CNPq / No meio da ampla biodiversidade da flora brasileira, a ora-pro-nobis (Pereskia aculeata Miller) desperta especial interesse, pela alta quantidade de mucilagem em suas folhas. Plantas mucilaginosas são estudadas há algum tempo no processo de floculação/coagulação em tratamentos de água, com a intenção de, reduzir ou até mesmo suceder a utilização do sulfato de alumínio. A mucilagem é um biopolímero com grande capacidade de formar gel, soluções viscosas e estabilizar sistemas de emulsão. O presente trabalho teve como finalidade, avaliar o rendimento da mucilagem em processos de extração, caracterizar a mucilagem não clarificada, e clarificada e aplicar o biopolímero clarificado da P. aculeata, no processo de coagulação/floculação. Para tal as folhas foram secas em estufa até peso constante, foi feita a extração da mucilagem em solução aquosa por duas metodologias diferentes avaliando assim o rendimento, caracterização da morfologia por microscopia eletrônica de varredura (MEV) e difratometria de raio X (DRX), composição estrutural por infravermelho com transformada de Fourier (FT-IR), determinação do pH potencial de carga zero e do comportamento térmico por análise termogravimétrica (TG/DSC). Para a avaliação de coagulação e floculação, o biopolímero foi avaliado em água do Rio Pato Branco por ensaios em Jar Test avaliando a eficiência da remoção de turbidez, remoção de substâncias húmicas, e aromáticas. A extração da mucilagem foi avaliada no rendimento da produção, em que a extração a 95 ºC (30 min) apresentou rendimento três vezes maior que a extração a 60 ºC (6 horas). A caracterização morfológica exibiu uma estrutura amorfa, esponjosa e com adesão de partículas menores à superfície das partículas maiores, indicando um material higroscópico que pode ser usado como coagulante, sendo semelhante a outras mucilagens pesquisadas, em aspectos de grupos funcionais e de comportamento térmico. A P. aculeata se confirmou como auxiliar no processo de coagulação/floculação em relação aos parâmetros e faixas estudadas, sendo mais eficaz em conjunto com o sulfato de alumínio. Como é uma planta de fácil cultivo, atóxica e com custo relativamente baixo para a extração do seu biopolímero é uma alternativa promissora no tratamento de água e efluentes diminuindo a utilização do sulfato de alumínio no processo de floculação/coagulação. / In the midst of the wide biodiversity of Brazilian flora, the ora-pro-nobis (Pereskia aculeata Miller) arouses special interest because of the high amount of mucilage in its leaves. Mucilage plants have been studied for some time in the flocculation / coagulation process in water treatments, with the intention of reducing or even succeeding the use of aluminum sulphate. Mucilage is a biopolymer with great gelforming, viscous solutions and stabilizing emulsion systems. The purpose of this study was to evaluate the yield of the mucilage in extraction processes, to characterize the clarified and clarified mucilage and to apply the clarified biopolymer of P. aculeata in the coagulation / flocculation process. For this, the leaves were oven dried to constant weight, the mucilage was extracted in aqueous solution by two different methodologies, evaluating the yield, characterization of the morphology by scanning electron microscopy (SEM) and X-ray diffractometry (XRD) (FT-IR), determination of potential zero charge pH and thermal behavior by thermogravimetric analysis (TG / DSC). For the evaluation of coagulation and flocculation, the biopolymer was evaluated in water of the Pato Branco River by tests in Jar Test evaluating the efficiency of the removal of turbidity, removal of humic and aromatic substances. The extraction of the mucilage was evaluated in the yield of the production, in which the extraction at 95 ºC (30 min) yielded a three times higher yield than the extraction at 60 ºC (6 hours). The morphological characterization showed an amorphous structure, spongy and with adhesion of smaller particles to the surface of larger particles, indicating a hygroscopic material that can be used as a coagulant, being similar to other mucilages studied, in aspects of functional groups and thermal behavior. P. aculeata was confirmed as an aid in the coagulation / flocculation process in relation to the parameters and ranges studied, being more effective in conjunction with aluminum sulphate. As it is an easy-to-grow, non-toxic plant with relatively low cost for the extraction of its biopolymer, it is a promising alternative in the treatment of water and effluents by reducing the use of aluminum sulphate in the flocculation / coagulation process.

A procura por novos materiais que possam substituir parcial ou totalmente os derivados do petróleo, representa um desafio para os pesquisadores na área de ciências dos materiais. Dentro deste contexto, o desenvolvimento de materiais biodegradáveis surge como uma das opções viáveis. A introdução de biopolímeros ou aditivos naturais nas formulações de poliolefinas, utilizadas na indústria de embalagens, tem sido objeto de estudo de vários trabalhos de pesquisa. Acelerar a degradação desses materiais, de modo que a razão custo/benefício de sua produção seja favorável, é um dos objetivos desses estudos. Tem sido relatado que a adição de polidroxibutirato (PHB) à poliolefinas pode contribuir para acelerar a degradação desses materiais. Neste trabalho, misturas de polietileno (PEBD) e PHB foram preparadas em extrusora de rosca dupla, utilizando como carga, a torta de mamona, subproduto do biodiesel. Há um número muito escasso de trabalhos versando sobre a utilização da torta de mamona como aditivo na indústria de plásticos. Há, entretanto, necessidade de se encontrar maiores aplicações para esse resíduo, de forma a tornar a cadeia produtiva do biodiesel mais viável. A avaliação da biodegradação dos produtos obtidos é um dos objetivos específicos deste trabalho. A processabilidade dos materiais e as propriedades mecânicas foram avaliadas por meio dos ensaios convencionais prescritos pelas normas ASTM.. As metodologias de planejamento de experimentos: planejamento fatorial e modelagem de misturas foram utilizadas, respectivamente, para determinação das melhores condições de processamento e para avaliar o efeito da proporção dos componentes das misturas nas propriedades obtidas. O software Minitab foi usado com esta finalidade. A morfologia das misturas foi avaliada através de microscopia eletrônica de varredura (MEV). A biodegradação foi avaliada em solo simulado por diferentes períodos de tempo através de determinações de perda de massa das amostras. Os resultados obtidos demonstraram que a adição do PHB e da mamona ao PEBD levam a obtenção de propriedades superiores de flexão e ao aumento de Módulo de Young. A resistência à tração e as propriedades de impacto do PEBD se deterioraram com a adição do PHB, assim como com a adição da carga. As misturas ternárias com maior teor de PHB apresentaram biodegradação mais acentuada. A mistura com a composição polietileno, poli(3-hidroxibutirato) e torta de mamona ( 70%/20%/10%) sofreu degradação mais acelerada que as misturas binárias. Este fato sugere que a torta de mamona catalisa a degradação dos materiais, fato este que pode ser atribuído à morfologia da mistura ternária.

Orientadores: Telma Teixeira Franco, Cristiana Maria Pedroso Yoshida / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-06T18:08:42Z (GMT). No. of bitstreams: 1 Reis_ArleteBarbosados_M.pdf: 1735903 bytes, checksum: de3ef62122076a76e44326331e797276 (MD5) Previous issue date: 2005 / Resumo: Um novo conceito de embalagens para alimentos vem sendo estudado, conhecido como embalagem ativa, combinando áreas da tecnologia de alimentos, biotecnologia, embalagem e ciência dos materiais. Estes sistemas consistem na incorporação de aditivos tais como, agentes antimicrobiano, antioxidantes, antiumectantes, microrganismos antagonistas, bactericidas, antibióticos, enzimas e outros, na embalagem ao invés de serem adicionados diretamente nos alimentos. Os filmes de quitosana vem sendo estudados para aplicação como embalagem ativa devido às suas propriedades antimicrobianas, elasticidade, flexibilidade, biodegradabilidade e por fornecerem uma boa barreira ao oxigênio. O objetivo deste trabalho foi agregar valor ao filme de quitosana incorporando aditivos e, a partir de então, a aplicação deste em coberturas de papelão, formando uma embalagem bioativa. De acordo com a atuação esperada, diferentes aditivos foram incorporados à matriz padrão (filme de quitosana). Com o intuito de reduzir a passagem de umidade para o interior das embalagens foi incorporado o agente sequestrante de umidade, sílica micronizada Siloyd FP244 (filme-sílica) e para atuar na oxidação no interior das embalagens foi incorporado ácido cítrico, um agente antioxidante. Após a obtenção dos filmes bioativos, estes foram aplicados em coberturas de papelão, dando origem ao sistema embalagem papelão-filme, o qual foi caracterizado quanto às propriedades de barreira (permeabilidade ao vapor d¿água, permeabilidade ao oxigênio e isotermas de sorção) e quanto às propriedades mecânicas (esmagamento de onda, compressão na coluna e absorção de água). A incorporação de sílica nos filmes de quitosana e consequente aplicação em coberturas de papelão reduziu a passagem de umidade através das coberturas de papelão, absorvendo a umidade. As propriedades mecânicas do sistema embalagem papelão filme-sílica demonstraram um decréscimo no esmagamento, quando comparado aos outros sistemas de embalagem, mas apresentou uma maior capacidade de absorção de água. O sistema embalagem papelão filme-cítrico atuou reduzindo a passagem de oxigênio através das coberturas de papelão e promoveu uma melhoria nas propriedades mecânicas, devido à maior rigidez do papelão / Abstract: Active packaging can be defined as a kind of packaging where package, product the environment interact to increase shelf life, maintaining the final quality. It combines advances in food technology, biotechnology, packaging and material science. These packaging systems are based on additives incorporation directly into polymeric matrix, such as antimicrobial agents, antioxidants, antiumectants, antagonists, bactericides, antibiotics, enzymes, etc. Chitosan is natural polymer derived by deacetylation of chitin. Chitosan presents a good film- form properties and has studied as a potential polymers of food packaging. This natural polymers are biodegradable, easily decomposable and environmentally friendly. This work studied a new package system formed by a bilayer of paperboard card and chitosan films containing different additives and moisture-absorbing agent (silica siloyd FP 244) were incorporated into chitosan matrix films. The barrier properties (water vapor and oxygen permeabilities) and mechanical properties were characterized. WVP reduced as silica was incorporated into chitosan films. The water absorbing capacity increased, indicating that the silic acted as a moisture absorbing agent. The mechanical properties of active moisture package systems decreases in comparisom of paperboard cards without coating. The active package systems containing citric acid reduced the oxygen permeability and increase the rigidity / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

Orientador: Yoon Kil Chang / Tese (doutorado)- Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-03T16:41:50Z (GMT). No. of bitstreams: 1 Sebio_Leonard_D.pdf: 5261418 bytes, checksum: c5f42d63b358e2b0af36c89bdbdd0259 (MD5) Previous issue date: 2003 / Resumo: Devido ao crescente acúmulo de lixo proveniente de plásticos sintéticos, agredindo o ecossistema, diferentes estratégias estão sendo seguidas com o intuito de procurar diminuir essa agressão através da prevenção, redução, reciclagem, valorização química dos materiais sintéticos e especialmente oo uso de polímeros biodegradáveis. O uso de amido como materiais termoplásticos é promissor devido principalmente à disponibilidade natural desse produto, que é extraído de uma fonte inesgotável de matérias-primas (cereais, raízes, tubérculos, etc.). No entanto, as blendas não são totalmente biodegradáveis. Nessa ótica a presente pesquisa envolveu o uso de processo de extrusão termoplástica de dupla rosca e uma matriz retangular apropriada para produzir materiais laminados termoplastificados biodegradáveis a base de amido e gelatina plastificados por glicerol e água susceptíveis de serem moldados na forma de descartáveis, etc. Foi empregada a metodologia de superfície de resposta (MSR) para estabelecer modelos matemáticos preditivos baseados em Modelo Central Composto Rotacional (CCDR), num planejamento fatorial completo 23 de 5 níveis e de 3 variáveis independentes, a saber as concentrações de gelatina (50,0; 100,0, 150,0 g/g base úmida), de glicerina (50,0, 100,0, 150,0 g/g) em 1000g da blenda e umidade (30, 35, 40 %). As respostas obtidas das combinações 2 a 2 dos 3 fatores foram avaliadas considerando as propriedades mecânicas de tração e de barreira dos laminados termoplásticos obtidos após extrusão, tais como: a Resistência Máxima à Tração, Percentagem de Alongamento, Elasticidade (Modulo de Young), Permeabilidade ao vapor de água e Índice de desintegração em meio aquoso. Foi em seguida, desenvolvida uma metodologia matemática de otimização de ensaios que permitiu a partir de uma fórmula de combinação de melhores respostas, escolher 6 ensaios principais entre os 18 do delineamento. Após escolher as amostras de melhores propriedades foram avaliadas as ropriedades fisico-químicas e morfológicas, a saber: Microscopia Eletrônica de varredura (MEV), Estimativa de Condições de Armazenamento, Absorção de Água, Difratometria de Raios-X e Índice de Cristalinidade Relativa. Para observar o comportamento térmico dos laminados, avaliou-se as seguintes propriedades térmicas: Condutividade Térmica, Análise Termogravimétrica (TGA), Análise Térmica Dinâmica Mecânica (TDMA) e Calorimetria Diferencial de Varredura (DSC). As propriedades mecânicas foram principalmente influenciadas pelas concentrações de gelatina e de glicerol na avaliação dos laminados termoplásticos que apresentaram valor médio de resistência máxima à tração de 4,87 MPa; com valor máximo de 12,62 MPa; valor médio de porcentagem de alongamento de 46,46 % com máximo em 81,58% e valor médio de Módulo de Elasticidade de 160,70 MPa com máximo em 568,49 MPa. Quanto à permeabilidade ao vapor de água, apesar de ser influenciada exclusivamente pela concentração de glicerol, apresentou uma pequena variabilidade, pois o menor valor foi próximo do maior valor. Enquanto que o índice de desintegração em água foi dependente das concentrações de gelatina e do plastificante, onde foi observado que quanto menores ambas as concentrações, menor a desintegração. Avaliando o comportamento dos laminados em condições ambientais simuladas, verificou-se que alguns não sofreram alterações nas suas propriedades durante 25 dias de armazenamento a 65 e 75 % de UR. Os resultados de microscopia Eletrônica de Varredura indicaram que as diversas formulações empregadas em diferentes ensaios provocaram alterações na morfologia da matriz polimérica. As concentrações de gelatina e de glicerol influenciaram a cristalinidade dos laminados onde o laminado controle mostrou ser mais cristalino que os laminados dos ensaios formulados. O valor da condutividade térmica dos laminados revelou-se maior que o dos materiais sintéticos. Na degradação térmica, observou-se uma estabilidade até cerca de 230 oC quando iniciou-se a perda de massa observada através da termogravimetria, enquanto que as transições vítreas determinadas através de DMTA e DSC foram dependentes dos componentes das formulações dos ensaios e do tempo de armazenamento / Abstract: Due to the increasing accumulation of synthetic plastic rubbish, damaging the ecosystem, various strategies are being followed aimed at decreasing this aggression by way of prevention, reduction, recycling and chemical valorization of the synthetic materials, and especially by the use of biodegradable polymers. The use of starch to make thermoplastic materials is promising, due principally to the natural availability of the product, which is extracted from an endless stock of raw materials (cereals, roots, tubers etc.). However, the blends are not completely biodegradable. Thus this research involved the use of twin screw thermoplastic extrusion with an appropriate rectangular matrix, to produce biodegradable thermoplastic laminated materials based on starch and gelatin and plastified by glycerol and water, capable of being molded into the form of discardable products etc.. Response Surface Methodology (RSM) was used to establish predictive mathematical models based on the Central Compound rotational Design (CCRD) in a 23 complete factorial plan with 5 levels and 3 independent variables, these being the gelatin (50.0; 100.0; 150.0 g/g, wet basis) and glycerin (50.0; 100.0; 150.0 g/g, wet basis) concentrations in 1000g of mix, and the moisture content (30, 35, 40%). The responses obtained to the 2 x 2 combinations of the three factors were evaluated, considering the barrier and strain mechanical properties of the thermoplastic laminates obtained after extrusion, such as: Maximum resistance to strain, Percentage of stretching, Elasticity (Young's modulus), Water vapor permeability and the disintegration index in an aqueous medium. Mathematical methodology to optimize the trials was then developed which allowed one to choose the 6 main trials from the total of 18 from the design using a combination formula of best responses. After choosing those samples showing the best properties, the physical, chemical e morphological properties were evaluated using the following techniques: scanning electron microscopy (SEM), an estimate of the storage conditions, water absorption, X-ray diffraction and relative crystallinity index. The following thermal properties were evaluated in order to observe the thermal behavior of the laminates: Thermal Conductivity, Thermogravimetric analysis (TGA), Thermal Dynamic Mechanical analysis (TDMA) and Differential Scanning Calorimetry (DSC). The mechanical properties of the thermoplastic laminates were mostly influenced by the gelatin and glycerol concentrations, presenting a mean value for maximum resistance to strain of 4.87 MPa and a maximum value of 12.62 MPa; a mean value for % stretching of 46.46% with a maximum of 81.58% and a mean value for the Young's Modulus of 160.70 Mpa with a maximum of 568.49 MPa. With respect to water vapor permeability, despite being influenced exclusively by the glycerol concentration, this presented only slight variation, with the smallest value being similar to the largest value, whilst the disintegration index in water was dependant on both the gelatin and plastifier concentrations and the smaller the concentrations of these two concentrations, the smaller the disintegration. An evaluation of the behavior of the laminates under simulated environmental conditions, showed that some of them presented no alterations in their properties during 25 days of storage at 65 and 75% RH. The SEM results indicated that several of the various formulations used in the different trials caused alterations in the morphology of the polymeric matrix. The concentrations of gelatin and glycerol influenced the crystallinity of the laminates, the control laminate being more crystalline than those formulated in the trials. The Thermal Conductivity of the laminates was shown to be greater than that of the synthetic materials. For thermal degradation, stability was observed at about 230°C, point at which the materials started to loose mass as observed by the Thermogravimetric analysis, whilst the vitreous transitions determined by TDMA and DSC were dependant on the components of the trial formulations and storage time / Doutorado / Doutor em Tecnologia de Alimentos

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-05-22T17:32:38Z No. of bitstreams: 1 DISSERTAÇÃO LEANDRO V.G..pdf: 1206910 bytes, checksum: d288e295aca8fbcbcdb1c961d22a8d96 (MD5) / Made available in DSpace on 2017-05-22T17:32:38Z (GMT). No. of bitstreams: 1 DISSERTAÇÃO LEANDRO V.G..pdf: 1206910 bytes, checksum: d288e295aca8fbcbcdb1c961d22a8d96 (MD5) / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geoquímica, Niterói, RJ / Lagoa hipersalina de Araruama - RJ, nas últimas décadas, vem sofrendo uma ocupação desordenada de sua bacia de drenagem e o conseq üente aporte de matéria orgânica (M.O.) proveniente de esgoto doméstico, alterando drasticamente seu estado trófico, de oligo para hipertr ófico. O presente trabalho pr etende avaliar a composição matéria orgânica e os processos micr obiológicos na Lagoa de Araruama (RJ) e relacionar às condições hipertróficas at uais. Neste sentido, foram considerados eventos distintos, tais como período chuv oso, seco e marés (vazante e enchente). Os locais de amostragem da co luna d’água e sedimento foram selecionados para caracterizar o aporte fluvial – estação Ar aruama (AR), a ciclagem interna – estação São Pedro da Aldeia (SP) e as trocas com o oceano – estação Cabo Frio (CF). A elevada produção primária encontrada (concentração média de clorofila: 450 μ g.L -1 ) e as baixas concentrações das formas nitrogenadas na coluna d’água (NO 2 , NO 3 e NH 4 ), indicam consumo pelo fitoplâncton. Fo ram encontradas elevadas concentrações de carbono orgânico dissolvido (média de 17,5mgC.L -1 ), refletindo numa elevada taxa respiratória (média de 2,08 μ MO 2 .L -1 .h -1 ). As concentrações de biopolímeros foram elevadas no sedimento, principalmente li pídios e carboidratos (2,99 e 2,57mg.g -1 , respectivamente), apresentando a relação [lipídios]>[carboidratos]>[proteínas], diferindo ao descrito pela li teratura para o hemisfério norte. O carbono orgânico estocado nos sedimentos da lagoa apresentou valores médios de 5,5%, C/N de 10,4 e δ 13 C (‰) e δ 15 N (‰) de -14,8 e 6,21, respectivam ente. Os valores em geral apontam para uma mistura de fontes ao carbono depositado nos se dimentos. A proporção relativa entre os esteróis pesqui sados demonstrou uma predominância de estigmasterol na maioria das amostras, que poder ia ter como fonte o fitoplâncton uma vez que sua relação com as plantas vascula res não é válida para um sistema com poucos rios. O coprostanol apresentou elevadas concentrações em AR (média de 263 μ g.g -1 ), sendo encontrado em menor escala em Cabo Frio e São Pedro, e se apresentou como melhor indicador de es goto em ambiente hipersalino que os coliformes termotolerantes. A biomassa e atividades bacterianas no sedimento (metabólica e enzimática) apresentara m-se elevadas, evidenciando a intensa ciclagem da M.O. neste co mpartimento e indicando que a lagoa poderá retornar à melhores condições em curto ou médio praz o, caso sejam adotadas medidas efetivas para sua recuperação / ABSTRACT The hypersaline lagoon of Araruama - RJ is suffering, in the last decades, disordered occupation of its drainage basin and consequent contribution of M.O. originating from domestic sewage, altering drastically your trophic characteristics, from oligo to hypertrophic. The present work intends to evaluate the organic matter composition and the microbial processes in the Araruama Lagoon (R J) and to relate to the current hypertrophic conditions. Thus, di fferent events were considered, such as rainy, dry and tide (low and high) periods. The sites for water column and sediment sampling were selected to characterize the fluvial contri bution in Araruama stat ion (AR), the intern cycling - São Pedro da Aldeia station (SP) and the exchanges with the ocean - Cabo Frio station (CF). The high prim ary production found (chlorophyll: 450 μ g.L -1 ) and the reduced concentrations of the nitrogen forms in the water column (NO 2 , NO 3 and NH 4 ) indicate phytoplankton consumption. High c oncentrations of dissolved organic carbon were observed (average of 17.5mgC.L -1 ), resulting in a high re spiratory rate (average of 2.08 μ MO 2 .L -1 .h -1 ). The biopolymer concentrations were high in the sediment, mostly lipids and carbohydrates (2.9 and 2.57mg.g -1 , respectively), presenting the relationship lipids>carbohydrates>proteins, which differs fr om what is described by the literature for the Northern Hemisphere. The organic carbon stocked in the lagoon’s sediments presented medium values of 5,5%, 10,4 for C/N a nd -14.8‰ and 6.21‰ for δ 13 C and δ 15 N, respectively. Generally, those results indicate a mixture of sources for the deposited carbon in the sedi ments. The relative propor tion among the researched sterols demonstrated a predominanc e of stigmasterol in most of the samples, probably coming from phytoplankton. Despite of this compound are commonly related to vascular plants the absence of a high amount of rivers in the drainage basin turn this source without importance. Coprostanol wa s present in high concentrations at AR station (average of 263 μ g.g -1 ), but it was also found in sm all scale at Cabo Frio and less at São Pedro, and it seems to be a better sewage indicator at the hypersaline environment than the termotolerant coliforms. The bacterial biomass and activities in the sediment (metabolic and enzymatic) were high, evidencing the intense cycling of organic matter in this compartment and indica ting that the lagoon can return to better conditions in short or medium period, if e ffective programs for its recovery are adopted

Controlling conformation of macromolecules, both in solution and solid state, has remained an exciting challenge till date as it confronts the entropy driven random coil conformation. Folded forms of biomacromolecules, like proteins and nucleic acids, have served as role-models to the scientists in terms of designing synthetic foldamers. The folded functional forms of proteins and nucleic acids have been shown to rely heavily on various factors, like directional hydrogen bonding, intrinsic conformational preferences of the backbone, solvation (e.g. hydrophobic effects), coulombic interactions, charge-transfer interactions, metal-ion complexation, etc. Chapter-1 discusses various designs of synthetic polymers explored by research groups world-over to emulate the exquisite conformational control exercised by biomacromolecular systems. Our laboratory has been extensively involved since 2004 in designing charge-transfer complexation induced folding of flexible donor-acceptor (DA) polymeric systems, such as those shown in Scheme 1. It was observed that such polymers adopt a folded conformation in polar solvents, like methanol, in the presence of an excess of an appropriate alkali metal ion. To explore folding in the solid state, Jonas and co-workers recently showed that a polyethylene-like polyester with long alkylene segments containing periodically located pendant propyl group forms a semicrystalline morphology with alternating crystalline and amorphous regions primarily because of the periodic folding of the backbone due to the steric exclusion of the propyl branches from the crystalline domains. In order to explore immiscibility-driven folding of polyethylene-like polyesters, Roy et al. designed a periodically grafted amphiphilic copolymer (PGAC) containing long alkylene segments (mimicking polyethylene) and pendant oligoethyleneglycol chains at periodic intervals (Scheme 2). Scheme 2: Proposed folding of a periodically grafted amphiphilic copolymer It was demonstrated that immiscibility between the hydrocarbon backbone and pendant PEG segments drives the polymer to adopt a folded zigzag conformation as shown in Scheme 2. The above synthetic strategy, however, does not permit easy structural variation of the side chain segments because the side-chain segment is covalently linked to the malonate monomer. In Chapter-2, a more general strategy to prepare periodically grafted copolymers has been described. In an effort to do so, we designed a series of clickable polyesters carrying propargyl/allyl functionality at regular intervals along the polymer backbone, as shown in Scheme 3. Scheme 3: Periodically clickable polyesters for the preparation of periodically grafted copolymers The polyesters were prepared by reacting either 2-propargyl-1,3-propanediol, 2,2-dipropargyl-1,3-propanediol or 2-allyl-2-propargyl-1,3-propanediol with an alkylene diacid chloride, namely 1,20-eicosanedioic acid chloride, under solution polycondensation conditions. Since these polyesters carry either, one propargyl, two propargyls or one propargyl and one allyl group on every repeat unit, it provides us an opportunity to synthesise exact graft copolymers with one side chain, two side chains or even two dissimilar side chains per repeat unit. In Chapter-3, the periodically clickable polyesters were reacted with MPEG-350 (PEG 350 monomethyl ether) azides using Cu(I) catalyzed azide-yne click reaction to generate periodically grafted amphiphilic copolymers (PGAC) carrying crystallizable hydrophobic backbone and pendant hydrophilic MPEG-350 side-chains (Scheme 4). Since the PGACs carry either one or two pendant MPEG-350 chains on every repeat unit, it allowed us to examine the effect of steric crowding on the crystallization propensity of the central alkylene segment. Scheme 4: Functionalization of periodically clickable polyesters with MPEG 350 azide by azide-yne click reaction From DSC studies, it was observed that increase in steric crowding at junctions resulting from increased side-chain volume hinders effective packing of the hydrocarbon backbone. As a result, both transition temperatures and the enthalpies associated with these transitions decreases. SAXS and AFM studies revealed the formation of lamellar morphology with alternate domains of PEG and hydrocarbon. Based on these observations, we proposed that self-segregation between hydrophobic backbone and hydrophilic side-chains induce the backbone to adopt a folded zigzag conformation (Scheme 5). Scheme 5: Schematic depiction of self-segregation induced folding of PGAC and their assembly on mica surface (AFM image) In order to study the effect of solvent polarity on conformational evolution of the periodically grafted amphiphilic copolymers, we randomly incorporated pyrene in the backbone of the polymer by reacting a small fraction (~ 5 mole %) of the propargyl groups with pyrene azide. Fluorescence study of the pyrene labelled polymer showed that increase in solvent polarity increases the intensity of the excimer band dramatically; this suggests the possible collapse of the polymer chain to the folded zigzag form. In an extension of this work, the PGAC was further used as template to synthesise layered silicates that appears to replicate the lamellar periodicity seen in the polymer. In order to study the effect of reversing the amphiphilicity on self-segregation, in Chapter-4, we synthesised a series of clickable polyesters carrying PEG segments of varying lengths, namely PEG 300, PEG 600 and PEG 1000, along the polymer backbone. The polymers were prepared by trans-esterification of 2-propargyl dihexylmalonate with different PEG-diols. These polyesters were then clicked with docosyl (C22) azide using Cu(I) catalyzed azide-yne click reaction to generate the desired periodically grafted amphiphilic polymers carrying crystallizable hydrophobic pendant chains at periodic intervals; the periodicity in this case was governed by the length of the PEG diols (Scheme 6). Scheme 6: PGACs carrying hydrophilic PEG backbone and crystallizable hydrophobic pendant docosyl chains Varying the average periodicity of grafting provided an opportunity to examine its consequences on the self-segregation behavior. Given the strong tendency of the pendant docosyl segments to crystallize, DSC studies proved useful to analyse the self-segregation; DOCOPEG 300 clearly exhibited the most effective self-segregation, whereas both DOCOPEG 600 and DOCOPEG 1000 showed weaker segregation. Based on the observations from DSC studies, we proposed that the PEG backbone adopts a hairpin like conformation (Scheme 7). Scheme 7: Proposed self-segregation through hairpin like conformation of backbone PEG segments In order to confirm the bulk morphology, we carried out small angle X-ray scattering (SAXS) and atomic force microscopic (AFM) studies. The SAXS profiles confirmed the observations from DSC studies, and only DOCOPEG 300 exhibited well-defined lamellar ordering. Thus, it is clear that the length of the backbone PEG segment (volume-fraction) strongly influences the morphology of the PGACs. Based on the inter-lamellar spacing from SAXS and the height measurements from AFM studies (Scheme 8), we proposed that these polymers form lamellar morphology through inter-digitation of the pendant docosyl side-chains. The observations from Chapters 3 and 4 suggested that the crystallization of the backbone has a dramatic effect on the conformation of the polymer backbone. In order to explore the possibility of independent crystallization of both backbone and pendant side-chains, the periodically clickable polyesters, described in Chapter-2, were quantitatively reacted with a fluoroalkyl azide, namely CF3(CF2)7CH2CH2N3 using Cu(I) catalyzed azide-yne click reaction; Chapter-5 describes these polyesters carrying long chain alkylene segments along the backbone and either one or two perfluoroalkyl segments located at periodic intervals along the polymer chain (Scheme 9). DSC thermograms of two of the samples showed two distinct endotherms associated with the melting of the individual domains, while the WAXS patterns confirm the existence of two separate peaks corresponding to the inter-chain distances within the crystalline lattices of the hydrocarbon (HC) and fluorocarbon (FC) domains; this confirmed the occurrence of independent crystallization of both the backbone and side chains. Scheme 10: Left-variation of SAXS profile of all three polymers as a function of temperature, Right- molecular modelling of representative FC-HC-FC triblock structures. Interestingly, a smectic-type liquid crystalline phase was observed at temperatures between the two melting transitions. SAXS data, on the other hand, revealed the formation of an extended lamellar morphology with alternating domains of HC and FC (Scheme 10). The inter-lamellar spacing calculated from SAXS matches reasonably well with those estimated from TEM images. Based on these observations, we proposed that the FC modified polymers adopt a folded zigzag conformation whereby the backbone alkylene (HC) segment becomes colocated at the center and is flanked by the perfluoroalkyl (FC) groups on either side, as depicted in Scheme 11. Melting of alternate HC domains first leads to the formation of a smectic-type liquid crystalline mesophase, wherein the crystalline FC domains retain the smectic ordering; this was confirmed by polarizing light microscopic observations. Scheme 11: Schematic presentation of self-segregation induced folding of polymer chains; and hence crystallization assisted assembly of these singly folded chains to form lamellar structure One interesting challenge would be to create unsymmetrical folded structures, wherein the top and bottom segments of the zigzag folded form would be occupied by two different segments, such as PEG and FC, whereas the backbone alkylene segment would form the central domain; this would lead to the possible formation of consecutive domains of PEG, HC and FC through immiscibility driven self-segregation process. In Chapter-6, several approaches to access such systems have been described; one such design that could have resulted in the successful synthesis of a periodically clickable polymer carrying orthogonally clickable propargyl and allyl groups along the backbone in an alternating fashion is depicted in (Scheme 12). The parent polyester was successfully synthesized and the propargyl group was first clicked with the FC-azide to yield the FC-clicked polyester; however, several attempts to click MPEG-SH onto the allyl groups using thiol-ene click reaction failed. Scheme 12: Scheme for the synthesis of alternating orthogonally clickable polymer In order to accomplish our final objective, we chose to first prepare the FC-clicked diacid chloride and polymerize it with an azide-alkyne clickable macro-diol, as depicted in Scheme 13; this approach was successful and yielded the desired clickable polyester bearing the FC segments at every alternate location. This polymer was then clicked with PEG-750 azide to yield the final targeted polymer that carries mutually immiscible FC and PEG-750 segments at alternating positions along the polymer backbone. The occurrence of self-segregation of FC, PEG-750 and the alkylene backbone (HC) was first examined by DSC studies, which appeared to suggest the presence of three peaks, although these were not very well-resolved. Scheme 13: Schematic for the synthesis of the polymer carrying FC and PEG 750 alternatingly along the backbone A schematic depiction of the anticipated organization of such unsymmetric folded macromolecules is shown in Scheme 15; it is evident that because of mutual immiscibility, the layers will be organized such that the FC domains of adjacent layers will be together and similarly the PEG domains of adjacent layers will also be together. Such an organization would lead to an estimated spacing that would correspond to a bilayer of the folded structures. Interestingly, SAXS study (Scheme 14) reveals the formation of lamellar morphology with a d-spacing of 14.6 nm. Scheme 14: Figure 6.10: SAXS profile of the polymer PE-FC-PEG 750 In order to gain an estimate of the expected inter-lamellar spacing, the end-to-end distance of a model repeat-unit was computed to be ~ 9.4 nm. It is, therefore, evident that the inter-lamellar spacing of 14.6 nm seen in the SAXS is significantly larger and must represent a bilayer type organization (Scheme 15). In this regard it is important to say that the organization of these alternatingly functionalized folded chains should give a variety of d-spacings. Because of highest electron density contrast of FC among PEG, HC and FC, we proposed that the d-spacing calculated from the SAXS profile corresponds to ‘d4’ in Scheme 15. This first demonstration of the formation of zigzag folded unsymmetric entities bearing dissimilar segments on either side of the folded chain holds exciting potential for a variety of different applications and beckons further investigations. Scheme 15: Schematic for the proposed self-assembly of the singly folded polymer chains

Ce travail s'inscrit dans le cadre général de la mise au point et de l'étude d'agents potentiellement photothérapeutiques. Dans cette optique, les recherches menées dans notre laboratoire sont consacrées principalement à l'étude de complexes photooxydants de ruthénium(II) contenant des ligands &61552;-déficients TAP (1,4,5,8-tétraazaphénanthrène). Ces composés sont en effet capables, sous illumination, d'oxyder différentes biomolécules pour mener, notamment, à la formation de photoadduits qui pourraient perturber le fonctionnement d'enzymes cellulaires in vivo.<p><p>La première partie de ce travail a été consacrée à la mise au point d'un nouveau système d'ancrage de ces complexes. Elle décrit les voies de synthèse et de purification de deux nouveaux ligands fonctionnalisés: la phen" et le TAP", ainsi que celles de trois nouveaux complexes chélatés par ces nouveaux ligands: le &61531;Ru(TAP)2phen"&61533;2+, le &61531;Ru(TAP)2TAP"&61533;2+ et le &61531;Ru(phen)2phen"&61533;2+. Ces composés ont été attachés, via une liaison oxime, sur oligonucléotides synthétiques et sur polymères biodégradables.<p>La seconde partie de notre travail a été consacrée à l'étude photochimique de conjugués oligonucléotide-complexe sous forme de simples et de doubles brins. Pour les conjugués à base du &61531;Ru(TAP)2phen&61533;2+, nous avons pu mettre en évidence un photocrosslinking lorsque des guanines étaient présentes dans le brin complémentaire. La formation de ce photoadduit est moins efficace que celle observée avec l'ancien système et montre une dépendance en l'extrémité d'ancrage du complexe (5' ou 3'). Pour les conjugués fonctionnalisés avec le &61531;Ru(TAP)3&61533;2+, nous avons montré que le photocrosslinking, dans le duplexe avec guanines, était moins efficace à cause de la photodéchélation de ce composé. De plus, nous avons pu mettre en évidence un quenching de la luminescence par les bases adénines dans les conjugués simples et doubles brins sans guanine ainsi qu'un photocrosslinking dans le duplexe sans guanine. Enfin, nous avons pu déterminer pour la première fois le rendement quantique de la réaction de photojonction via les bases guanines.<p>Nous avons ensuite étudié, d'un point de vue photophysique et photochimique, des conjugués complexe-polymère biodégradable dont le rôle sera de faire pénétrer les composés photoréactifs à l'intérieur des cellules. D'une part, nous avons montré que la présence du polymère avait peu d'influence sur les propriétés photophysiques des complexes. D'autre part, l'utilisation de différentes techniques, nous a permis de démontrer que les complexes ancrés chimiquement sur ces macromolécules sont toujours capables de photooxyder la guanine et de mener à la formation de photoadduits sur GMP et sur oligonucléotides.<p>Finalement, la dernière partie de notre travail a été consacrée à l'étude des complexes photoréactifs &61531;Ru(TAP)2phen&61533;2+ et &61531;Ru(TAP)3& / Doctorat en sciences, Spécialisation chimie / info:eu-repo/semantics/nonPublished

Dans le but de développer des matériaux actifs antimicrobiens biodégradables à libération contrôlée, des mélanges de deux polymères biodégradables incompatibles ont été mis en oeuvre par les voies classiques de transformation des matériaux plastiques (extrusion). L'originalité de ces mélanges réside dans la recherche d'une stratégie de contrôle de la libération d'espèces actives incorporées dans l'une des phases du système et générée par la tortuosité/disponibilité de chemins de diffusion sélectifs obtenue en jouant sur les proportions relatives des 2 polymères en présence. Les systèmes binaires étudiés sont : [amidon de maïs plastifié, PLS et poly(butylène succinate-co-adipate) ou PBSA] et un système référence [(poly(oxyethylène) PEO et PBSA]. Dans ces mélanges, les polymères polaires (PLS ou PEO) jouent le rôle de matrice hôte pour solubiliser les migrants actifs ou modèles, souvent polaires et le polymère semipolaire,le PBSA, compense la faiblesse des propriétés mécaniques et barrières à l'eau de la phase amylacée et /ou hydrophile tout en présentant une température de fusion basse (85°C) compatible avec une stratégie à plus long terme d'incorporation d'actifs peu thermostables. Les systèmes obtenus sont caractérisés afin de corréler les différentes morphologies obtenues en jouant sur la composition des mélanges (phase dispersées dans une matrice continue, ou continuité partielle ou totale, systèmes pseudo-multicouches) aux phénomènes de transport de diverses molécules. Les caractérisations effectuées ont alors pour objectif d'élucider les morphologies obtenues par i) extraction sélective par voie solvant (ou hydrolyse) enrichie par des observations microscopiques ii) par utilisation de sondes gazeuses via les propriétés de transport de vapeur d'eau (qui privilégiera les chemins offerts par la matrice polaire) ou de l'oxygène (qui, lui, privilégiera les chemins de diffusions offerts par le PBSA) iii) par la réalisation des isothermes et cinétiques de sorption d'eau et enfin iv) par l'étude de la libération dans l'eau de migrants actifs ou modèles préalablement incorporés dans la phase polaire (fluorescéinate de sodium, acides organiques, glycine, di-glycine). Il a ainsi pu être montré pour les mélanges PLS/PBSA que les phénomènes de diffusion sont contrôlés par la tortuosité générée par la présence de PBSA dans le cas du relargage de la fluorescéine et par l'hydratation limitée de la phase polaire en présence de fortes teneurs en PBSA dans le mélange pour les phénomènes de sorption d'eau. Ainsi, la diffusion de la fluorescéine, par exemple, est nettement plus influencée que celle de l'eau par la tortuosité (elle-même gouvernée par la composition du mélange), très probablement en raison de sa plus grande masse moléculaire. Pour les mélanges PEO/PBSA, des comportements distincts ont été mis en évidence selon la composition des mélanges. Pour les mélanges à faibles teneurs ou teneurs intermédiaires en PBSA, un transport rapide se produit principalement via la dissolution du PEO. La morphologie ne semble pas influencer les cinétiques de libération. Pour des teneurs élevées en PBSA, la cinétique de libération est cette fois dépendante de la morphologie présente un temps de latence caractéristique d'une cinétique de perméation (libération proportionnelle au temps). En conclusion, les matériaux élaborés par les voies migrants polaires tels que des conservateurs pour élaborer par exemple des emballages actifs antimicrobiens / In order to develop biodegradable and active materials s, blends of two incompatible biodegradable polymers have been implemented by conventiona plastic material processing (extrusion). The originality of these blends lies in the search for a strategy to control the release of active species included in one of the phases of the system. Therefore, the tortuosity / availability of selective diffusion paths obtained by varying the relative proportions of the two polymers involved will be exploited. Studied binary systems consist of: [plasticized corn starch, PLS and poly (butylene succinate-co-adipate) or PBSA] and a reference system [(poly (oxyethylene) PEO and PBSA]. In these blends, polar polymers (PLS or PEO) play the role of host matrix to solubilize the active migrants or model molecules which are often polar, and the semi-polar polymer (PBSA) compensates for the weakness of the mechanical properties of the starchy and / or hydrophilic phase while having a low melting temperature (85 ° C) consistent with a longer-term strategy of incorporation of thermostable active molecules such as lysozyme or nisin. The resulting systems were characterized to correlate the different morphologies obtained by varying the composition of the blends (dispersed phase in a continuous matrix, partial or total continuity, or pseudo-layer systems) to the transport phenomena of various molecules. The performed characterizations aim to elucidate the morphologies by i) selective solvent extraction method (or hydrolysis) enriched by microscopical observations ii) using gaseous probes via the determination of water vapor transport properties (water will favor the paths provided by the polar matrix) or oxygen transport properties (O2 will favor the diffusion paths provided by the PBSA matrix) iii) by determining water sorption isotherms and kinetics and finally iv) by the study of the release in water of active or model migrants previously incorporated in the polar phase (sodium fluoresceinate, organic acids, glycine, diglycine). It has been observed that the diffusion phenomena in PLS / PBSA blends are controlled by the tortuosity generated by the presence of PBS and by the limited hydration of the polar phase at high PBSA contents in the blends for water sorption phenomena. Thus, the diffusion of fluorescein, for example, is much more influenced by the tortuosity (itself governed by the composition of the blends) than that of water, which is likely due to its higher molecular weight. For PEO / PBSA blends, distinct behaviors were observed according to the blends composition. For the blends with low or intermediate content of PBSA, rapid transport occurs mainly via the dissolution of the PEO. The morphology did not seem to influence the release kinetics. For high contents of PBSA, the release kinetics were dependent on the morphology and a time lag which is characteristic of permeation kinetics (release proportional to time) appeared. In conclusion, the multiphasic materials prepared by plastic processing look promising for the controlled release of polar migrants such as food preservatives to develop antimicrobial active packaging

Cette thèse a pour objectif d’étudier les propriétés physico-chimiques de capsules à cœur liquide à base d'hydrogel d'alginate et de contrôler leur perméabilité et propriétés mécaniques par ajout des biopolymères. Ces capsules sont préparées par un procédé de sphérification inverse par extrusion goutte à goutte d’une solution de chlorure de calcium dans un bain à base d’alginate. Dans un premier travail, l’influence des polymères utilisés pour contrôler la viscosité du cœur liquide lors de la préparation des capsules sur la perméabilité et la stabilité mécanique a été étudiée. Les propriétés mécaniques des capsules ont été corrélées avec les propriétés viscoélastiques d’hydrogels d’alginate caractérisés par rhéologie oscillatoire aux faibles amplitudes. Un second travail, a consisté à élaborer des capsules composites avec une membrane de caséinate de sodium/alginate qui présentent une meilleure stabilité et une libération pH-dépendante d’un colorant utilisé comme molécule modèle. Comme perspective a cette étude, des hydrogels sphériques à base d’alginate et de caséinate de sodium, avec différentes architecture ont été développés et leur efficacité a été testée sur trois colorants. Enfin, l’influence de l’incorporation de la gomme laque dans la membrane ou comme revêtement externe a permis de mettre en évidence une amélioration des propriétés barrières vis-à-vis de molécules de faible masse moléculaire (riboflavine dans ce cas). Les capsules à base d’alginate ont un large spectre d’utilisation allant de la cuisine moléculaire à la biotechnologie ce qui nécessite une meilleure compréhension et contrôle de leurs propriétés physicochimiques en fonction de l’application visée / The aim of this thesis is to study the physicochemical properties of alginate liquid-core capsules and to control their permeability and mechanical properties by biopolymers blending. These millimeter-scale size capsules are prepared by a reverse spherification process by dripping a solution of calcium chloride into an alginate gelling bath. In a first work, the influence of polymers used to control capsule liquid-core viscosity (thickening agent) during capsules preparation on permeability and mechanical stability of the alginate membrane was investigated. The mechanical properties of capsules were correlated with viscoelastic properties of plane alginate hydrogels characterized by small amplitude oscillatory shear rheology. In a second work, composite capsules with a membrane of sodium caseinate / alginate were developed and showed improved stability and pH-dependent release of a dye used as a model molecule. As a perspective, composite alginate/sodium caseinate microspheres with different architectures were developed and their effectiveness was tested against three anionic dyes. This type of system has applications in the removal of dyes from industrial wastewater by an adsorption mechanism. Finally, the influence of shellac incorporation in alginate membrane or as an external coating layer resulted in enhanced physicochemical properties and decreased membrane permeability against low molecular weight molecules (riboflavin in this case). Alginate capsules have a wide range of applications ranging from molecular gastronomy to biotechnology which requires a better understanding and control of their physicochemical properties according to the target application

Made available in DSpace on 2017-06-01T18:20:39Z (GMT). No. of bitstreams: 1 jaceline_maria_negreiros_lima.pdf: 862576 bytes, checksum: 0dbb4a9357bfef84bcb5012f24964cae (MD5) Previous issue date: 2013-08-23 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Chitosan is a natural polysaccharide originated from the deacetylation of chitin. It is soluble in acid because of the presence of amino groups, free along the polymer chain. The fungal class Zygomycetes, in particular Rhizopus oryzae, presents in its cell wall chitin and chitosan, and they may be linked through the polyphosphate or proteins and other components, respectively. The polyphosphate is a biopolymer with wide applicability in environmental biotechnology. Manipueira is the result of the process for production of pressed cassava flour and used as carbon source in fermentation processes. The corn steep liquor is a by-product of corn starch and regarded as nitrogen source. Investigations were carried out with Rhizopus oryzae in submerged fermentation for production of biomass and chitosan-polyphosphate complex, through cultivation in agro waste, cassava supplemented with corn steep liquor, using a full factorial design on 23 agitation at 150 rpm for 96h. The test with the greatest amount of biomass and chitosan was selected to perform a growth kinetics to evaluate the production of biomass and chitosan-polyphosphate complex. In this sense, was used bottles of 500ml capacity Erlenmyers containing 100mL of medium formulated being inoculated in 1-ml suspension of 107 spores per ml, incubated under orbital agitation at 150 rpm. Samples were collected every 12 hours until the period of 120h. The results showed a maximum increase of biomass with 48 hours of cultivation at pH 7.3, with maximum production of chitosan by R. oryzae 116mg / g biomass at 36h of cultivation. The polyphosphate complexed to chitosan had the highest yield in 36 h corresponding to 13mg/mg chitosan. Because the results in the production of biomass and chitosan-polyphosphate complex from Rhizopus oryzae, have become economically viable due to the use of industrial wastes to obtain these polymers. / A quitosana é um polissacarídeo natural originado da deacetilação da quitina. É solúvel em ácido devido à presença de grupos amino, livres ao longo da cadeia do polímero. Os fungos de classe Zygomycetes, em especial Rhizopus oryzae, apresenta em suas paredes celulares quitina e quitosana, podendo as mesmas estar ligadas através de proteínas e polifosfato ou outros componentes, respectivamente. O polifosfato é um biopolímero de ampla aplicabilidade na biotecnologia ambiental. A manipueira é o resultado do processo da mandioca prensada para produção de farinha e utilizada como fonte de carbono nos processos fermentativos. A milhocina é um subproduto da produção de amido de milho e considerada como fonte de nitrogênio. Investigações foram realizadas com Rhizopus oryzae em fermentação submersa para produção de biomassa e do complexo quitosana-polifosfato, através do cultivo em rejeito agroindustrial, manipueira suplementado com milhocina, utilizando um planejamento fatorial completo 23 sobre agitação de 150rpm por 96h. O ensaio com a maior quantidade de biomassa e quitosana foi selecionado para realizar uma cinética de crescimento para avaliar a produção de biomassa e do complexo quitosanapolifosfato. Neste sentido, foi utilizado frascos de Erlenmyers de 500mL de capacidade, contendo 100mL do meio formulado, sendo inoculados em 1mL da suspensão de 107 esporos por mL, incubados sob agitação orbital de 150rpm. As amostras foram coletadas a cada 12 horas até o período de 120h. Os resultados obtidos demonstraram um aumento máximo de biomassa com 48h de cultivo em pH 7,3, com produção máxima da quitosana por R. oryzae de 116mg/g de biomassa em 36h de cultivo. O polifosfato complexado à quitosana apresentou maior rendimento em 36h correspondendo a 13mg/mg de quitosana. Devido os resultados obtidos na produção de biomassa e o complexo de quitosanapolifosfato por Rhizopus oryzae, tornaram-se economicamente viáveis devido à utilização de rejeitos industriais para obtenção desses polímeros.