eletrodo. Verificou-se também que a presença das interações de hidratação entre os íons e entre o eletrodo e os íons promove o surgimento de uma pequena região de depleção de carga nas proximidades do eletrodo, similar à camada de Stern. / This work aims to analyze electrostatic interactions on surfaces and macromolecules through the use of computational simulations based on the Monte Carlo method. In the first part of this study, we discuss the interaction between polyelectrolytes – more specifically homopolymers and block-copolymers which are susceptible to variations in pH – and macromolecules with helical charge distribution compatible with that found in polynucleotides. The macromolecule was represented by an infinite rigid cylinder, which mimics the central core of RNA/DNA, totally inaccessible to the polyelectrolyte. In order to simulate DNA grooves, two additional spheres complete the model: one being centered at the position of the phosphate groups (outer sphere) and the other being located between the outer sphere and the cylinder (inner sphere). The charge distribution of the macromolecule is given by a helical set of monovalent negative charges centered at the outer spheres. The polyelectrolyte was represented by a chain with charged hard spheres connected by harmonic bonds and presenting a specific pKa value. The electrolyte solution was treated at the Debye-Hückel level. The effects of pH, salt concentration, primary structure and stiffness of the polymer chain on the conformational and physicochemical properties of the adsorbed chain were investigated. Results show that the presence of the macromolecule modifies the acid/base properties of the polyelectrolyte and that the effect of charge regulation affects the adsorption/desorption process. Furthermore, a dependence between the conformations adopted by the polyelectrolyte on the surface of the macromolecule and the salt concentration of the solution was also observed. In the second part of this study, we investigated the influence of hydration interactions on the differential capacitance of an electric double layer by means of Monte Carlo simulations and by theoretical models based on mean-field approximation. A charged planar electrode was inserted in an electrolyte solution composed of monovalent ions and with concentration close to that found at physiological conditions. The hydration interactions were modeled through Yukawa potentials, which were added to Coulomb and excluded volume interactions among the ions and between the ions and the electrode. The proposed mean-field model not only include hydration interactions to the cation-cation, anion-anion and cationanion pairs, but also take into account the finite size of the ions through two distinct approaches: i) the Carnahan-Starling equation of state, and ii) the lattice gas model. We found that both our Monte Carlo simulations and mean-field approaches predict a characteristic double-peak (the so-called camel shape) of the differential capacitance, where its decrease reflects the packing of the counterions near the electrode. We also found that the presence of hydration interactions among the ions and between the ions and the electrode promotes the emergence of a small region of charge depletion near the electrode, similar to the Stern layer. / FAPESP: 2013/13151-7