Temperature-and pH-Sensitive Nanohydrogels of Poly(N-Isopropylacrylamide) for Food Packaging Applications: Modelling the Swelling-Collapse Behaviour

Temperature-sensitive poly(N-isopropylacrylamide) (PNIPA) nanohydrogels were synthesized by nanoemulsion polymerization in water-in-oil systems. Several cross-linking degrees and the incorporation of acrylic acid as comonomer at different concentrations were tested to produce nanohydrogels with a wide range of properties. The physicochemical properties of PNIPA nanohydrogels, and their relationship with the swelling-collapse behaviour, were studied to evaluate the suitability of PNIPA nanoparticles as smart delivery systems (for active packaging). The swelling-collapse transition was analyzed by the change in the optical properties of PNIPA nanohydrogels using ultraviolet-visible spectroscopy. The thermodynamic parameters associated with the nanohydrogels collapse were calculated using a mathematical approach based on the van't Hoff analysis, assuming a two-state equilibrium (swollen to collapsed). A mathematical model is proposed to predict both the thermally induced collapse, and the collapse induced by the simultaneous action of two factors (temperature and pH, or temperature and organic solvent concentration). Finally, van't Hoff analysis was compared with differential scanning calorimetry. The results obtained allow us to solve the problem of determining the molecular weight of the structural repeating unit in cross-linked NIPA polymers, which, as we show, can be estimated from the ratio of the molar heat capacity (obtained from the van't Hoff analysis) to the specific heat capacity (obtained from calorimetric measurements).

Estimates of body sizes at maturation and at sex change, and the spawning seasonality and sex ratio of the endemic Hawaiian grouper (Hyporthodus quernus, F. Epinephelidae)

A case study of the reproductive biology of the endemic Hawaiian grouper or hapu’upu’u (Hyporthodus quernus) is presented as a model for comprehensive future studies of economically important epinephelid groupers. Specimens were collected throughout multiple years (1978–81, 1992–93, and 2005–08) from most reefs and banks of the Northwestern Hawaiian Islands. The absence of small males, presence of atretic oocytes and brown bodies in testes of mature males, and both developed ovarian and testicular tissues in the gonads of five transitional fish provided evidence of protogynous hermaphroditism. No small mature males were collected, indicating that Hawaiian grouper are monandrous (all males are sex-changed females). Complementary microscopic criteria also were used to assign reproductive stage and estimate median body sizes (L50) at female sexual maturity and at adult sex change from female to male. The L50 at maturation and at sex change was 580 ±8 (95% confidence interval [CI]) mm total length (TL) and 895 ±20 mm TL, respectively. The adult sex ratio was strongly female biased (6:1). Spawning seasonality was described by using gonadosomatic indices. Females began ripening in the fall and remained ripe through April. A February–June main spawning period that followed peak ripening was deduced from the proportion of females whose ovaries contained hydrated oocytes, postovulatory follicles, or both. Testes weights were not affected by season; average testes weight was only about 0.2% of body weight—an order of magnitude smaller than that for ovaries that peaked at 1–3% of body weight. The species’ reproductive life history is discussed in relation to its management.

Consumption to biomass (Q/B) ratio and estimates of Q/B-predictor parameters for Caribbean fishes

Estimates of the Q/B ratio and parameters of equations to 'predict' Q/B values for 116 fish stocks in the Gulf of Salamanca, Colombia are presented. A compilation of these estimates available for Caribbean Sea fishes (264 stocks) is also provided for comparison purposes. General trends in the value of Q/B resulting from differences in the equation and parameter values used are briefly discussed.

Materiais tipo hidrotalcita contendo Cu como precursores de catalisadores para a redução de NO pelo CO

Dentre os óxidos de nitrogênio, o N2O é um gás do efeito estufa altamente nocivo. Devido ao potencial contaminante que este possui, torna-se importante a implementação de processos capazes de reduzir a sua emissão, bem como a dos NOx. Tradicionalmente, têm-se empregado catalisadores baseados em metais nobres, porém estes apresentam como principal desvantagem o elevado custo. Desse modo, sempre houve o interesse pelo uso de outros tipos de catalisadores e metais neste sistema de reação. Nesse contexto, na presente dissertação procurou-se sintetizar precursores de catalisadores tipo hidrotalcita Cu-AlCO3 e avaliar o seu desempenho na reação de redução do NO pelo CO, visando melhorar a atividade e a seletividade a N2. Foram estudados diversos parâmetros de síntese e diferentes composições. Os parâmetros mais influentes na síntese foram a relação molar H2O/(Al+Cu) e a temperatura de secagem do sólido, cujos melhores valores foram 434 e 25C, respectivamente. Testaram-se dois sólidos, o primeiro composto pela fase hidrotalcita quase pura e o segundo com uma clara mistura entre fases hidrotalcita e malaquita. As análises térmica e química revelaram presença da fase malaquita em ambos os materiais com porcentagens de 14 e 40%, respectivamente. Os resultados de difração de raios X indicaram a presença da fase CuO para os catalisadores provenientes da calcinação dos materiais tipo hidrotalcita, porém a espectroscopia Raman evidenciou a presença de Cu2O no catalisador proveniente do material com maior mistura de fases. Os ciclos redox mostraram uma melhora na redutibilidade dos catalisadores após um ciclo de oxidação-redução. Além disso, foi estudado o impacto do envelhecimento térmico a 900C por 12 h no desempenho dos catalisadores. Pelos resultados de teste catalítico os melhores desempenhos foram alcançados pelos catalisadores envelhecidos, contudo o catalisador proveniente do precursor mais puro apresentou-se melhor tanto novo como envelhecido em termos de menor rendimento de N2O. Uma comparação com catalisadores à base de metal nobre mostrou um bom desempenho dos catalisadores à base de cobre, com a vantagem destes apresentarem menor emissão de N2O em temperaturas menores