Extração e análise da fração lipídica da microalga monoraphidium sp., síntese e caracterização do seu biodiesel

The cultivation of microalgae biomass in order to produce biodiesel arises as an extremely promising aspect, in that the microalgae culture includes short cycle of reproduction, smaller areas for planting and residual biomass rich in protein content. The present dissertation evaluates the performance and features, through spectrometry in the region of infrared with transformed Fourier (FTIR) and spectrometry in the region of UVvisible (UV-Vis), of the extracted lipid material (LM) using different techniques of cell wall disruption (mechanical agitation at low and at high spin and agitation associated with cavitation). The technique of gas chromatography (GC) brought to light the success of alkaline transesterification in the conversion of oil into methyl monoesters (MME), which was also analyzed by spectroscopic techniques (FTIR, proton magnetic resonance (1H NMR) and carbon (13C NMR). Through thermogravimetric analysis (TGA) were analyzed the lipid material (LM), biodiesel and the microalgae biomass. The method which provided the best results concerning the efficiency in extraction of the LP of Monoraphidium sp. (12,51%) was by mechanical agitation at high spin (14 000 rpm), for 2 hours being the ideal time, as shown by the t test. The spectroscopic techniques (1H NMR, 13C NMR and FTIR) confirmed that the structure of methyl monoesters and the chromatographic data (CG) revealed a high content of saturated fatty acid esters (about 70%) being the major constituent eicosanoic acid (33,7%), which justifies the high thermal stability of microalgae biodiesel. The TGA also ratified the conversion rate (96%) of LM into MME, pointing out the quantitative results compatible with the values obtained through GC (about 98%) and confirmed the efficiency of the extraction methods used, showing that may be a good technique to confirm the extraction of these materials. The content of LM microalgae obtained (12,51%) indicates good potential for using such material as a raw material for biodiesel production, when compared to oil content which can be obtained from traditional oil for this use, since the productivity of microalgae per hectare is much larger and requires an extremely reduced period to renew its cultivation

Avaliação da estabilidade térmica e oxidativa do biodiesel de algodão e do efeito da adição de antioxidantes (α-tocoferol e BHT)

This work aims to study the effects of adding antioxidants, such as, α- tocopherol and BHT on the thermal and oxidative stability of biodiesel from cottonseed (B100). The Biodiesel was obtained through the methylical and ethylical routes. The main physical and chemical properties of cotton seed oil and the B100 were determined and characterized by FTIR and GC. The study of the efficiency of antioxidants, mentioned above, in concentrations of 200, 500, 1000, 1500, 2000ppm, to thermal and oxidative stability, was achieved by Thermogravimetry (TG), Differential Thermal Analysis (DTA), Differential Scanning Calorimetry (DSC), Differential Scanning Calorimetry - Hi-Pressure (P-DSC) and Rancimat. The Biodiesel obtained are within the specifications laid down by Resolution of ANP No7/2008. The results of TG curves show that the addition of both antioxidants, even in the lowest concentration, increases the thermal stability of Biodieseis. Through the DTA and DSC it was possible to study the physical and chemical transitions occurred in the process of volatilization and decomposition of the material under study. The initial time (OT) and temperature (Tp) of oxidation were determined through the P-DSC curve and they showed that the α-tocopherol has a pro-oxidant behavior for some high concentrations. The BHT showed better results than the α-tocopherol, with regard to the resistance to oxidation

Bioprospecção química da esponja callyspongia vaginalis (Callyspongiidae)

Recently, marine organisms have attracted attention because of the complexity and potent biological activity from your secondary metabolites. Our planet has 80% it surface covered by oceans and seas, therefore, housing a wide number of different forms of life, among them, the sponges. These sessile and filtrating animals, according to numerous researches, come showing like true chemistry factories. The substances from these animals, sometimes show as news targets to therapeutics agents, and some countries has already use them for treatment of some diseases. Further of the secondary metabolites, the polysaccharides of marine origin also have been target of studies, because the presence of the sulfates groups in its molecules. Polysaccharides with differents biological activities have been related in a large number of researches. Actually, many studies show the sponges as source of promising medicine. These studies inspire new researches, because the few number of sponges species studied until now. Because of that, the present work shows the chemistry prospection of the sponge Callyspongia vaginalis. Chromatographic methods in silica gel allowed the isolations of two secondary metabolites: the known β- sitosterol and a ceramide, no reported in the genus Callyspongia, previously. The analysis of the their lipid extracts show different kinds of fatty acids with a variety of chain length (saponifiable fraction), and others metabolites like Lupenone and stigmasterol, also unprecedented in the genus. The Polysaccharide characterization and the elucidation of the secondary metabolites acquired through of chromatography analysis (CC, molecular exclusion) and spectrometric (NMR 1H and 13C, mass, IR), respectively and comparison with literature data

Degradação térmica e catalítica do resíduo atmosférico de petróleo (RAT), utilizando materiais nanoestruturados do tipo SBA-15

In this work were synthesized and characterized the materials mesoporous SBA-15 and Al- SBA-15, Si / Al = 25, 50 and 75, discovered by researchers at the University of California- Santa Barbara, USA, with pore diameters ranging from 2 to 30 nm and wall thickness from 3.1 to 6.4 nm, making these promising materials in the field of catalysis, particularly for petroleum refining (catalytic cracking), as their mesopores facilitate access of the molecules constituting the oil to active sites, thereby increasing the production of hydrocarbons in the range of light and medium. To verify that the materials used as catalysts were successfully synthesized, they were characterized using techniques of X-ray diffraction (XRD), absorption spectroscopy in the infrared Fourier transform (FT-IR) and adsorption nitrogen (BET). Aiming to check the catalytic activity thereof, a sample of atmospheric residue oil (ATR) from the pole Guamaré-RN was performed the process by means of thermogravimetry and thermal degradation of catalytic residue. Upon the curves, it was observed a reduction in the onset temperature of the decomposition process of catalytic ATR. For the kinetic model proposed by Flynn-Wall yielded some parameters to determine the apparent activation energy of decomposition, being shown the efficiency of mesoporous materials, since there was a decrease in the activation energy for the reactions using catalysts. The ATR was also subjected to pyrolysis process using a pyrolyzer with gas chromatography coupled to a mass spectrometer. Through the chromatograms obtained, there was an increase in the yield of the compounds in the range of gasoline and diesel from the catalytic pyrolysis, with emphasis on Al-SBA-15 (Si / Al = 25), which showed a percentage higher than the other catalysts. These results are due to the fact that the synthesized materials exhibit specific properties for application in the process of pyrolysis of complex molecules and high molecular weight as constituents of the ATR

Síntese de catalisadores nanoporosos na ausência total e parcial de direcionadores orgânicos para pirólise catalítica de óleos pesados e intermediários

The processing of heavy oil produced in Brazil is an emergency action and a strategic plan to obtain self-sufficiency and economic surpluses. Seen in these terms, it is indispensable to invest in research to obtain new catalysts for obtaining light fraction of hydrocarbons from heavy fractions of petroleum. This dissertation for the degree of Doctor of Philosophy reports the materials preparation that combine the high catalytic activity of zeolites with the greater accessibility of the mesoporosity, more particularly the HZSM-5/MCM-41 hybrid, done by synthesis processes with less environmental impact than conventional ones. Innovative methodologies were developed for the synthesis of micro-mesoporous hybrid material by dual templating mechanism and from crystalline zeolitic aluminosilicate in the absence of organic template. The synthesis of hybrid with pore bimodal distribution took place from one-single organic directing agent aimed to eliminate the use of organic templates, acids of any kind or organic solvents like templating agent of crystalline zeolitic aluminosilicate together with temperature-programmed microwave-assisted, making the experimental procedures of preparation most practical and easy, with good reproducibility and low cost. The study about crystalline zeolitic aluminosilicate in the absence of organic template, especially MFI type, is based on use of H2O and Na+ cation playing a structural directing role in place of an organic template. Advanced characterization techniques such as X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Highresolution Transmission Electron Microscopy (HRTEM), Adsorption of N2 and CO2, kinetic studies by Thermogravimetric Analysis (TGA) and Pyrolysis coupled to Gas Chromatography/Mass Spectrometry (Pyrolysis-GC/MS) were employed in order to evaluate the synthesized materials. Achieve the proposed objectives, has made available a set of new methodologies for the synthesis of zeolite and hybrid micro-mesoporous material, these suitable for catalytic pyrolysis of heavy oils aimed at producing light fraction

Avaliação da remoção catalítica de compostos orgânicos monoaromáticos em água utilizando materiais nanoestruturados de sílica

Statistics of environmental protection agencies show that the soil has been contaminated with problems often resulting from leaks, spills and accidents during exploration, refining, transportation and storage oil operations and its derivatives. These, gasoline noteworthy, verified by releasing, to get in touch with the groundwater, the compounds BTEX (benzene, toluene, ethylbenzene and xylenes), substances which are central nervous system depressants and causing leukemia. Among the processes used in remediation of soil and groundwater contaminated with organic pollutants, we highlight those that use hydrogen peroxide because they are characterized by the rapid generation of chemical species of high oxidation power, especially the hydroxyl radical ( OH), superoxide (O2 -) and peridroxil (HO2 ), among other reactive species that are capable of transforming or decomposing organic chemicals. The pH has a strong effect on the chemistry of hydrogen peroxide because the formation of different radicals directly depends on the pH of the medium. In this work, the materials MCM-41 and Co-MCM-41 were synthesized and used in the reaction of BTEX removal in aqueous media using H2O2. These materials were synthesized by the hydrothermal method and the techniques used to characterize were: XRD, TG/DTG, adsorption/desorption N2, TEM and X-Ray Fluorescence. The catalytic tests were for 5 h of reaction were carried out in reactors of 20 mL, which was accompanied by the decomposition of hydrogen peroxide by molecular absorption spectrophotometry in the UV-Vis, in addition to removal of organic compounds BTEX was performed as gas chromatography with detection photoionization and flame ionization and by static headspace sampler. The characterizations proved that the materials were successfully synthesized. The catalytic tests showed satisfactory results, and the reactions containing BTEX + Co-MCM-41 + H2O2 at pH = 12.0 had the highest percentages of removal for the compounds studied

Aplicabilidade da voltametria de pulso diferencial na quantificação de ácido fólico e ácido oxálico: um método comparativo

The development of more selective and sensitive analytical methods is of great importance in different areas of knowledge, covering, for example, food, biotechnological, environmental and pharmaceutical sectors. The study aimed to employ the technique electroanalytical differential pulse voltammetry (DPV) as an innovative and promising alternative for identification and quantification of organic compounds. The organic compounds were investigated in this study oxalic acid (OA) and folic acid (FA). The electrochemical oxidation of oxalic acid has been extensively studied as a model reaction in the boundary between the organic and inorganic electrochemistry. Since the AF, an essential vitamin for cell multiplication in all tissues, which is essential for DNA synthesis. The AF has been investigated using analytical techniques, liquid chromatography and molecular absorption spectrophotometry. The results obtained during the experimental procedure indicated that the process of electrochemical oxidation of oxalic acid is strongly dependent on the nature of the anode material and the oxidation mechanism, which affects their detection. Efficient removal was observed in Ti/PbO2 anodes, graphite, BDD and Pt 90, 85, 80 and 78% respectively. It was also shown that the DPV employing glassy carbon electrode offers a fast, simple, reliable and economical way to determine the AO during the process of electrochemical oxidation. Furthermore, electroanalytical methods are more expensive than commonly used chromatographic analysis and other instrumental methods involving toxic reagents and higher cost. Compared with the classical method of titration and DPV could be a good fit, confidence intervals and detection limits confirming the applicability of electroanalytical technique for monitoring the degradation of oxalic acid. For the study of AF was investigated the electrocatalytic activity of the carbon paste electrode for identification and quantification in pharmaceutical formulations by applying the DPV. The results obtained during the experimental procedure showed an irreversible oxidation peak at 9.1 V characteristic of FA. The carbon paste sensor showed low detection limit of 5.683×10−8 mol L-1 reducing matrix effects. The spectrophotometric analysis showed lower concentrations of HF compared with those obtained by HPLC and DPV. The levels of AF were obtained according to the methodology proposed by the Brazilian Pharmacopoeia. The electroanalytical method (DPV) proposed is cheaper than GC analysis commonly used by the pharmaceutical industry. The results demonstrated the potential of these electroanalytical techniques for future applications in environmental, chemical and biological sensors

Usos potenciais de moringa oleifera lam., uma matriz para produção de biodiesel e tratamento de água no semiárido nordestino

The current environmental crisis demands transformations in the relations among society, nature and development, considering sustainability. In this context, an important theme is replacing fossil fuels with biofuels, such as biodiesel. Moringa oleifera Lam. is a species that can be used as a raw material to produce biodiesel. Besides, it is a multiple purposes plant, which can be used also in water treatment. Thus, the aims of this work were to analyze the anatomical adaptations found in the stem and in the leaf and the seed s oil stores of M. oleifera., to investigate chemical characteristics of M. oleifera s seed oil, considering biodiesel production, and to evaluate the coagulation activity of these seeds in water treatment. Semipermanent histological laminas were made and it follows that the stem has thick cuticle, stomata whose cells guard are below the epidermis line, hollow medulla, druses and tector trichomes as adaptations to climate and soil conditions in which the species is found and the leaf is dorsiventral and it has thick cuticle, tector trichomes and druses. The seed has great reserves of oil. These features favor the use of Moringa oleifera Lam. as a raw material to produce biodiesel in Brazil s Northeast semiarid region. Chemical analysis were made through oil solvent extraction using mechanic stirrer. The oil was analyzed in UV spectrophotometer. A transesterification was made and biodiesel was analyzed in gas chromatography. Oil yield was high and good quality biodiesel was obtained. To evaluate seeds coagulantion activity, coagulation and flocculation essays in jartest were made, using seed extract to treat raw water. Seeds were efficient in cogulation process to treat water. So, they can be used in rudimentary systems or as a raw material to coagulant proteins extraction, as an alternative to traditional coagulants. M. oleifera has characteristics that favor its use to biodiesel production and water treatment

Contribuição da glicemia pós-desjejum para o controle glicêmico do paciente com diabetes melito tipo 2

Estudos epidemiológicos observaram que glicemias pós-prandiais (GPPs) elevadas são fator principal na ocorrência de doenças cardiovasculares. Sabe-se que a hemoglobina glicada (HbA1C) reflete a glicemia média dos últimos 2-3 meses, entretanto é controversa a contribuição relativa da glicemia de jejum (GJ) e GPP para o valor da HbA1C. OBJETIVO: Avaliar a contribuição da GJ e GPPs para o valor da HbA1C em pacientes com diabetes melito tipo 2 (DM2). MÉTODOS: Participaram 53 indivíduos com DM2, estáveis e em tratamento com antidiabéticos orais (n= 27) e/ou insulina (n= 26). Cada paciente comparecia a 3 visitas a intervalos de 2 meses. em cada visita era medida a GJ, as GPPs (2h pós-desjejum: GPD e pós-almoço: GPA) e a HbA1C, sendo fornecido o desjejum e o almoço segundo seus hábitos alimentares. Mediu-se a glicose plasmática pela glicose-oxidase e a HbA1C, pela cromatografia de troca iônica. Realizou-se a análise das associações pelo coeficiente de correlação de Spearman, com P< 0,05. RESULTADOS: A HbA1C correlacionou-se melhor em cada visita ao longo do estudo com a GPD (r: 0,66­0,48), a glicemia média (r: 0,64­0,41), a área abaixo da curva glicêmica (r : 0,64­0,46) e a GPP média (r: 0,59­0,41). CONCLUSÕES: A GPD mostrou-se um parâmetro eficaz adicional no monitoramento glicêmico dos pacientes com DM2.

Purificação e caracterização estrutural de homogalactanas sulfatadas anticoagulantes da alga verde Codium isthmocladum

Conselho Nacional de Desenvolvimento Científico e Tecnológico

Prevalência de talassemia alfa+ (deleção -3.7) na população adulta do estado do Rio Grande do Norte

Alpha thalassemia, the most common monogenic disorder in the world, is characterized by deletions of one (+-thalassemia) or both alpha genes (0-thalassemia) located on human chromosome 16 (16p13.3). The most common case of +-thalassemia is a deletion of 3.7 kb of DNA (-3.7 deletion). It is most prevalent in African and Middle East regions. In the few studies carried out in Brazilian population -3.7 deletion was the most common deletion, mainly in African descendants. This study was conducted to determine the prevalence of +- thalassemia (deletion 3.7kb) in adult population from Rio Grande do Norte. We obtained blood samples from 713 unrelated individuals of both genders, aged between 18 and 59 years old. All individuals were born in Rio Grande do Norte. The hematological indices were obtained in an automatic cell counter (Micros 60, ABX Diagnostics). The hemoglobin measurement (A2 and Fetal hemoglobin) and the profile confirmation were carried out by high performance liquid chromatography (HPLC) methodology. Genomic DNA was obtained from peripheral blood leukocytes using Illustra Blood GenomicPrep Mini Spin kit and -3.7 deletion was investigated by PCR. Among the 713 individuals studied, 80 (11,2%) presented +- thalassemia: 79 (11,1%) were heterozygous and 1 (0,1%) homozygous for the -3.7 deletion. Considering the ethnic group, negroes showed the greatest prevalence of +-thalassemia (12,5%), followed by mulattoes (12,3%) and caucasian (9,6%). Statistical comparison of hematological parameters between normal individuals and heterozygous to +-thalassemia showed significant differences in RBC (p<0,001), MCV (p<0,001), MCH (p<0,001), Hb A2 (p=0,007) as well as female hemoglobin concentration (p=0,003). This is one of the first studies to research +-thalassemia in general population of Rio Grande do Norte state and these results attest the importance of investigation of this condition to define the etiology of microcytosis and hypochromia.

Influência de tensoativos não iônicos na destilação molecular de petróleo

The molecular distillation is show as an alternative for separation and purification of various kinds of materials. The process is a special case of evaporation at high vacuum, in the order from 0.001 to 0.0001 mmHg and therefore occurs at relatively lower temperatures, preserves the material to be purified. In Brazil, molecular distillation is very applied in the separation of petroleum fractions. However, most studies evaluated the temperature of the evaporator, condenser temperature and flow such variables of the molecular distillation oil. Then, to increase the degree of recovery of the fraction of the distillate obtained in the process of the molecular distillation was evaluated the use nonionic surfactants of the class of nonylphenol ethoxylate, molecules able to interact in the liquid-liquid and liquid-vapor interface various systems. In this context, the aim of this work was to verify the influence of commercial surfactant (Ultranex-18 an Ultranex-18-50) in the molecular distillation of a crude oil. The physicochemical characterization of the oil was realized and the petroleum shown an API gravity of 42°, a light oil. Initially, studied the molecular distillation without surfactant using star design experimental (2H ± ) evaluated two variables (evaporator temperature and condenser temperature) and answer variable was the percentage in distillate obtained in the process (D%). The best experimental condition to molecular distillation oil (38% distillate) was obtained at evaporator and condenser temperatures of 120 °C and 10 ° C, respectively. Subsequently, to determine the range of surfactant concentration to be applied in the process, was determined the critical micellar concentration by the technique of scattering X-ray small angle (SAXS). The surfactants Ultranex-18 an Ultranex-18-50 shown the critical micelle concentration in the range of 10-2 mol/L in the hydrocarbons studied. Then, was applied in the study of distillation a concentration range from 0.01 to 0.15 mol/L of the surfactants (Ultranex- 18 and 50). The use of the nonionic surfactant increased the percentage of hydrocarbons in the range from 5 to 9 carbons in comparison to the process carried out without surfactant, and in some experimental conditions the fraction of light compounds in the distilled was over 700% compared to the conventional process. The study showed that increasing the degree of ethoxylation of Ultranex18 to Ultranex-50, the compounds in the range of C5 to C9 reduced the percentage in the distilled, since the increase of the hydrophilic part of the surfactant reduces its solubility in the oil. Finally, was obtained an increase in the degree of recovery of light hydrocarbons, comparing processes with and without surfactant, obtained an increase of 10% and 4% with Ultranex-18 and Ultranex-50, respectively. Thus, it is concluded that the Ultranex- 18 surfactant showed a higher capacity to distillation compared with Ultranex-50 and the application of surfactant on the molecular distillation from petroleum allowed for a greater recovery of light compounds in distillate

Perfil Fosfolipídico Pulmonar em Recém-nascidos de Ratas Diabéticas

Objetivo: avaliar as repercussões do diabete materno sobre o perfil fosfolipídico pulmonar de fetos de ratas com diabete moderado e grave pelas dosagens de lecitina (L), esfingomielina (E), fosfatidil-glicerol (PG), fosfatidil-inositol (PI) e relações L/E e PG/PI. Métodos: foram utilizadas 54 ratas Wistar, em idade reprodutiva, introduzidas na seqüência experimental de diabete e prenhez¹. O diabete foi induzido por aloxana (42 mg/kg de peso, iv) e compostos três grupos: controle, diabete moderado (DM, glicemia entre 120 e 200 mg/dl) e diabete grave (DG, níveis superiores a 200 mg/dl). Realizou-se cesárea no 21º dia, os pulmões fetais foram macerados, reunidos em pool e os fosfolipídios dosados por cromatografia em camada delgada unidirecional. Resultados: os pulmões dos filhotes das ratas com diabete moderado tiveram maior peso (0,159 g) e menor concentração de PG (3,0 µg/ml) e PI (3,4 µg/ml) que o grupo controle (0,155 g; 6,8 e 6,7 µg/ml), e as mesmas relações L/E (2,2) e PG/PI (2,0); os pulmões dos filhotes das ratas com diabete grave tiveram menor peso (0,145 g), os mesmos valores das relações L/E (1,9) e PG/PI (2,1) e menor valor de PI (5,1 µg/ml) que o grupo controle. Conclusões: 1) o retardo do amadurecimento pulmonar dos recém-nascidos de ratas com diabete moderado é explicado pelo maior peso pulmonar associado à menor concentração de PG e PI; 2) a aceleração do amadurecimento pulmonar dos recém-nascidos de ratas com diabete grave é explicada pelo menor peso pulmonar associado à mesma concentração de PG e PI.

Conjugação e validação de controle isotípico IgG1-FITC para uso em citometria de fluxo

Em meados da década de 50 iniciou-se o desenvolvimento da citometria de fluxo, tecnologia que permite verificar características físico-químicas de células ou partículas suspensas em meio fluido. Esta tecnologia utiliza anticorpos monoclonais marcados com fluorocromos como ferramenta de investigação em diversas análises e necessita de controles isotípicos para definição da região negativa (background). Estes controles são constituídos por imunoglobulinas de mesmo isotipo e fluorocromo dos anticorpos testes, sendo o isotiocianato de fluoresceína (FITC) o marcador fluorescente mais utilizado na conjugação de anticorpos. Os controles isotípicos têm como função definir a fluorescência inespecífica (células negativas) e as regiões fluorescentes (células positivas). No presente estudo foi selecionado anticorpo monoclonal murino (AcMm) dirigido contra antígeno eritrocitário canino, produzido no Laboratório de Anticorpos Monoclonais do Hemocentro de Botucatu, o qual reage positivamente com hemácias de cães, mas nunca com leucócitos humanos, tendo, portanto, potencial utilidade como controle negativo em citometria de fluxo. A purificação do AcMm da subclasse IgG1 foi feita por cromatografia de afinidade em Proteína-A Sepharose, e o controle da purificação realizado por eletroforese em géis de ágarose e poliacrilamida (SDS-PAGE). A imunoglobulina purificada foi conjugada ao FITC e filtrado em coluna de Sephadex G-25 para separação das proteínas marcadas e não-marcadas. O AcMm conjugado foi testado contra hemácias de cães, e o êxito da conjugação comprovado por testes de fluorescência, sendo a mediana de positividade de 94,70. Frente a leucócitos humanos a mediana de positividade foi 0,03 contra 0,50 dos reagentes comerciais. Os testes estatísticos não-paramétricos de Wilcoxon e correlação de Spearman comprovaram a eficiência e validam o controle isotípico produzido em comparação aos reagentes comerciais testados.

Liberação intraocular de ofloxacina associada a lente de contato biossintética em ceratite bacteriana experimental em cães

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