Morfoanatomia e ontogênese do fruto e semente de Styrax camporum Pohl. (Styracaceae), espécie de cerrado do Estado de São Paulo

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

Aggregation behaviour of hydrophobically modified poly(allylammonium) chloride

The behaviour of hydrophobically modified poly(allylammonium) chloride having octyl, decyl, dodecyl and hexadecyl side chains has been studied in aqueous solution using fluorescence emission techniques. Micropolarity studies using the I-1/I-3 ratio of the vibronic bands of pyrene show that the formation of hydrophobic microdomains depends on both the length of the side chain and the polymer concentration. The I-1/I-3 ratio of the polymers with low hydrophobe content (less than 5% mel) changes substantially when reaching a certain concentration. These changes are assigned to aggregation originating from interchain interactions. This behaviour is also confirmed by the behaviour of the monomer/excimer emission intensities of pyrene- dodecanoic acid used as a probe. For polymers having dodecyl side chains and hydrophobe contents higher than 10%, aggregates are formed independently of the polymer concentration. Anisotropy measurements show that microdomains resulting from the inter- and/or intramolecular interactions are similar to those observed for cationic surfactants. Viscosity measurements show that the coil dimensions are substantially decreased for the polymers having high hydrophobe contents, indicating intramolecular associations.

Fluorescence probe study of the interaction between acrylic acid-co-ethyl methacrylate copolymers and sodium dodecylsulfate

The interaction between sodium dodecylsulfate (SDS) and acrylic acid (AA)-ethyl methacrylate (EMA) copolymers has been investigated using steady state fluorescence and conductimetric measurements to assess the effect of the polymer composition on the aggregation process. Micropolarity studies using the ratio between the emission intensities of the vibronic bands of pyrene (I-1/I-3) and the shift of the fluorescence emission of pyrene-3-carboxaldehyde show, that the interaction of SDS with AA-EMA copolymers occurs at surfactant concentrations smaller than that observed for the pure surfactant in water and depends on the copolymer composition. The increase of ethyl methacrylate in the copolymers lowers the critical aggregation concentration (CAC) due to the larger hydrophobic character of the polymer backbone. The formation of aggregates on the macromolecule is induced mainly, by hydrophobic interactions, but the process is also influenced by the ionic strength due to the counter-ions of the polyelectrolyte.

Aqueous solution behavior of thermosensitive (N-isopropylacrylamide-acrylic acid-ethyl methacrylate) terpolymers

A series of N-isopropylacrylamide (NIPAM)-acrylic acid-ethyl methacrylate terpolymers with varied monomer compositions was prepared by radical polymerization. The solution behavior of these polymers was studied in dilute aqueous solution using spectrophotometry, fluorescence spectroscopy and high-sensitivity differential scanning calorimetry. The results obtained revealed that the lower critical solution temperatures depend strongly on the copolymer composition, solution pH and ionic strength. At a high pH, the ionization of acrylic acid (AA) units leads to an increase in solution cloud points (T-c). Solutions of polymers containing 10% or less of AA display a constant T-c for pH above 5.5, with 15% there is a continuous increase in T-c with pH and, for higher AA contents, no clouding was observed within the studied temperature range. Fluorescence probe studies were conducted by following the I (1)/I (3) ratio of pyrene vibronic bands and the emission of anilinonaphtalene sulfonic acid, sodium salt (ANS), both approaches revealing the existence of hydrophobic domains for polymers with higher ethyl methacrylate content at temperatures lower than T-c, suggesting some extent of aggregation and/or a coil-to-globule transition. Scanning calorimetry measurements showed an endothermic transition at temperatures agreeing with the previously detected cloud points. Moreover, the transition curves became broader and with a smaller transition enthalpy, as both the AA content and the solution pH were increased. These broader transitions were interpreted to be the result of a wider molecular distribution upon polymer ionization, hence, displaying varied solution properties. The decrease in transition enthalpy was rationalized as a consequence of reminiscent hydration of NIPAM units, even after phase separation, owing to the presence of electric charges along the polymer chain.

Interaction of the nonionic surfactant C12E8 with high molar mass poly(ethylene oxide) studied by dynamic light scattering and fluorescence quenching methods

Dynamic light scattering has been used to investigate ternary aqueous solutions of n-dodecyl octaoxyethylene glycol monoetber (C12E8) with high molar mass poly(ethylene oxide) (PEO). The measurements were made at 20 °C, always below the cloud point temperature (Tc) of the mixed solutions. The relaxation time distributions are bimodal at higher PEO and surfactant concentrations, owing to the preacute of free surfactant micelles, which coexist with the slower component, representing the polymer coil/micellar cluster comptex. As the surfactant concentration is increased, the apparent hydrodynamic radius (RH) of the coil becomes progressively larger. It is suggested that the complex structure consists of clusters of micelles sited within the polymer coil, as previously concluded for the PEO-C12E8-water system. However. C12E8 interacts less strongly than C12E8 with PEO; at low concentrations of surfactant the complex does not contribute significantly to the total scattered intensity. The perturbation of the PEO coil radius with C12E8 is also smaller than that in the C12E8 system. The addition of PEO strongly decreases the clouding temperature of the system, as previously observed for C12E8/PEO mixtures in solution Addition of PEO up to 0.2% to C12E8 (10 wt %) solutions doss not alter the aggregation number (Nagg) of the micelles probably because the surfactant monomers are equally partitioned as bound and unbound micelles. The critical micelle concentration (cmc), obtained from the I1/I3 ratio (a measure of the dependence of the vibronic band intensities on the pyrene probe environment), does not change when PEO is added, suggesting that for neutral polymer/surfactant systems the trends in Nagg and the cmc do not unambiguously reflect the strength of interaction.

Phase behavior of synthetic amphiphile vesicles investigated by calorimetry and fluorescence methods

The understanding of biological membranes may be improved by investigating physical properties of vesicles from natural or synthetic amphiphiles. The application of vesicles as mimetic agents depends on the knowledgment of their structure and properties. Vesicles having different curvature and size may be obtained using different preparation protocols. We have used differential scanning calorimetry (DSC) and steady-state fluorescence to investigate the gel to liquid-crystal phase transition of vesicles prepared by sonication (SUV) and non-sonication (GUV) of the synthetic dioctadecyldimethylammonium bromide (DODAB) in aqueous solution. DSC thermograms for a non-sonicated dispersion show a well-defined pre- and main transition corresponding to two narrow peaks at 36 and 45°C in the first upscan, while in a second upscan, only the main peak was observed. The sharpness of the peaks indicate a cooperative phase behavior for GUV. For a sonicated DODAB dispersion, the first upscan shows a third peak at 40.3°C, whereas for the second upscan the peaks are not well-defined, indicating a less cooperative phase behavior. Alternatively, the fluorescence quantum yield (Φ f) and the anisotropy (r) of trans, trans, trans-1-[4-(3-carboxypropyl)-phenyl]-6-[4-butylphenyl]-1,3,5-hexatriene (4H4A) and the ratio I 1/I 3 of the first to the third vibronic peaks of the pyrene emission spectrum as function of temperature are used as well to describe the phase behavior of DODAB sonicated and non-sonicated dispersions. It is in good agreement with the DSC results that the cooperativity of the thermotropic process is diminished under sonication of the DODAB dispersion, meaning that sonication changes from homogeneous to heterogeneous populations of the amphiphile aggregates. The pre- and main transitions obtained from these techniques are in fairly good accord with results from the literature.

Toxicogenetic monitoring in urban cities exposed to different airborne contaminants

Microparticles found in the air may be associated with organic matter that contains several compounds, such as Polycyclic Aromatic Hydrocarbons (PAHs) and nitro-PAHs, and may pose a significant risk to human health, possibly leading to DNA mutations and cancers. This study associated genotoxicity assays for evaluating human exposure with the atmospheric air of two urban areas in southern Brazil, that received different atmospheric contributions. Site 1 was under urban-industrial influence and the other was a non-industrial reference, Site 2. Organic extracts from the airborne particulate matter were tested for mutagenicity via the Salmonella/microsome assay and analyzed for PAH composition. Cells samples of people residing in these two cities were evaluated using the comet and micronucleus assay (MN).Concentrations of the individual PAHs ranged from 0.01ng/m3 (benzo[a]anthracene) to 5.08ng/m3 (benzo[ghi]perylene). As to mutagenicity analysis of airborne, Site 1 presented all the mutagenic responses, which varied from 3.2±1.22rev/m3 (TA98 no S9) to 32.6±2.05rev/m3 (TA98, S9), while Site 2 ranged from negative to minimal responses. Site 1 presented a high quantity of nitro and amino derivatives of PAHs, and peaked at 56.0±3.68rev/μg (YG1024 strain). The two groups presented very low DNA damage levels without intergroup difference. Although Site 1 presented high mutagenic responses in the air samples, high PAH levels, healthy people exposed to this environment did not show significative damage in their genetic material. However, the evaluation of different environmental and genetic damage in such population is necessary to monitor possible damages. © 2013 Elsevier Inc.

Ultrasound-assisted extraction of Na and K from swine feed and its application in a digestibility assay: A green analytical procedure

The study is aimed to evaluate the efficiency of ultrasound-assisted extraction (UAE) as a simple strategy focused on sample preparation for metal determination in biological samples. The extraction of sodium and potassium extraction was carried out from swine feed followed by determination of the concentration of these metals by flame atomic emission spectrometry (FAES). The experiment was performed to cover the study of the variables influencing the extraction process and its optimal conditions (sample mass, particle size, acid concentration, sonication time and ultrasound power); the determination of these analytical characteristics and method validation using certified reference material; and the analysis of pre-starter diets. The optimal conditions established conditions were as follows: mass: 100 mg, particle size:<60 μm, acid concentration: 0.10 mol L-1 HCl, sonication time: 50 s and ultrasound power: 102 W. The proposed method (UAE) was applied in digestibility assays of those nutrients present in different piglet pre-starter feeds and their results proved to be compatible with those obtained from mineralized samples (P < 0.05). The ultrasound extraction method was demonstrated to be an excellent alternative for handless sampling and operational costs and the method also has the advantage of does not generating toxic residues that may negatively affect human health and contaminate the environment. © 2013 Elsevier B.V. All rights reserved.

Síntese, caracterização e estudos em solução de terpolímeros antififílicos termo-sensíveis ao pH: uma perspectiva para obtenção de sistemas transportadores de fármacos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Planejamento, sintese e avaliação biológica de derivados furoxânicos e benzofuroxânicos potencialmente antichagásicos

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

Desenvolvimento metodológico e avaliação de contaminação por HPAs em sedimentos da baia de Guajará

Os Hidrocarbonetos Policíclicos Aromáticos (HPAs) são poluentes de efeito tóxico, prejudiciais ao meio ambiente e à saúde humana, fazem parte de um grupo de compostos poluentes orgânicos persistentes (POPs), que por suas características tem impactado o ambiente, sendo por esse motivo bastante estudados. Podem estar presentes nas formas particulada, dissolvida e/ou gasosa, estando presentes em diferentes ambientes; solo, sedimento, ar, água, material particulado na atmosfera, organismos e alimentos (Kennish, 2007). As fontes naturais de HPAs incluem atividades vulcânicas, queimadas naturais, exsudação de óleos, além de processos biogênicos. HPAs antrogênicos podem ocorrer pela combustão incompleta de óleos combustíveis (automotores e industriais), queima intencional de madeira e plantações, efluentes domésticos e/ou industriais, drenagens pluviais urbanas, derrames acidentais de óleos e derivados. Hidrofóbicos e lipofílicos, essas substâncias podem ser facilmente adsorvidas em sedimentos, sendo este compartimento um importante reservatório desses poluentes. Para avaliar a presença desses compostos no ambiente, utilizou-se nesse trabalho a Cromatografia Líquida de Alta Eficiência. As amostras utilizadas no desenvolvimento e otimização da metodologia foram coletadas na baia do Guajará (Belém – PA). O presente trabalho constituiu-se dessa forma em um desenvolvimento de um procedimento metodológico (com adaptações e otimizações) para quantificar 16 HPAs em 10 pontos na baia do Guajará, Belém – PA, em duas etapas de campo, totalizando 20 amostras analisadas. Na etapa de desenvolvimento do método analítico foram testados sistemas de eluição, polaridade do sistema e fluxo do eluente entre outros. Para validação do método foram avaliados os parâmetros fidelidade, linearidade, limite de detecção, limite de quantificação do método. Razões diagnósticas foram calculadas para identificação das fontes primárias do HPAs encontrados na baia. Foram identificadas, a partir de razões diagnósticas da ΣHPAs BMM/ΣHPAsAMM; Fen/Ant; Flt/Pir; Ant/Σ178; Flt/Σ202; B(a)P/Σ228 e Ind(123cd) pireno/Σ276 as fontes primárias dos 16 HPAs estudados no sedimento da baia. A somatória das concentrações dos HPAs leves na primeira etapa de campo, variou de 132,13 ng.g^-1 a 1704,14 ng.g^-1, a ΣHPAs dos pesados de 125,82 g.g^-1 a 1269,71 ng.g^-1 e ΣHPAs totais de 317,84 ng.g^-1 a 3117,06 ng.g^-1.. Na segunda etapa de campo, as concentrações dos HPAs leves variou de 76,12 ng.g^-1 a 1572,80 ng.g^-1 ; a ΣHPAs pesados variou entre 213,90 ng.g^-1 a 1423,03 ng.g^-1, e Σ HPAs totais teve concentrações de 290,02 ng.g^-1 a 2995,82 ng.g^-1. A partir dos resultados obtidos pode-se classificar a baia do Guajará como moderadamente impactada. A combustão constitui a fonte predominante de HPAs nos sedimentos da baia do Guajará, seguida da combustão de biomassa vegetal e aporte de petróleo e derivados. A maioria dos pontos estudados nesse trabalho, nas duas etapas de campo, apresentaram concentrações de HPAs individuais acima dos VGQS.

Aplicação da cromatografia líquida de alta eficiência na investigação de hidrocarbonetos policíclicos aromáticos em testemunhos sedimentares

Hidrocarbonetos policíclicos aromáticos (HPAs) são compostos orgânicos originários de fontes naturais e antrópicas e, por apresentarem potencial carcinogênico e mutagênico, são considerados poluentes prioritários por agências ambientais. Desta forma, métodos analíticos para investigação de tais compostos que sejam rápidos e de baixo custo são de relevância considerável para o monitoramento ambiental. O presente trabalho teve como objetivos otimizar um método analítico para HPAs utilizando cromatografia líquida com detecção por arranjo de diodos (HPLC-DAD) e aplicar em testemunho sedimentar de região estuarina. Para otimização e avaliação do método, uma coluna sedimentar de 46 cm de comprimento foi coletada na foz do Rio Tucunduba (Belém, Pará) e seccionada em porções de 2 cm (subamostras). Após secagem, 30 g de cada porção foram extraídos com mistura de diclorometano em acetona (1:1) em ultrassom por 40 min. Os extratos obtidos foram centrifugados, purificados em sílica-gel, adaptação em funil necessária principalmente para reter partículas finas, e em seguida concentrados em rotaevaporador à vácuo e, por fim, filtrados com membrana de nylon 0,22 μm antes da injeção no HPLC. Amostras fortificadas com padrões analíticos de 16 HPAs e brancos também foram processados da mesma maneira. Um conjunto de parâmetros para validação do método foi investigado e observou-se: (1) boa linearidade: as curvas de calibração (analíticas) apresentaram coeficientes de correlação elevadas; (2) precisão adequada: obteve-se desvio padrão relativo dentro do aceitável, sendo o mínimo de 2,1% para acenaftileno e máximo de 19,7% para o fluoranteno; (3) limites de detecção baixos: entre 0,004 a 1,085 ng g g^-1, viabilizando análises em concentrações reais in situ; (4) recuperação adequada para traços: sendo a mínima de 40,0% para o acenaftileno e máxima de 103,1% para o benzo(k)fluoranteno. As concentrações de HPAs totais variaram nas seções do testemunho sedimentar entre 60,77 - 783,3 ng g^-1 de sedimento seco. O método otimizado mostrou-se vantajoso com relação aos tradicionais que utilizam extrator soxhlet e colunas de adsorventes para purificação de extratos por minimizar o tempo de extração e reduzir custos com uso de volumes menores de solventes para purificação do extrato. A limitação do método, porém, foi a coeluição do criseno e do benzo(a)antraceno e a sobreposição do fluoreno e acenafteno, além da quantificação benzo(g,h,i)perileno. Essa limitação provavelmente está associada à eficiência da coluna cromatográfica disponível para a análise, que é para aplicação geral. O método mostrou-se aplicável a amostras estuarinas complexas e ricas em silte e argila. Razões diagnósticas de HPAs parentais indicam fontes petrogênicas a profundidades de 24 – 26 cm, 28 – 30 cm; e fontes pirolíticas a profundidades de 6 – 8 cm, 10 – 12 cm e 14 – 16 cm respectivamente.

Síntese, caracterização e estudo da auto-associação em solução aquosa de derivados anfifílicos zwiteriônicos de quitosana

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Diurnal and nocturnal measurements of PAH, nitro-PAH, and oxy-PAH compounds in atmospheric particulate matter of a sugar cane burning region

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

Exposure to lard-based high-fat diet during fetal and lactation periods modifies breast cancer susceptibility in adulthood in rats

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