Obtenção de polímeros graftizados de quitosana e estudo das propriedades físico-químicas para aplicação na indústria do petróleo

Chitosan is a biopolymer derived from the shells of crustaceans, biodegradable, inexpensive and renewable with important physical and chemical properties. Moreover, the different modifications possible in its chemical structure generate new properties, making it an attractive polysaccharide owing to its range of potential applications. Polymers have been used in oil production operations. However, growing concern over environmental constraints has prompted oil industry to search for environmentally sustainable materials. As such, this study sought to obtain chitosan derivatives grafted with hydrophilic (poly(ethylene glycol), mPEG) and/or hydrophobic groups (n-dodecyl) via a simple (one-pot) method and evaluate their physicochemical properties as a function of varying pH using rheology, small-angle Xray scattering (SAXS), dynamic light scattering (DLS) and zeta potential. The chitosan derivatives were prepared using reductive alkylation under mild reaction conditions and the chemical structure of the polymers was characterized by nuclear magnetic resonance (1H NMR) and CHN elemental analysis. Considering a constant mPEG/Chitosan molar ratio on modification of chitosan, the solubility of the polymer across a wide pH range (acidic, neutral and basic) could only be improved when some of the amino groups were submitted to reacetylation using the one-pot method. Under these conditions, solubility is maintained even with the simultaneous insertion of n-dodecyl. On the other hand, the solubility of derivatives obtained only through mPEG incorporation using the traditional methodology, or with the ndodecyl group, was similar to that of its precursor. The hydrophilic group promoted decreased viscosity of the polymer solutions at 10 g/L in acid medium. However, at basic pH, both viscosity and thermal stability increased, as well as exhibited a pronounced pseudoplastic behavior, suggesting strong intermolecular associations in the alkaline medium. The SAXS results showed a polyelectrolyte behavior with the decrease in pH for the polymer systems. DLS analyses revealed that although the dilute polymer solutions at 1 g/L and pH 3 exhibited a high density of protonated amino groups along the polymer chain, the high degree of charge contributed significantly to aggregation, promoting increased particle size with the decrease in pH. Furthermore, the hydrophobic group also contributed to increasing the size of aggregates in solution at pH 3, whereas the hydrophilic group helped reduce their size across the entire pH range. Nevertheless, the nature of aggregation was dependent on the pH of the medium. Zeta potential results indicated that its values do not depend solely on the surface charge of the particle, but are also dependent on the net charge of the medium. In this study, water soluble associative polymers exhibit properties that can be of great interest in the petroleum industry

Avaliação das propriedades físico-químicas de sistemas a base de carboximetilcelulose e poli (N-isopropilacrilamida) em soluções aquosas para aplicação na indústria do petróleo

Sustainable development is a major challenge in the oil industry and has aroused growing interest in research to obtain materials from renewable sources. Carboxymethylcellulose (CMC) is a polysaccharide derived from cellulose and becomes attractive because it is water-soluble, renewable, biodegradable and inexpensive, as well as may be chemically modified to gain new properties. Among the derivatives of carboxymethylcellulose, systems have been developed to induce stimuli-responsive properties and extend the applicability of multiple-responsive materials. Although these new materials have been the subject of study, understanding of their physicochemical properties, such as viscosity, solubility and particle size as a function of pH and temperature, is still very limited. This study describes systems of physical blends and copolymers based on carboxymethylcellulose and poly (N-isopropylacrylamide) (PNIPAM), with different feed percentage compositions of the reaction (25CMC, 50CMC e 75CMC), in aqueous solution. The chemical structure of the polymers was investigated by infrared and CHN elementary analysis. The physical blends were analyzed by rheology and the copolymers by UV-visible spectroscopy, small-angle X-ray scattering (SAXS), dynamic light scattering (DLS) and zeta potential. CMC and copolymer were assessed as scale inhibitors of calcium carbonate (CaCO3) using dynamic tube blocking tests and chemical compatibility tests, as well as scanning electron microscopy (SEM). Thermothickening behavior was observed for the 50 % CMC_50 % PNIPAM and 25 % CMC_75 % PNIPAM physical blends in aqueous solution at concentrations of 6 and 2 g/L, respectively, depending on polymer concentration and composition. For the copolymers, the increase in temperature and amount of PNIPAM favored polymer-polymer interactions through hydrophobic groups, resulting in increased turbidity of polymer solutions. Particle size decreased with the rise in copolymer PNIPAM content as a function of pH (3-12), at 25 °C. Larger amounts of CMC result in a stronger effect of pH on particle size, indicating pH-responsive behavior. Thus, 25CMC was not affected by the change in pH, exhibiting similar behavior to PNIPAM. In addition, the presence of acidic or basic additives influenced particle size, which was smaller in the presence of the additives than in distilled water. The results of zeta potential also showed greater variation for polymers in distilled water than in the presence of acids and bases. The lower critical solution temperature (LCST) of PNIPAM determined by DLS corroborated the value obtained by UV-visible spectroscopy. SAXS data for PNIPAM and 50CMC indicated phase transition when the temperature increased from 32 to 34 °C. A reduction in or absence of electrostatic properties was observed as a function of increased PNIPAM in copolymer composition. Assessment of samples as scale inhibitors showed that CMC performed better than the copolymers. This was attributed to the higher charge density present in CMC. The SEM micrographs confirmed morphological changes in the CaCO3 crystals, demonstrating the scale inhibiting potential of these polymers

Caracterização química e toxicológica da água produzida descartada em plataformas de óleo e gás na costa brasileira e seu comportamento dispersivo no mar

The production of oil and gas is usually accompanied by the production of water, also known as produced water. Studies were conducted in platforms that discharge produced water in the Atlantic Ocean due to oil and gas production by Petrobras from 1996 to 2006 in the following basins: Santos (Brazilian south region), Campos (Brazilian southeast region) and Ceara (Brazilian northeast region). This study encompasses chemical composition, toxicological effects, discharge volumes, and produced water behavior after releasing in the ocean, including dispersion plumes modeling and monitoring data of the marine environment. The concentration medians for a sampling of 50 samples were: ammonia (70 mg L-1), boron (1.3 mg L1), iron (7.4 mg L-1), BTEX (4.6 mg L-1), PAH (0.53 mg L-1), TPH (28 mg L-1); phenols (1.3 mg L-1) and radioisotopes (0.15 Bq L-1 for 226Ra and 0.09 Bq L-1 for 228Ra). The concentrations of the organic and inorganic parameters observed for the Brazilian platforms were similar to the international reference data for the produced water in the North Sea and in other regions of the world. It was found significant differences in concentrations of the following parameters: BTEX (p<0.0001), phenols (p=0.0212), boron (p<0.0001), iron (p<0.0001) and toxicological response in sea urchin Lytechinus variegatus (p<0.0001) when considering two distinguished groups, platforms from southeast and northeast Region (PCR-1). Significant differences were not observed among the other parameters. In platforms with large gas production, the monoaromatic concentrations (BTEX from 15.8 to 21.6 mg L-1) and phenols (from 2 to 83 mg L-1) were higher than in oil plataforms (median concentrations of BTEX were 4.6 mg L-1 for n=53, and of phenols were 1.3 mg L-1 for n=46). It was also conducted a study about the influence of dispersion plumes of produced water in the vicinity of six platforms of oil and gas production (P-26, PPG-1, PCR-1, P-32, SS-06), and in a hypothetical critical scenario using the chemical characteristics of each effluent. Through this study, using CORMIX and CHEMMAP models for dispersion plumes simulation of the produced water discharges, it was possible to obtain the dilution dimension in the ocean after those discharges. The dispersion plumes of the produced water modelling in field vicinity showed dilutions of 700 to 900 times for the first 30-40 meters from the platform PCR-1 discharge point; 100 times for the platform P-32, with 30 meters of distance; 150 times for the platform P-26, with 40 meters of distance; 100 times for the platform PPG-1, with 130 meters of distance; 280 to 350 times for the platform SS-06, with 130 meters of distance, 100 times for the hypothetical critical scenario, with the 130 meters of distance. The dilutions continue in the far field, and with the results of the simulations, it was possible to verify that all the parameters presented concentrations bellow the maximum values established by Brazilian legislation for seawater (CONAMA 357/05 - Class 1), before the 500 meters distance of the discharge point. These results were in agreement with the field measurements. Although, in general results for the Brazilian produced water presented toxicological effects for marine organisms, it was verified that dilutions of 100 times were sufficient for not causing toxicological responses. Field monitoring data of the seawater around the Pargo, Pampo and PCR-1 platforms did not demonstrate toxicity in the seawater close to these platforms. The results of environmental monitoring in seawater and sediments proved that alterations were not detected for environmental quality in areas under direct influence of the oil production activities in the Campos and Ceara Basin, as according to results obtained in the dispersion plume modelling for the produced water discharge

Caracterização química e toxicológica da água produzida descartada em plataformas de óleo e gás na costa brasileira e seu comportamento dispersivo no mar

The production of oil and gas is usually accompanied by the production of water, also known as produced water. Studies were conducted in platforms that discharge produced water in the Atlantic Ocean due to oil and gas production by Petrobras from 1996 to 2006 in the following basins: Santos (Brazilian south region), Campos (Brazilian southeast region) and Ceara (Brazilian northeast region). This study encompasses chemical composition, toxicological effects, discharge volumes, and produced water behavior after releasing in the ocean, including dispersion plumes modeling and monitoring data of the marine environment. The concentration medians for a sampling of 50 samples were: ammonia (70 mg L-1), boron (1.3 mg L1), iron (7.4 mg L-1), BTEX (4.6 mg L-1), PAH (0.53 mg L-1), TPH (28 mg L-1); phenols (1.3 mg L-1) and radioisotopes (0.15 Bq L-1 for 226Ra and 0.09 Bq L-1 for 228Ra). The concentrations of the organic and inorganic parameters observed for the Brazilian platforms were similar to the international reference data for the produced water in the North Sea and in other regions of the world. It was found significant differences in concentrations of the following parameters: BTEX (p<0.0001), phenols (p=0.0212), boron (p<0.0001), iron (p<0.0001) and toxicological response in sea urchin Lytechinus variegatus (p<0.0001) when considering two distinguished groups, platforms from southeast and northeast Region (PCR-1). Significant differences were not observed among the other parameters. In platforms with large gas production, the monoaromatic concentrations (BTEX from 15.8 to 21.6 mg L-1) and phenols (from 2 to 83 mg L-1) were higher than in oil plataforms (median concentrations of BTEX were 4.6 mg L-1 for n=53, and of phenols were 1.3 mg L-1 for n=46). It was also conducted a study about the influence of dispersion plumes of produced water in the vicinity of six platforms of oil and gas production (P-26, PPG-1, PCR-1, P-32, SS-06), and in a hypothetical critical scenario using the chemical characteristics of each effluent. Through this study, using CORMIX and CHEMMAP models for dispersion plumes simulation of the produced water discharges, it was possible to obtain the dilution dimension in the ocean after those discharges. The dispersion plumes of the produced water modelling in field vicinity showed dilutions of 700 to 900 times for the first 30-40 meters from the platform PCR-1 discharge point; 100 times for the platform P-32, with 30 meters of distance; 150 times for the platform P-26, with 40 meters of distance; 100 times for the platform PPG-1, with 130 meters of distance; 280 to 350 times for the platform SS-06, with 130 meters of distance, 100 times for the hypothetical critical scenario, with the 130 meters of distance. The dilutions continue in the far field, and with the results of the simulations, it was possible to verify that all the parameters presented concentrations bellow the maximum values established by Brazilian legislation for seawater (CONAMA 357/05 - Class 1), before the 500 meters distance of the discharge point. These results were in agreement with the field measurements. Although, in general results for the Brazilian produced water presented toxicological effects for marine organisms, it was verified that dilutions of 100 times were sufficient for not causing toxicological responses. Field monitoring data of the seawater around the Pargo, Pampo and PCR-1 platforms did not demonstrate toxicity in the seawater close to these platforms. The results of environmental monitoring in seawater and sediments proved that alterations were not detected for environmental quality in areas under direct influence of the oil production activities in the Campos and Ceara Basin, as according to results obtained in the dispersion plume modelling for the produced water discharge

Inter-relação da produtividade de madeira do pinus com atributos físico-químicos de um latossolo do cerrado brasileiro

Com relação aos atributos do solo, a produtividade de madeira do pinus varia substancialmente em função do pH, do teor de matéria orgânica e da resistência à penetração. No ano de 2007, no Município de Selvíria (MS) foi analisada a produtividade de madeira do Pinus caribaea var. hondurensis, em função de alguns atributos físico-químicos de um Latossolo Vermelho Distrófico estabelecido num maciço florestal com 21 anos de idade. O objetivo foi selecionar, entre os atributos pesquisados do solo, aquele que melhor se apresentasse para explicar a variabilidade da produtividade de madeira. Para tanto, foi instalado um grid geoestatístico, para a coleta dos dados do solo e da planta, contendo 121 pontos amostrais, numa área de 3 ha do referido maciço. A produtividade de madeira variou diretamente com o pH do solo, tanto linear quanto espacialmente, com valores de 27,0-32,6 m³ ha-1 ano-1 e 3,9-4,4, respectivamente. Nos maiores, 32,6-36,9 m³ ha-1 ano-1 e 4,4-4,9. Dessa forma, o pH revelou ser um apreciável indicador da qualidade química do solo quando o objetivo foi estimar, linear e espacialmente, a produtividade de madeira da essência florestal pesquisada nas condições do Cerrado brasileiro do Sudeste do Estado do Mato Grosso do Sul.

Características físico-químicas de amidos modificados de grau alimentício comercializados no Brasil

Amidos nativos e modificados têm grande importância na indústria de alimentos, sendo empregados principalmente como espessantes e/ou estabilizantes. As limitações das pastas e géis obtidos a partir de amidos nativos tornaram necessário o desenvolvimento de muitos tipos de amidos modificados para aplicações alimentícias. Neste trabalho, algumas amostras de amidos modificados (n=20) disponíveis no Brasil foram recebidas de empresas produtoras e analisadas em relação a algumas características físico-químicas e propriedades tecnológicas. Um levantamento do uso de amidos modificados em alimentos também é apresentado, revelando crescente interesse pela indústria nesses ingredientes. Constatou-se que, enquanto alguns alimentos industrializados, como maioneses contêm em suas formulações amidos modificados, outros como condimento preparado de mostarda contêm apenas amido nativo. As análises físico-químicas permitiram concluir que alguns amidos modificados apresentavam teores elevados de acidez, relacionados à presença de reagentes utilizados em sua obtenção, não havendo presença de carboxilas nas suas macromoléculas. de maneira geral, os resultados de algumas propriedades tecnológicas avaliadas, tais como viscosidade aparente das pastas, resistência a congelamento/descongelamento e propriedade de expansão, estavam de acordo com a descrição dos produtos. As fontes mais observadas nas modificações foram, em ordem decrescente de importância, a mandioca, o milho ceroso e o milho regular.

Caracterização física e química de acerolas provenientes de diferentes regiões de cultivo

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Avaliação física e química da polpa de maracujá congelada comercializada na região de Bauru

A indústria de polpa de maracujá tem como objetivo a obtenção de produtos com características sensoriais e nutricionais próximas da fruta in natura. O objetivo deste trabalho foi avaliar as informações nutricionais das embalagens e as características físico-químicas das polpas de maracujá congeladas. Foram analisadas 25 amostras, de 07 marcas diferentes, adquiridas em supermercados de Bauru-SP, e região. Apenas uma das marcas analisadas (14,3%) encontra-se em acordo com a legislação vigente, sendo que as demais apresentam tabelas ultrapassadas ou incompletas. As características físico-químicas diferem entre as marcas comercializadas, principalmente quanto ao teor de ácido ascórbico, sendo que 64,0% das amostras se encontram em desarcordo com o Regulamento Técnico para Fixação dos Padrões de Identidade e Qualidade (PIQ) para polpa de maracujá do Ministério da Agricultura. As variações observadas entre a polpa in natura e a congelada são menores nos itens: densidade, pH, sólidos solúveis totais, acidez em ácido cítrico e ratio, mas altas quanto ao teor de ácido ascórbico.

Correlação entre métodos tradicionais e espectroscopia de ultra-som na determinação de características físico-químicas do leite

Compararam-se a espectroscopia de ultra-som (US) e os métodos tradicionais (MT) utilizados para a determinação de características físico-químicas do leite e estimaram-se as correlações entre esses métodos e suas acurácias. As características densidade, extrato seco desengordurado (ESD), teor de proteínas e teor de gordura foram determinadas em 65 amostras de leite cru por ambos os métodos. As densidades médias determinadas pelo US e pelos MT não diferiram entre si (P=0,14), e a correlação encontrada entre os dois métodos para a determinação da densidade não foi significativa (P= 0,08). Os teores médios de ESD, proteína e gordura encontrados pelo US e pelos MT foram diferentes (P=0,04, P<0,0001 e P<0,0001, respectivamente), as correlações entre os dois métodos utilizados para a análise dessas características foram positivas e significativas (r=0,0109, r=0,0007, r= <0,0001, respectivamente) e as acurácias dos métodos para essas determinações foram de 0,160, 0,062 e 0,145, respectivamente. Foi determinada a equação de regressão linear, que associa o teor de gordura obtido no método de espectroscopia de ultra-som ao do método butirométrico, que apresentou coeficiente de determinação de 0,5936.

Protocolo para ensaios físico-químicos de estabilidade de fitocosméticos

The growing demand for stable, safe and effective cosmetics has required increasingly complex studies by the scientific community and the use of more efficient techniques to determine the stability of these products. The use of active principles from the Brazilian flora has led to the development of numerous products, in the most varied pharmaceutical forms, making it, even more difficult to standardize experimental protocols to certify the stability of cosmetic preparations. While in Brazil there is no one protocol that standardizes the tests that should be carried out to determine product stability, several studies have been conducted in academic laboratories to determine the stability of specific raw materials. The rheological properties of topical use products have to be taken into account in their manufacture, storage and application. The determination of the rheological behavior of a formulation helps in evaluating the physicochemical nature of the vehicle, allowing early signs of physical instability to be detected and thus enabling quality control of the constituents, test formulations and final products. Thermal analysis has also been used to assist in the study of cosmetic stability and differential scanning calorimetry to guide the development of new products. Other tools, such as fluorimetry and laser granulometry can be used to help the study and development of both emulsified and non-emulsified systems. The aim of the present study is to develop a protocol for the investigation of the physical and chemical stability of phytocosmetics - systems containing active compounds extracted from the Brazilian biodiversity.

Aspectos sensoriais e físico-químicos de iogurtes de soja com espessantes/estabilizantes à base de fécula de inhame (Dioscorea alata), amido modificado e gelatina

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Propriedades físico-químicas de abacate submetido à secagem convectiva e desidratação osmótica

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Qualidade físcio-química e microbiológica de refrigerantes sabor guaraná em embalagens PET-2000mL e ocorrência de leveduras

Pós-graduação em Engenharia e Ciência de Alimentos - IBILCE

Fatores físico-químico e bacteriológicos do sistema de lavagem e pré-resfriamento de carcaças de frango e sua relação com a pesquisa de Salmonella spp. em carcaças pré-resfriadas

Pós-graduação em Alimentos e Nutrição - FCFAR

Estudo comparativo do estado de conservação de acrne moída através de métodos microbiológicos e físico-químicos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)