This research is intended to contribute toward the understanding, development, and implementation of a more fundamental design process for bituminous pavement materials, utilizing thermodynamic properties of the materials involved. The theory developed by van Oss, Chaudhury and Good forms the basis of this research. Optimization of techniques to characterize surface energy, as well as consideration and evaluation of additional factors that influence adhesion in the presence of water, are pursued. A synthesis of theories and mechanisms of bitumen-aggregate adhesion is presented, and existing and potential techniques for surface energy characterization are reviewed to establish firm background knowledge on this subject. The Wilhelmy plate technique was scrutinized and improved methodologies and analysis procedures are proposed. Inverse gas chromatography (IGC) is introduced as an alternative technique. A reasonable comparison of total surface energy values form these techniques with mechanical surface tension values were found. Results suggest that bitumen surface energies do not vary substantially. Inability of these techniques to detect the effect of a liquid additive is rationalized by the ‘potential’ surface energy concept. Suggestions for a more realistic characterization of bitumen polar surface energy components are presented. A static gravimetric sorption technique was employed to characterize aggregate surface energies. Dynamic vapor sorption was identified as a candidate alternative technique for aggregate surface energy characterization. A study on the effect of pH on surface energy components of water revealed that this effect is practically negligible. Calculation of the free energy of electrostatic interaction (DGEL) indicated that this term contributes less than 1% to the total free energy of adhesion. Despite this finding, it is shown that DGEL alone is able to distinguish moisture sensitive mixtures. The significance of electrical phenomena at the interface is elucidated through another mechanism following the work of M.E. Labib. The relationship between pH and electron donor-acceptor properties of aggregate surfaces is presented. The Labib approach potentially offers the solution to quantify the effect of pH on adhesion. In addition, it should be possible to resolve issues with the acid-base scale proposed by the founders of the current theory, by replacing it with a more absolute donor-acceptor scale.

Electrostatic interactions between charged species play a prominent role in determining structures and states of physical system, leading to important technological and biological applications. In coarse-grained simulations, accurate description of electrostatic interactions is crucial in addressing physical phenomena at larger spatial and longer temporal scales. In this thesis, we implement ENUF method, an abbreviation for Ewald summation based on non-uniform fast Fourier transform technique, into dissipative particle dynamics (DPD) scheme. With determined suitable parameters, the computational complexity of ENUF-DPD method is approximately described as O(N logN). The ENUF-DPD method is further validated by investigating dependence of polyelectrolyte conformations on charge fraction of polyelectrolyte and counterion valency of added salts, and studying of specific binding structures of dendrimers on amphiphilic membranes. In coarse-grained simulations, electrostatic interactions are either explicitly calculated with suitable methods, or implicitly included in effective potentials. The effect of treatment fashion of electrostatic interactions on phase behavior of [BMIM][PF6] ionic liquid (IL) is systematically investigated. Our systematic analyses show that electrostatic interactions should be incorporated explicitly in development of effective potentials, as well as in coarse-grained simulations to improve reliability of simulation results. Detailed image of microscopic structures and orientations of [BMIM][PF6] at graphene and vacuum interfaces are investigated by using atomistic simulations. Imidazolium rings and alkyl side chains of [BMIM] lie preferentially flat on graphene surface. At IL-vacuum interface, ionic groups pack closely together to form polar domains, leaving alkyl side chains populated at interface and imparting hydrophobic character. With the increase of IL filmthickness, orientations of [BMIM] change gradually from dominant flat distributions along graphene surface to orientations where imidazolium rings are either parallel or perpendicular to IL-vacuum interface with tilted angles. The interfacial spatial ionic structural heterogeneity formed by ionic groups also contributes to heterogeneous dynamics in interfacial regions.

Doxorubicin (DOX) and Pluronic-PAA interaction was investigated using isothermal titration calorimetry (ITC). DOX/polymer interaction is governed primarily by electrostatic interaction. The uptake of DOX results in the formation of insoluble polymer/DOX complex. Addition of salt weakens the interaction of drug and polymer by charge shielding effect between positive ionized amino group on DOX and oppositely charged polymer chains. However high drug-loading capacity in high salt condition implied that self-association property of DOX also play a role in the drug loading process. / Singapore-MIT Alliance (SMA)

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第20426号 / 農博第2211号 / 新制||農||1048(附属図書館) / 学位論文||H29||N5047(農学部図書室) / 京都大学大学院農学研究科応用生命科学専攻 / (主査)教授 加納 健司, 教授 植田 充美, 教授 三上 文三 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第20715号 / 農博第2244号 / 新制||農||1053(附属図書館) / 学位論文||H29||N5081(農学部図書室) / 京都大学大学院農学研究科応用生命科学専攻 / (主査)教授 加納 健司, 教授 宮川 恒, 教授 三芳 秀人 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

Interparticle interactions determine the microstructure, stability, rheology, and optical properties of concentrated colloidal suspensions involved in paint, paper, cosmetic, and pharmaceutical industries, etc. Frequency domain photon migration (FDPM) involves modeling the photon transport in a multiple scattering medium as a diffusion process in order to simultaneously determine isotropic scattering and absorption coefficients from measured amplitude attenuation and phase shift of the propagating photon density wave. Using FDPM, we investigated the impact of electrostatic interaction upon the optical properties and structure of dense charged suspensions. We demonstrated that electrostatic interactions among charged polystyrene latex may significantly affect the light scattering properties and structure of dense suspensions at low ionic strength (<0.06 mM NaCl equivalent) by actual FDPM measurement. We showed that the structure factor models addressing electrostatic interaction can be used to describe the microstructure of charged suspensions and quenched scattering due to electrostatics, and demonstrated that FDPM has the potential to be a novel structure and surface charge probe for dense suspensions. We also showed that the FDPM measured isotropic scattering coefficients may respond to the change in effective particle surface charge, and displayed the potential of using FDPM for probing particle surface charge in concentrated suspensions. We presented that the interference approximation implies a linear relationship between the absorption coefficient and volume fraction of suspension. We illustrated that FDPM measured absorption coefficient varies linearly with suspension volume fraction and affirmed the interference approximation from a perspective of light absorption. The validation of the interference approximation enables us to develop the methodology for estimating absorption efficiencies and imaginary refractive indices for both particles and suspending fluid simultaneously using FDPM. We further demonstrated a novel application of FDPM measured absorption coefficients in determining pigment absorption spectra, and displayed the potential of using FDPM as a novel analytical tool in pigment and paint industry.

Orientador: Carlos Raimundo Ferreira Grosso / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-24T21:13:36Z (GMT). No. of bitstreams: 1 TelloCelis_Fernando_D.pdf: 4202305 bytes, checksum: d181431b673bfa76df0560500eb7767b (MD5) Previous issue date: 2014 / Resumo: A encapsulação permite a formação de estruturas que apresentam propriedades como a proteção e liberação controlada do material encapsulado. As características do material encapsulado determinam a escolha do material de parede da matriz encapsulante e da técnica de encapsulação. Proteínas e polissacarídeos têm sido investigados para a formação destas matrizes. Diferentes técnicas produzem partículas com diferentes propriedades. A associação de técnicas de encapsulação permite a obtenção de matrizes com melhores propriedades tecnológicas. A gelificação iônica é uma técnica de encapsulação branda, simples e rápida onde polissacarídeos aniônicos interagem com íons divalentes como o Ca2+ para a encapsulação de diversos tipos de compostos incluindo lipídicos. Neste estudo, pectina e alginato foram utilizados para produção de partículas por gelificação iônica. Na primeira parte do estudo, partículas produzidas por gelificação iônica com alginato ou pectina foram revestidas com proteínas da clara de ovo, de soro do leite e da mistura (1:1) das referidas proteínas utilizando-se diferentes concentrações de proteínas em solução a pH 4,0. Partículas de alginato aumentaram de tamanho após revestimento proteico enquanto partículas de pectina diminuíram de tamanho. Aumento da concentração desta na solução produziu aumento na quantidade de proteína adsorvida e de matéria seca nas partículas. Para o maior nível de adsorção proteica, um óleo modelo contendo alto teor de ácidos graxos insaturados foi utilizado como material de recheio e as partículas avaliadas quanto a estabilidade oxidativa. Partículas sem recobrimento proteico foram menos protetivas e quando recobertas com proteínas, apresentaram menor formação de peróxidos quando clara de ovo foi utilizada. Na segunda parte do estudo as partículas obtidas por gelificação iônica foram recobertas com diferentes quantidades de gelatina tipo A, proteínas do soro do leite e mistura das proteínas (1:1). A complexação eletrostática foi estimada pelo potencial zeta e pela quantidade de proteína adsorvida, avaliando-se o efeito do pH e das diferentes relações estequiométricas proteína : polissacarídeo. Partículas que apresentaram maior adsorção proteica foram adicionalmente avaliadas quanto à resistência física e solubilidade proteica quando submetidas a condições gastrointestinais in vitro. O aumento da quantidade de proteína em solução produziu aumento da proteína adsorvida produzindo também aumento de tamanho da partícula quando alginato foi utilizado. Morfologicamente as partículas sem revestimento proteico foram resistentes às condições gastrointestinais in vitro. Independente da proteína utilizada partículas com alginato revestidas com proteína mantiveram integridade física após ensaio intestinal enquanto partículas com pectina e revestidas com gelatina foram destruídas após ensaio intestinal e muito danificadas quando proteínas do soro do leite e mistura gelatina : proteínas do soro do leite foram utilizadas. Quando a solubilidade proteica foi utilizada como parâmetro no ensaio gastrointestinal in vitro, partículas de pectina revestidas com gelatina, a mistura proteica e a proteína do soro do leite apresentaram solubilidades no ambiente gástrico de ~ 56, 38 e 37 % enquanto as partículas de alginato recobertas liberaram ~ 32, 12 e 11 %, respectivamente. Após passagem pelo sistema intestinal, partículas de pectina liberaram praticamente todo o conteúdo proteico adsorvido (> 96 %) enquanto partículas de alginato liberaram quantidades superiores a 82 % / Abstract: Encapsulation allows the formation of structures with properties such as protection and controlled release of the encapsulated material. The characteristics of the core material determine the choice of the wall material and encapsulation technique. Proteins and polysaccharides have been investigated for the formation of these matrices. Different techniques yield particles with different properties. The association of encapsulation techniques allows obtaining matrices with better technological properties. The ionic gelation is a gentle, simple and rapid encapsulation technique in which anionic polysaccharides interact with divalent ions such as Ca2+ for the encapsulation of various types of materials including lipid compounds. In this study, alginate and pectin have been used to produce particles of ionic gelation. In the first part of the study, gelling ionic particles produced with alginate or pectin were coated with proteins from egg white, whey protein and mixture (1:1) of these proteins using different concentrations of proteins in solution at pH 4.0. Particle size increased after coating alginate particles with protein and coated pectin particles had the size reduced. Increasing the protein concentration of the solution produced an increase in the amount of adsorbed protein and dry matter in the particles. For the highest level of protein adsorbed, a model oil containing high content of unsaturated fatty acids was used as core material and the particles evaluated with respect to oxidative stability. Particles without protein coating were less protective and when coated with proteins, showed lower peroxide formation when egg white was used. In the second part of the study the particles obtained by ionic gelation were coated with different amounts of gelatin type A, protein, whey protein and a mixture of both (1:1). The electrostatic complexation was estimated by zeta potential and the amount of adsorbed protein, assessing the effect of pH and the stoichiometry of the various proteins: polysaccharide ratios. Particles showed higher protein adsorption were further evaluated for physical resistance and protein solubility when subjected to in vitro gastrointestinal conditions. The increased amount of protein in solution produced also increases the adsorbed protein causing an increase in particle size when alginate was used. Morphologically, the protein particles without coating were resistant to gastrointestinal conditions in vitro. Independent of protein used, alginate particles coated with protein maintained physical integrity after intestinal assay, while pectin particles coated with gelatin were destroyed after intestinal assay and damaged when the whey protein or and gelatin : whey proteins mixture were used. When protein solubility was used as a parameter in the gastrointestinal in vitro assay, pectin particles coated with gelatin, whey protein and gelatin : whey proteins mixture showed solubility in the gastric environment of 56, 38 and 37% while the coated alginate particle released 32, 12 and 11 %, respectively. After passage through the intestinal tract, coated pectin particles released substantially all adsorbed protein content (> 96%). Coated alginate particles released quantities above 82% / Doutorado / Consumo e Qualidade de Alimentos / Doutor em Alimentos e Nutrição

Orientador: Flavia Maria Netto / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-25T15:30:20Z (GMT). No. of bitstreams: 1 Sadahira_MitieSonia_D.pdf: 5351794 bytes, checksum: 3b4bdc18fc4978c11662cb3791bc6fe6 (MD5) Previous issue date: 2014 / Resumo: Nos confeitos aerados (marshmallow e nougat), a espuma é produzida pela aeração de xaropes de açúcares, estabilizada por proteínas tais como proteínas da clara de ovo (PCO). A pectina, polissacarídeo aniônico, pode formar complexos eletrostáticos com proteína em pH abaixo do ponto isoelétrico da proteína. A hidroxipropilmetilcelulose (HPMC) é um polissacarídeo neutro com propriedades emulsificantes. O trabalho visou estudar as propriedades espumantes (capacidade de aeração e estabilidade da espuma) da PCO na presença destes polissacarídeos em solução aquosa e sistema modelo de açúcares. Na primeira etapa, foram avaliados os efeitos das interações PCO/polissacarídeo nas propriedades espumantes em solução aquosa. Os efeitos da concentração de biopolímeros (2,0-4,0% p/p), proporção PCO:pectina (15:1-55:1) e temperatura (70-80 °C) nas propriedades espumantes no pH 3,0 foram avaliados, utilizando delineamento composto central. Na proporção PCO:pectina 15:1, os complexos eram próximos da eletroneutralidade e com tamanho médio de 95,91+ ou - 8,19 µm, conduzindo para maior estabilidade da espuma quanto à desproporção. Na proporção 55:1, os complexos não eram eletricamente neutros e com tamanho médio de 45,92+ ou - 3,47 µm, resultando em espumas com menor drenagem de líquido e coalescência. Foram avaliados os efeitos de concentração de biopolímeros (2,0-5,0% p/p), proporção PCO:HPMC (2:1-18:1) e pH (3,0-6,0) a 75 °C utilizando delineamento composto central rotacional (DCCR) e do comportamento dos biopolímeros na solução aquosa em diferentes pH nas propriedades espumantes. No pH 3,0, os biopolímeros eram compatíveis, conduzindo a melhores propriedades espumantes enquanto nos pH 4,5 e 6,0, os biopolímeros eram incompatíveis, resultando em menor estabilidade com relação a desproporção. Na segunda etapa do trabalho, foram avaliados os efeitos das interações PCO/polissacarídeo em sistema modelo de açúcares com características de marshmallow (densidade<0,50 g/mL; atividade de água<0,75). A composição da solução de açúcares (42,5% sacarose, 42,5% xarope de glicose e 15% de açúcar invertido) foi definida utilizando delineamento experimental de mistura. Os efeitos da concentração de biopolímeros (1,40¿5,60% p/p) e proporção PCO:pectina (7:1¿63:1) nas respostas foram avaliadas utilizando um DCCR, no pH 3,0. As respostas foram viscosidade aparente da mistura açúcares/PCO/pectina antes do batimento e densidade, overrun, parâmetros reológicos da amostra aerada recém-processada e após 24 horas (módulo elástico G¿, módulo viscoso G" e 'delta'). Na proporção PCO:pectina 7:1, a mistura apresentou baixa capacidade de aeração e uma espuma com característica menos sólida e baixa estabilidade. Na proporção 49:1, a mistura apresentou maior capacidade de aeração e comportamento elástico da espuma. Os efeitos da concentração de biopolímeros (1,4-5,6% p/p) e proporção clara de ovo:HPMC (2:1-18:1) nas respostas das misturas açúcar/PCO/HPMC foram avaliados, utilizando um DCCR no pH 3,0 e as mesmas respostas avaliadas no estudo com misturas açúcar/PCO/pectina. Na concentração de biopolímeros 5,0% p/p e proporção PCO:HPMC 14:1 foram realizados experimentos em diferentes pH. No pH 3,0, foram obtidos maior capacidade de aeração e comportamento elástico. No pH 4,5, a espuma apresentou melhor estabilidade comparada a espuma no pH 3,0. No pH 6,0, a espuma apresentou propriedades espumantes ruins e comportamento viscoso. Portanto, o controle das interações proteína/polissacarídeo é um fator chave para o desenvolvimento de produtos aerados com maior estabilidade física / Abstract: In aerated confectionery (marshmallow and nougat), foam is produced by aeration of sugar syrups and stabilized by proteins such as egg white protein (EW). Pectin, an anionic polysaccharide, may form electrostatic complexes with protein at pH values bellow the isoeletric point (pI) of the protein. Hydroxypropylmethylcellulose (HPMC) is a neutral polysaccharide with emulsifying properties. The study aimed at studying the foaming properties (foaming capacity and foam stability) of EW in the presence of these polysaccharides in aqueous solution and high sugar system. Firstly, the effects of EW/polysaccharide interaction on the foaming properties in aqueous solution were evaluated. The effects of biopolymer concentration (2.0-4.0% w/w), EW:pectin ratio (15:1-55:1) and temperature (70-80 °C) were evaluated at pH 3.0, using a central composite design. At EW:pectin ratio 15:1, the complexes were close to electroneutrality and with an average size of 95.91+ or - 8.19 µm, leading to greater stability related to disproportionatin. At ratio 55:1, the complexes were not electrically neutral and with an average size of 45.92+ or - 3.47 µm, resulting in a low drainage of liquid and coalescence. The effects of biopolymer concentration (2.0-5.0% w/w), EW:HPMC ratio (2:1-18:1) and pH (3.0-6.0) at 75 °C were evaluated using central composite rotatable design (CCRD) and the behavior of biopolymer in aqueous solution on the foaming properties at different pH. At pH 3.0, EW and HPMC were compatible leading to better foaming properties whereas at pH 4.5 and 6.0, EW and HPMC were incompatible resulting in lower stability related to disproportionation. In the second part of the study, the effects of EW/polysaccharide interactions on a model system of sugar with characteristics of marshmallow (density<0.50 g/mL; water activity<0.75) were evaluated. For that, a sugar solution composition (42.5% of sucrose, 42.5% of glucose syrup and 15.0% of invert sugar) was defined by a mixture experimental design. The effects of biopolymer concentration (1.40-5.60% w/w) and EW:pectin ratio (7:1-63:1) on the reponses were evaluated using CCRD, at pH 3.0. The responses were apparent viscosity of sugar/EW/pectin mixture before whipping, overrun, foam density and, rheological parameters of fresh foam and foam aged for 24 h (elastic modulus G¿, viscous modulus G" and phase angle 'delta'). At EW:pectin ratio 7:1, the mixture showed low foaming capacity and a foam with less solid character and low stability. At ratio 49:1, the mixture presented greater foaming capacity and elastic behavior of foam. The effects of biopolymer concentration (1.4-5.6% w/w) and EW:HPMC ratio (2:1-18:1) on the responses of sugar/EW/HPMC mixtures were evaluated using CCRD at pH 3.0 and the same responses evaluated in the study of sugar/EW/pectin mixtures. At biopolymer concentration 5.0% w/w and EW:HPMC ratio 14:1, experiments were carried out at different pH. At pH 3.0, the higher foaming capacity and elastic behavior were obtained. At pH 4.5, foam showed better stability than foam at pH 3.0. At pH 6.0, foam presented the poorest foaming properties and viscous behavior. Thus, the control of protein/polysaccharide interactions is a key factor for the aerated products developing with higher stability / Doutorado / Consumo e Qualidade de Alimentos / Doutora 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 2018-08-22T05:50:23Z (GMT). No. of bitstreams: 1 Almeida_TalitaEmanuelaMeloe_M.pdf: 2060488 bytes, checksum: 4adc0b3a48b5ba83103d990622a1286a (MD5) Previous issue date: 2013 / Resumo: Este estudo teve como objetivo a produção de micropartículas por técnicas combinadas de gelificação iônica e interação eletrostática utilizando alginato de sódio, concentrado proteico do soro do leite (WPC) e manteiga fundida para imobilização do micro-organismo Erwinia sp. D12 e avaliação da conversão de sacarose em isomaltulose por células íntegras livres e imobilizadas em processo descontínuo durante quatro dias. No estudo preliminar, os biopolímeros alginato de sódio e WPC foram caracterizados para produção de micropartículas com boas propriedades. A análise da carga elétrica disponível de alginato de sódio em solução ou emulsão com diferentes concentrações de manteiga fundida e das proteínas do WPC em solução indicou que em uma faixa de pH de 3,0 - 4,5 pode ocorrer uma interação de natureza eletrostática entre os biopolímeros. Misturas formadas em diferentes proporções entre emulsão de alginato de sódio com diferentes concentrações de manteiga fundida e solução proteica de WPC foram caracterizadas com relação à carga elétrica e tamanho médio dos coacervados insolúveis formados. Maiores tamanhos de coacervados, variando entre 29,12 µm a 33,72 µm, foram obtidos na proporção volumétrica 1:6 (emulsão de alginato e manteiga fundida:WPC) sendo que a adição de diferentes concentrações de manteiga fundida não modificou o tamanho dos coacervados formados. As micropartículas de alginato contendo manteiga fundida foram preparadas pela técnica de gelificação iônica associado com recobrimento, por interação eletrostática, com solução de WPC em diferentes concentrações e em seguida foi avaliada a adsorção proteica sobre as micropartículas em sistemas diluídos e concentrados. Um aumento da adsorção proteica pôde ser observado com o aumento da concentração de proteína em solução e diminuição da concentração de manteiga adicionada. Utilizando-se solução de WPC na concentração de 4% (m/m) foram obtidas maiores quantidades de proteínas adsorvidas sobre as micropartículas com taxas de adsorção variando de 44,35% para micropartículas com baixo nível de manteiga fundida, de 37,58% para micropartículas contendo nível intermediário de manteiga e de 30,61% para micropartículas contendo alto nível de manteiga. Micropartículas com elevado teor de umidade, conteúdo proteico acima de 30% e tamanho variando entre 130,0 µm a 161,5 µm puderam ser produzidas pela técnica de gelificação iônica com posterior recobrimento, por interação eletrostática, com solução 4% (m/m) de WPC. A partir do estudo preliminar, as micropartículas com os diferentes tratamentos foram estudadas para imobilização celular do micro-organismo Erwinia sp. D12 com uma contagem inicial de 108-107 UFC/mL e atividade enzimática de 10,7 U/mL. A incorporação de diferentes concentrações de manteiga fundida modificou a atividade enzimática do micro-organismo encapsulado sendo que uma maior adição de manteiga fundida (2%, m/m) acarretou em uma maior atividade enzimática (17,68 U/mL). O tamanho médio das micropartículas sem recobrimento variou entre 91,54 ¿ 106,52 µm sendo observado um aumento no tamanho, 118,34 ¿ 143,12 µm, após o recobrimento. Células íntegras na forma livre e imobilizadas com os diferentes tratamentos foram avaliadas com relação à conversão de sacarose em isomaltulose em processo descontínuo durante quatro dias. Maiores taxas de conversão foram obtidas no primeiro dia de análise empregando células livres ou imobilizadas com os diferentes tratamentos. A taxa de conversão diminuiu no decorrer dos dias, em todos os tratamentos, sendo observada uma queda mais acentuada na conversão utilizando células íntegras livres. As maiores médias aritméticas de conversão de sacarose em isomaltulose foram alcançadas por micropartículas de gelificação iônica sem adição de manteiga fundida e micropartículas de gelificação iônica adicionadas de 2% (m/m) de manteiga fundida, 33,77% e 35,12%, respectivamente, sem diferenças estatísticas entre as mesmas. O recobrimento adicional das micropartículas acarretou em uma diminuição na taxa de conversão devido provavelmente à diminuição no tamanho dos poros ou recobrimento total dos mesmos. Outra hipótese levantada está no pH utilizado para produção das micropartículas (pH 3,75) que encontra-se fora da faixa ótima de crescimento do micro-organismo. Os resultados indicam o potencial de emprego de células íntegras de Erwinia sp. D12 imobilizadas em hidrogel de alginato, sem recobrimento adicional das micropartículas, para conversão de sacarose em isomaltulose em processos descontínuos / Abstract: This study aimed to produce microparticles by combined techniques of electrostatic interaction and ionic gelation using sodium alginate, whey protein concentrated (WPC) and butter for immobilization of micro-organism Erwinia sp. D12 and evaluating the conversion of sucrose to isomaltulose by immobilized whole cells and free cells in a batch process during four days. In a preliminary study, biopolymers sodium alginate and WPC were characterized for production of microparticles having good properties. The analysis of electric charge available sodium alginate in solution or emulsion with different concentrations of butter and WPC solution indicated that in a pH range from 3.0 to 4.5 may occur electrostatic interactions between the biopolymers. Mixtures formed in different ratios emulsion of sodium alginate with different concentrations of butter and WPC solution were characterized with respect to size and load presented average coacervates insoluble formed. Larger coacervates sizes, ranging from 29.12 µm to 33.72 µm, were obtained in ratio 1:6 (emulsion alginate and butter: WPC) being that addition of different concentrations of butter not statistically change the size of coacervates formed. Alginate microparticles containing butter were prepared by ionic gelation associated with coating by electrostatic interaction with WPC at different concentrations and then the protein adsorption on the microparticles in dilute and concentrated was assessed. An increase in protein adsorption could be observed even in concentrated systems, with increasing concentration of protein in solution and decreased concentration of butter added. Using WPC solution at a concentration of 4% (w/w) were obtained larger quantities of proteins adsorbed on the microparticles with varying rates of adsorption of 44.35% for microparticles containing low level of butter , of 37.58% for microparticles containing intermediate level of butter and 30.61% for microparticles containing high level of butter. Microparticles content high moisture, protein content above 30% and size ranging from 130.0 µm to 161.5 µm could be produced by ionic gelation technique with subsequent coating by electrostatic interaction with solution 4% (w/w) WPC. From the preliminary study, the microparticles with different treatments were studied for cell immobilization of micro-organism Erwinia sp. D12 with an initial count of 108-107 CFU/mL and enzyme activity of 10.7 U/mL. The incorporation of different concentrations of butter modify the enzymatic activity of the encapsulated micro-organism being greater than the addition of butter (2%, w/w) resulted in an increased enzymatic activity (17.68 U/mL). The average size of uncoated microparticles ranged from 91.54 µm to 106.52 µm an increase in size was observed, 118.34 - 143.12 µm, after coating. The addition of different concentrations of butter not influence statistically the average size of microparticles. Whole cells in free form and immobilized with different treatments were evaluated for conversion of sucrose to isomaltulose in a batch process during four days. Higher rates of conversion of sucrose to isomaltulose were obtained on the first day of analysis using free cells or immobilized with the different treatments. The conversion rate decreased during the days, in all treatments, with a more pronounced decrease observed in conversion using free cells. The greatest average conversion of sucrose into isomaltulose were reached by microparticle ionic gelling without addition of butter and microparticles ionic gelling added 2% (w/w) of butter, 33.77% and 35.12% respectively, no statistical differences between them. The additional coating of microparticles by electrostatic interaction resulted in a decrease in conversion rate probably due to a reduction in pore size or full coating thereof. Another hypothesis is the pH used for production of microparticles, at pH 3.75, which is outside the optimum range for growth of the micro-organism. The results indicate the potential use of whole cells of Erwinia sp. D12 immobilized in alginate hydrogel without additional coating of microparticles for conversion of sucrose to isomaltulose in batch processes / Mestrado / Nutrição Experimental e Aplicada à Tecnologia de Alimentos / Mestra em Alimentos e Nutrição

Harnessing the Sun’s energy via the conversion of solar photons to electricity has emerged as a sustainable energy source to fulfill our future demands. In this regard, solution-processable, size-tunable PbS quantum dots (QDs) have been identified as a promising active materials for photovoltaics (PVs). Yet, there are still serious challenges that hinder the full exploitation of QD materials in PVs. This dissertation addresses two main challenges to aid these QDs in fulfilling their tremendous potential in PV applications. First, it is essential to establish a large-scale synthetic technique which maintains control over the reaction parameters to yield QDs with well-defined shape, size, and composition. Rigorous protocols for cost-effective production on a scale are still missing from literature. Particularly, previous reports of record-performance QD-PVs have been based on small-scale, manual, batch syntheses. One way to achieve a controlled large-scale synthesis is by reducing the reaction volume to ensure uniformity. Accordingly, we design a droplet-based continuous-flow synthesis of PbS QDs. Only upon separating the nucleation and growth phases, via a dual-temperature-stage reactor, it was possible to achieve high-quality QDs with high photoluminescence quantum yield (50%) in large-scale. The performance of these QDs in a PV device was comparable to batch-synthesized QDs, thus providing a promise in utilizing automated synthesis of QDs for PV applications. Second, it is crucial to study and control the charge transfer (CT) dynamics at QD interfaces in order to optimize their PV performance. Yet, the CT investigations based on PbS QDs are limited in literature. Here, we investigate the CT and charge separation (CS) at size-tunable PbS QDs and organic acceptor interfaces using a combination of femtosecond broadband transient spectroscopic techniques and steady-state measurements. The results reveal that the energy band alignment, tuned by the quantum confinement, is a key element for efficient CT and CS processes. Additionally, the presence of interfacial electrostatic interaction between the QDs and the acceptors facilitates CT from large PbS QD (bandgap < 1 eV); thus enabling light-harvesting from the broad near-infrared solar spectrum range. The advances in this work – from automated synthesis to charge transfer studies – pave new pathways towards energy harvesting from solution-processed nanomaterials.