Maria J. Sampaio

Nanodiamond–TiO2 composites for photocatalytic degradation of microcystin-LA in aqueous solutions under simulated solar light

Titanium dioxide (TiO2) has been under intensive investigation for photocatalytic degradation of cyanobacterial toxins. In order to develop more efficient photocatalysts, TiO2 and oxidized nanodiamonds (NDox) were combined as a composite catalyst (NDox–TiO2), which was tested in the photocatalytic oxidation of microcystin-LA (MC-LA), a cyanotoxin frequently found in freshwater. NDox–TiO2 and neat TiO2 photocatalysts were prepared by a liquid phase deposition method. A wide variety of analytical techniques, including physical adsorption of nitrogen, X-ray diffraction (XRD), UV-Vis and IR diffuse reflectance spectroscopies (DRUV-Vis and DRIFT), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), were used to characterize the materials. The performance of the photocatalysts was studied under both simulated solar and visible light. The kinetic results show remarkable efficiency for the NDox–TiO2 composite under simulated solar light irradiation with a synergistic factor of more than 15 relative to neat TiO2, while negligible photocatalytic activity was observed for the degradation of MC-LA when NDox–TiO2 was used under visible light illumination due to the wide band gap of the composite material. The photocatalytic efficiency of NDox–TiO2 was ascribed to the good dispersion of both phases in the composite material, facilitating the possible electronic interaction at the heterojunction interface between NDox and TiO2.

Box–Behnken factorial design to obtain a phenolic-rich extract from the aerial parts of Chelidonium majus L.

A Box-Behnken design (BBD) was developed to study the influence of four parameters (X1: % methanol; X2: extraction time; X3: extraction temperature; X4: solid/solvent ratio) on two responses, namely extraction yield and phenolics content of the aerial parts of Chelidonium majus L. The model presented a good fit to the experimental results for the extraction yield, being significantly influenced by X1 and X4. On the other hand a parameter reduction was necessary to run the model for phenolics content, showing that only X1 and X2 had great influence on the response. Two best extraction conditions were defined: X1=76.8% MeOH, X2=150.0 min, X3=60.0°C and X4=1:100 and X1=69.2%, X2=150 min, X3=42.5°C and X4=1:100. Moreover, the HPLC-DAD-ESI/MS(n) analysis conducted with the center point sample revealed the presence of 15 alkaloids and 15 phenolic compounds, from which the 9 flavonoids and 3 hydroxycinnamic acids are described for the first time. Only phenolic compounds were quantified by a validated HPLC-DAD method, the pair quercetin-3-O-rutinoside+quercetin-3-O-glucoside dominating all the 29 extracts. This study is of great importance for future works that seek to apply the phenolic profile to the quality control of C. majus samples.