Avaliação de protetores solares contendo filtros encapsulados/incorporados em matriz de sílica mesoporosa ordenada do tipo SBA-15 / Evaluation of sunscreens containing encapsulated/entrapped UV filters in ordered mesoporous silica type SBA-15

Filtros orgânicos são amplamente utilizados em formulações fotoprotetoras, com habilidade de absorver radiações ultravioleta (UV). Contudo, parte destes compostos possuem limitações, como: fotoinstabilidade, permeação cutânea e fotossensibilização e entre outros. Este trabalho envolveu a síntese de matriz mesoporosa do tipo SBA-15, encapsulação/incorporação de ρ-metoxicinamato de octila (MCO), benzofenona-3 (BZF-3) e avobenzona (AVO) na SBA-15 para aplicação em formulações fotoprotetoras. Fez-se a determinação da eficácia in vitro dos filtros encapsulados/incorporados combinados a ingrediente cosmético; o preparo de bastão fotoprotetor e determinação eficácia estimada; a avaliação do potencial de irritação ocular dos bastões por HET-CAM - Hen's Egg Test - Chorioallantoic Membrane, e a avaliação da permeação/retenção cutânea e perfil de biodistribuição dos filtros. Para a caracterização dos materiais foram empregadas técnicas físico-químicas e analíticas. As medidas de adsorção/dessorção de N2 mostrou que as amostras dos filtros solares encapsulados/incorporados apresentaram diminuição na área superficial e volume de poro (V), indicando que os filtros solares foram encapsulados/incorporados na superfície e nos poros da SBA-15. Os resultados de Espalhamento de raios X a baixo ângulo evidenciaram que os filtros solares não afetaram a estrutura hexagonal da SBA-15. Por TG/DTG e análise elementar foi possível determinar a quantidade de filtros solares na superfície e nos mesoporos da SBA-15. Enquanto, as curvas DSC e DTA revelaram aumento na estabilidade térmica da AVO e BZF-3, quando encapsulados/incorporados. Os resultados da eficácia fotoprotetora in vitro mostraram que a combinação dos três filtros solares encapsulados/incorporados na SBA-15 promoveram aumento de 52% no fator proteção solar (FPS), enquanto que, na formulação fotoprotetora contendo os três filtros encapsulados/incorporados, o aumento foi de 94%. O ensaio de HET-CAM evidenciou que os bastões contendo SBA-15 e os filtros encapsulados/incorporados não foram irritantes. O ensaio de permeação/retenção cutânea mostrou que o processo de encapsulação/incorporação da BZF-3 promoveu diminuição de sua permeação em todos os tempos de exposição. As quantidades permeadas de AVO e MCO ficaram abaixo do limite de quantificação nos tempos 6 e 12 h, no entanto, no tempo de 24 h foi possível quantificá-los. As quantidades dos filtros solares retidas na pele a partir da formulação contendo os filtros solares encapsulados/incorporados na SBA-15 (F4) foram menores (tempos 6 e 12 h) em comparação à formulação contendo os filtros solares não encapsulados (F3). A investigação da biodistribuição dos filtros solares mostrou que a retenção total na pele, como na derme, foi menor na formulação F4 em comparação à F3. O estudo comparativo entre pele suína e a pele humana mostrou que as quantidades de BZF-3 e AVO permeadas e retidas na pele suína foram superiores do que em relação à humana para ambas as formulações (F4 e FR). Pela técnica de biodistribuição, foi possível determinar que os filtros solares oriundos das formulações F3 e referência (FR) apresentaram maior retenção destes compostos na derme do que em outras camadas da pele. Contudo, observou-se que os filtros encapsulados apresentaram taxa reduzida de retenção na derme

Organic Filters are chemical compounds widely used in sunscreens formulations with the ability to absorb ultraviolet radiation (UV). Despite the effectiveness of these compounds in UV radiation protection, disadvantages related to their photo instability, potential skin permeation and photo sensibility pose significant challenges for improving these products. The aim of this work was to synthesize mesoporous matrix SBA-15, encapsulation/entrapping of octyl methoxycinnamate (OMC), benzophenone-3 (BZF-3) and avobenzone (AVO) into SBA-15 for application in photoprotective formulations. It was accessed in vitro photoprotection efficacy and in vitro photostability assay of encapsulated/entrapped UV filters combined with cosmetic ingredient and photoprotective stick formulations; evaluation of the ocular irritation potential of photoprotective stick formulations by in vitro method HET-CAM - Hen's Egg Test - Chorioallantoic Membrane; evaluation the skin permeation/deposition and biodistribution profile of photoprotective stick formulations. The decrease in the surface area and in mesoporous volume (V) observed in the nitrogen adsorption desorption isotherms of encapsulated/entrapped samples indicated that UV filters were efficiently encapsulated/entrapped into SBA-15. Additionally, SAXS results showed that UV filters did not affected the hexagonal structure of the mesoporous material and that these compounds filled the SBA-15 pores. TG/DTG and elemental analysis were efficient tools to confirm the presence and the quantity of UV filters into SBA-15. DTA and DSC curves of encapsulated/entrapped materials showed that the thermal stability of AVO and BZF-3 were increased. On the other hand, DSC curves of encapsulated/entrapped materials demonstrated that thermal stability of OMC was not increase. The in vitro photoprotective efficacy results demonstrated that the combination of the three sunscreens encapsulated/entrapped into SBA-15 increased 52.0% the SPF values, while the stick formulation containing the UV filters encapsulated/entrapped, the increase was 94.0%. Delivery experiments using porcine skin demonstrated that the encapsulation/entrapping process of UV filters resulted the decreased of BZF-3 permeation and deposition in skin (6 and 12 hours). The cutaneous biodistribution profile of UV filters showed that the deposition of these compounds from encapsulated/entrapped stick formulation (F4) was significantly lower than that from UV filters stick formulations (F3) in the total slices of the skin and dermis. The comparative study between porcine skin and human skin demonstrated that the amounts of BZF-3 and AVO permeated and deposited in porcine skin were higher than in human skin for both formulations (F4 and FR - reference formulation). By the biodistribution technique it was possible to determine that the UV filters from the formulations F3 and FR presented higher retention of these compounds in the dermis than in other layers of the skin. On the other hand, it was observed that the encapsulated UV filters presented low retention rate into dermis

Panus tigrinus as a potential biomass source for Reactive Blue decolorization: isotherm and kinetic study

Background: Textile and dye industries pose a serious threat to the environment. Conventional methods used for dye treatment are generally not always effective and environmentally friendly. This drove attention of scores of researchers to investigate alternative methods for the biodegradation of dyes using fungal strains. In this work, white-rot fungus (Panus tigrinus) was used as a biosorbent for the decolorization of Reactive Blue 19. The process parameters that were varied were initial concentration (50­150 mg/L), contact time (30­90 min), and pH (2­6). In addition, to gain important data for the evaluation of a sorption process, the equilibrium and kinetics of the process were determined. Results: White-rot fungus showed great potential in decolorizing Azo dyes. The strain showed the maximum decolorization of 83.18% at pH 2, a contact time of 90 min, and an initial concentration of 50 mg/L. The Langmuir isotherm described the uptake of the Reactive Blue 19 dye better than the Freundlich isotherm. Analysis of the kinetic data showed that the dye uptake process followed the pseudo second-order rate expression. Conclusion: The biosorption process provided vital information on the process parameters required to obtain the optimum level of dye removal. The isotherm study indicated the homogeneous distribution of active sites on the biomass surface, and the kinetic study suggested that chemisorption is the rate-limiting step that controlled the biosorption process. According to the obtained results, P. tigrinus biomass can be used effectively to decolorize textile dyes and tackle the pollution problems in the environment.

Overproduction of clavulanic acid by extractive fermentation

Background Clavulanic acid is an important beta-lactamase inhibitor produced as a secondary metabolite by the actinomycete Streptomyces clavuligerus. Clavulanic acid is chemically unstable; therefore, it is degraded during bacterial cultivation. In this work, the adsorbents clinoptilolite, activated carbon, calcined hydrotalcite, and Amberlite IRA 400 anionic exchange resin were studied in terms of their ability to adsorb clavulanic acid during extractive fermentation, in order to prevent product degradation and avoid product concentrations reaching inhibitory levels. Adsorption assays were used to investigate the effect of pH, and the decrease in the clavulanic acid concentration in the culture broth was measured for each adsorbent. Results IRA 400 was found to be most effective, with 78% adsorption of clavulanic acid. The maximum production of clavulanic acid in Erlenmeyer flask cultures increased 86% in terms of mass of CA, and 248% in cumulative CA concentration, with the use of Amberlite IRA 400 as adsorbent in extractive fermentation, compared to control fermentation performed without product removal. Conclusions The results indicated that extractive fermentation using a solid phase could be an important way of enhancing clavulanic acid titers. It was also possible to show that clavulanic acid acts as an inhibitor of its own synthesis.

Determinación de isotermas de desorción en jamón de cerdo cocido almacenado entre 4°C y 12°C / Desorption isotherms determination in cooked pork ham stored between 4°C and 12°C

Antecedentes: Las isotermas de sorción describen la relación termodinámica entre la actividad de agua (aw) y el contenido de humedad en base seca (g agua / g materia seca), de un producto alimentario a presión y temperatura constante. Estas pueden ser de adsorción o desorción. Su conocimiento es de gran importancia en la industria de alimentos, ya que brindan información apta para la selección del material de empaque, la predicción de la vida útil del producto y la evolución del contenido de humedad durante el tiempo de almacenamiento. Objetivos: Evaluar la relación existente entre la humedad y la aw en un jamón de cerdo cocido mediante el uso de isotermas de desorción a diferentes temperaturas de almacenamiento. Métodos: Para realizar el análisis se evaluaron dos lotes independientes de jamón donde se evaluó su composición fisicoquímica para luego ser almacenados en cámaras de almacenamiento a temperaturas de (4, 8 y 12°C). El proceso utilizado para determinar las curvas isotérmicas de sorción, fue el método recomendado por el proyecto COST 90, en un rango de aw entre 0,123 hasta 0,958 respectivamente. Los datos experimentales se modelaron utilizando cuatro modelos empíricos (Oswin, Caurie, Smith y Henderson) y dos teóricos (Guggenheim Anderson de Boer (GAB) y Brunauer, Emmett y Teller (BET)) comúnmente aplicados en la industria de alimentos. La calidad de ajuste se evaluó con el error medio relativo (%E), la raíz cuadrada del error cuadrático medio (RMSE) y la suma de errores cuadrados (SSE) respectivamente. Los datos se analizaron mediante la aplicación de modelos no lineales usando el método de mínimos cuadrados y se seleccionaron los modelos que presentaron mejores ajustes. Resultados: En relación con la cinética de desorción se observó que los modelos propuestos por GAB, BET y Oswin, tuvieron un mejor ajuste a los datos experimentales a las tres temperaturas de almacenamiento. Conclusión: En el jamón, las isotermas de desorción no presentan dependencia con la temperatura. Las curvas muestran un comportamiento tipo III, debido a la afinidad e interacción existente entre el sistema multicomponente y el agua disponible en el entorno.

The adsorption thermodynamics of sugarcane (Saccharum officinarum L. ) powder obtained by spray drying technology / Termodinámica de adsorción de polvo de caña de azúcar (Saccharum officinarum L. ) obtenido mediante la tecnología de secado por aspersión

Background: Sugarcane is one of the world's largest crop. It grows in the tropical and subtropical regions, and its harvest provides 80% of the world's sugar. In Latin America unrefined cane sugar is widely available and much less expensive than refined sugar. Sugarcane is a crop of great interest in Colombia due to the economic impact on the rural population and its application as sweetener agent. The powder of sugarcane (Saccharum officinarum L.) is widely used as a raw material in a wide range of industries such as foods, pharmaceutical, cosmetic and chemical. Objectives: The aim of the research work was the evaluation of the adsorption thermodynamics of sugarcane powder obtained by spray drying technology. Methods: The adsorption isotherms of sugarcane powder were evaluated at temperatures of 4 ± 0.1, 20 ± 0.2 and 30 ± 0.3 °C and its thermodynamic properties such as Gibbs free energy (G), differential heat of adsorption (∆H) and differential entropy (∆S) were calculated as a function of moisture content. Experimental data of adsorption isotherms were fitted to the GAB (Guggenheim ­ Andersen - de Boer), BET (Brunauer ­ Emmett - Teller), Henderson, Caurie, Smith, Hasley, Peleg, and Oswin models. Results: The results showed a type-II sigmoidal behavior, with temperature having a statistically significant effect. The GAB equation showed a better fit to the experimental data modeling (0.11≤aw≤0.87) although all models showed validity and goodness of fit to the experimental data. The net isosteric heat increased to a maximum value (57 kJ mol-1) and then decreased with the increase in moisture content. Conclusions: The sugarcane powder with maltodextrin, obtained by spray drying got low adsorption thermodynamic stability, as it required very low energy to occur this phenomenon, being obtained the maximum net isosteric heat when moisture content of 4.7% (d.b). This value is within the range of the monolayer moisture content found in the GAB and BET models.

Study on Thermodynamics and Adsorption kinetics of Purified endoglucanase (CMCase) from Penicillium notatum NCIM NO-923 produced under mixed solid-state fermentation of waste cabbage and Bagasse

In the current study, one thermostable endoglucanase was purified from Penicillium notatum NCIM NO-923 through mixed solid state fermentation of waste cabbage and bagasse. The molecular weight of the purified enzyme was 55kDa as determined by SDS polyacrylamide gel electrophoresis (SDS-PAGE). The enzyme had low activation energy (Ea) of 36.39KJ mol-1 for carboxymethyl cellulose hydrolysis and the enthalpy and entropy for irreversible inactivation was 87 kJ mol −1 and 59.3 J mol −1 K−1 respectively. The enzyme was quite thermostable with a Tm value of 62.2˚C. The pKa1 and pKa2 of ionizable groups of the active sites were 2.5 and 5.3 respectively. Apparent Km, Vmax and Kcat of the enzyme were found to be 5.2 mg mL-1, 80 U/gds and 322.4 sec-1 respectively. The enzyme showed about 1.4 fold increased activity in presence of 10mM MgSO4. Adsorption of endoglucanase on Avicel at wide pH range was studied at different temperatures. Langmuir type adsorption isotherm at 10˚C showed maximum adsorption strength of enzyme at pH 3.0, which was in a range of optimum pH of the enzyme.

Modelos de isotermas de sorcion para alimentos: usos y limitaciones / Models of sorption isotherms for food: uses and limitations

Las isotermas de sorción describen la relación entre el contenido de humedad y la actividad de agua de un alimento. Este trabajo presenta los conceptos básicos relacionados con la termodinámica de la sorción de agua, clasificación de las isotermas, “usos y limitaciones de los modelos”, y la medición de las isotermas de sorción de materiales alimenticios. Los modelos más utilizados en los alimentos son los de Brunauer- Emmett-Teller y Guggenheim-Anderson-de Boer. El éxito del modelo de Brunauer-Emmett-Teller es más bien cualitativo, considerando que en la mayoría de casos sólo es lineal en un rango limitado de actividad de agua de 0,05 a 0,45, por lo que su aplicabilidad principal es la estimación de áreas de superficies y el modelo de Guggenheim-Anderson-de Boer su uso es generalizado por su bases teóricas, simplicidad matemática y fácil interpretación, pero se desvía a actividad de agua superior a 0,93.

Sorption isotherms for food products: study of models agreement

The knowledge of sorption isotherms is important for establishing conditions of storage and of processes like drying. There are several models for fitting sorption isotherms. This work presents a study about the agreement of 40 mathematical models of sorption isotherms to experimental data of 53 food products. The quadratic residual sum and the standard error were the criteria of evaluation. For the major part of the products, the best agreement was obtained with equation of Jaafar and Michalowski, if temperature or saturation pressure were not considered as a variable. For cases where temperature or saturation pressure were considered, the equation of Strohman and Yoerger was the one with the best agreement for most of the products. Ross equation, based on thermodynamics aspects, was also tested for some products, but the agreement was just satisfactory.

Effect of silicification on the water sorption properties of microcrystalline cellulose II

The aim of this study was to investigate the water sorption behavior of cellulose II:SiO2 composites and to determine the influence of silicification on this property. These composites were prepared by spray-drying at a cellulose II:SiO2 ratio of 98:2, 95:5, 90:10 and 80:20. The nonlinear models of Guggenheim-Anderson-de Boer (GAB), Generalized D'Arcy and Watt (GDW) and Hailwood & Horrobin (HH), were used for the characterization and analysis of the isotherms. The infrared and powder X-rays characterization showed no signs of chemical modification or change in the polymorphic form of cellulose II by SiO2. The parameters derived from these models indicated that only a 20 percent level of silicification was able to hinder the water sorption properties of cellulose. Silicon dioxide was the most hydrophobic material since it had a lower ability to form hydrogen bonds with water than cellulose II. This finding was reflected in a delayed compact disintegration time when high levels of silicification (20 percent) and compression pressures higher than 120 MPa were used.

O objetivo deste estudo é investigar o comportamento de sorção de água a partir de misturas de celulose II e SiO2 e determinar a influência da silicificação nesse processo. Estas misturas foram preparadas por nebulização (spray-drying) usando misturas de celulose II e SiO2 nas proporções de 98:2, 95:5, 90:10 e 80:20. Os modelos não-lineares de Guggenheim-Anderson-de Boer (GAB), "Generalized" D'Arcy e Watt (GDW) e Hailwood & Horrobin (HH) foram utilizados para caracterização e análise das isotermas. As misturas foram caracterizadas por infravermelho e raio-X e os resultados não mostraram indicativo de modificação química ou polimórfica da celulose II em combinação com SiO2. Os parâmetros derivados desses modelos indicaram que as propriedades de sorção de água da celulose foram prejudicadas apenas quando empregado um nível de silicificação de 20 por cento. O dióxido de silício foi o material mais hidrofóbico, provavelmente por possuir uma menor capacidade de formar pontes de hidrogênio com a água quando comparado com a celulose II. Este resultado foi refletido em redução no tempo de desintegração, especialmente quando altos níveis de silicificação (20 por cento) e força de compressão (acima de 120 Mpa) foram utilizados.

Biosorption kinetics of a direct azo dye Sirius Blue K-CFN by Trametes versicolor

In this study, lyophilized Trametes versicolor biomass is used as a sorbent for biosorption of a textile dye, Sirius Blue K-CFN, from an aqueous solution. The batch sorption was studied with respect to dye concentration, adsorbent dose and equilibrium time. The effect of pH and temperature on dye uptake was also investigated and kinetic parameters were determined. Optimal initial pH (3.0), equilibrium time (2 hrs), initial dye concentration ( 100 mg l-1) and biomass concentration (1.2 mg l-1) were determined at 26ºC. The maximum biosorption capacity (q max) of Sirius Blue K-CFN dye on lyophilized T. versicolor biomass is 62.62 mg/g. The kinetic and isotherm studies indicated that the biosorption process obeys to a pseudo-second order model and Langmuir isotherm model. In addition, the biosorption capacities of fungal biomass compared to other well known adsorbents such as activated carbon and Amberlite, fungal biomass biosorptions capacities were found to be more efficient.

Effects of biosorption parameter: kinetics, isotherm and thermodynamics for Ni(II) biosorption from aqueous solution by Circinella sp

Circinella sp. was employed as a biosorbent for removal of Ni(II) from aqueous solution. The biosorption kinetics and isotherms were investigated. The effect of several parameters, such as biosorbent dosage, contact time, initial concentration, pH and temperature, on biosorption process was evaluated. The kinetic studies indicated that the biosorption followed pseudo-second order kinetic model. Biosorption behaviour of Ni(II) on Circinella sp. was expressed by both Langmuir and Freundlich isotherms. The equilibrium data fit better to the Langmuir model compared to the Freundlich model in concentration range studied (1.0-3.0 mM). The thermodynamic parameters (AG°, AH° and AS°) were also determined, and it was found that the Ni(II) biosorption by Circinella sp. was spontaneous and endothermic in nature.

Evaluación de la interacción vermicompost-Pb²+ a través de isotermas de adsorción y espectroscopia FTIR / Evaluation of interaction of vermicompost-Pb²+ through adsorption isothermals and FTIR spectroscopy

La adsorción de plomo por un vermicompost comercial fue estudiada a 284, 306 y 323 K aplicando los modelos de Langmuir y Freundlich, los cuales describen adecuadamente el proceso de adsorción. Las capacidades de adsorción máximas de 116,3; 113,6 y 123,5 mg.g-¹. De acuerdo a las funciones termodinámicas, la retención de plomo involucra una reacción endotérmica (ΔHadsorción = 4,25 ± 0,92 kCal.mol-¹) con un aumento de la entropía del sistema (ΔS = 7,55 a 8,62 kCal.K-1mol-¹) asociado a la ionización de los grupos carboxílicos. La baja espontaneidad de la reacción fue determinada por los valores positivos de la Energía Libre de Gibbs (ΔG = 2,11 a 1,49 kCal.mol-¹). Las diferencias observadas en los espectros FTIR del compost en la región de 1800 a 1300 cm-¹ a diferentes condiciones de pH fueron interpretadas como el resultado de la ionización de los grupos carboxílicos, reduciendo la intensidad de las bandas alrededor de 1725 cm-¹, generándose las señales a 1550 cm-¹ y 1390 cm-¹ de los grupos carboxilato. Los mismos cambios fueron observados a pH 3,8 en presencia del ión Pb²+, lo que sugiere que el acomplejamiento con el metal pesado se produce por medio de una reacción de intercambio catiónico.

The adsorption of Pb2+ by a comercial vermicompost was studied at 284, 306 and 323 K using Langmuir and Freunldich isotherms. The maximum adsorption capacities were 116.3; 113.6 and 123.5 mg.g-¹. Thermodinamic functions showed that the retention takes place by an endothermic reaction (ΔHadsorción = 4,25 ± 0,92 KCal.mol-¹) in which entropy increases (ΔS = 7,55 to 8,62 kCal.K-1mol-¹) along with the acidity of the solutions due to the ionization of carboxylic groups. The low spontaneity was reflected by positive values of the Gibbs free energy (ΔG = 2,11 a 1,49 kCal.mol-¹). The differences in FTIR spectra of vermicompost at pH 3.8 and 7.0 in the region between 1800 to 1300 cm-¹ were interpreted on the basis of caboxylic acids ionization thet reduced the band intensity around 1725 cm-¹, producing signals at 1550 and 1390 cm-1of the carboxylate groups. Similar changes were detected at pH 3.8 when ionic lead was present which suggested that heavy metal complexation by a cationic exchange reaction.