Reduction of Fusarium proliferatum growth and fumonisin accumulation by ZnO nanoparticles both on a maize based medium and irradiated maize grains.

This study evaluated the antifungal effect of ZnO nanoparticles (ZnO-NPs) on Fusarium proliferatum growth and fumonisin accumulation both on a maize-based medium (in vitro) and on irradiated maize grains (in situ). The ZnO-NPs were obtained by drop-by-drop synthesis without further thermal treatment and characterized by scanning electronic microscopy/ energy dispersive X-ray spectroscopy (SEM/EDS) and X-ray diffraction (XRD). SEM analysis showed them as thin flakes of 200 × 200 nm, ~30 nm thickness and its purity were confirmed by XRD. During the in vitro assay ZnO-NPs (0, 0.8; 4, 8 g L-1) were evaluated at 25 °C during 21 days under darkness or photoperiod incubation (12/12 h light (cold white and black fluorescent lamps)/darkness) to determine its possible photocatalytic influence. Fumonisins were detected by high performance liquid chromatography coupled to mass spectrometry (HPLC- MS/MS). All ZnO-NPs concentrations significantly affected growth rates and FB1 accumulation by F. proliferatum RCFP 5033 (p < 0.05). Similar reduction of growth and FB1 (%) was observed at 0.8 and 8 g L-1 ZnO-NPs under photoperiod or darkness incubation. FB1 reduction was observed after 14 and 21 days, although the highest reduction occurred after 14 days under photoperiod incubation (84-98%). No clear light enhancing effect on the antifungal and anti-mycotoxin capability of the ZnO-NPs was observed. Morphological alterations in mycelia and conidia were observed by SEM. Under the in situ assay, the effect of the ZnO-NPs (0, 0.4, 0.8, 2 g kg-1) on growth rates and fumonisin B1, B2 and B3 accumulation by two F. proliferatum strains was evaluated on irradiated maize grains adjusted to 0.995, 0.98 and 0.97 aW in darkness at 25 °C during 21 days. Also, zinc acetate at 0.8 g kg-1 was included to compare their antifungal effect against the same ZnO-NPs concentration. Growth rates decreased significantly as ZnO-NPs concentrations increased. Higher than 60% of growth reduction was observed for both F. proliferatum strains. Zinc acetate significantly reduced growth, although it was less efficient that the same ZnO-NPs concentration. ZnO-NPs reduced total fumonisins accumulation by 71-99% at 0.8-2 g kg-1 ZnO-NPs and 0.98-0.995 aW. Moreover, 0.4 g kg-1 ZnO-NPs also produced significant reduction of the 3 fumonisins. This study showed the application of ZnO-NPs in maize grains could be a low cost and environmental impact strategy to control phytopathogen and toxigenic fungi such as F. proliferatum and to reduce fumonisins accumulation, both during crop development at preharvest stage and during maize storage.

Spectroscopic evidence for intermediate species formed during aniline polymerization and polyaniline degradation.

Spectroscopic methods are used to investigate the formation of low molecular mass intermediates during aniline (ANI) oxidation and polyaniline (PANI) degradation. Studying ANI anodic oxidation by in situ Fourier transform infrared spectroscopy (FTIRS) it is possible to obtain, for the first time, spectroscopic evidence for ANI dimers produced by head-to-tail (4-aminodiphenylamine, 4ADA) and tail-to-tail (benzidine, BZ) coupling of ANI cation radicals. The 4ADA dimer is adsorbed on the electrode surface during polymerization, as proved by cyclic voltammetry of thin PANI films and its infrared spectrum. This method also allows, with the help of computational simulations, to assign characteristic vibration frequencies for the different oxidation states of PANI. The presence of 4ADA retained inside thin polymer layers is established too. On the other hand, FTIRS demonstrates that the electrochemically promoted degradation of PANI renders p-benzoquinone as its main product. This compound, retained inside the film, is apparent in the cyclic voltammogram in the same potential region previously observed for 4ADA dimer. Therefore, applying in situ FTIRS is possible to distinguish between different chemical species (4ADA or p-benzoquinone) which give rise to voltammetric peaks in the same potential region. Indophenol and CO(2) are also detected by FTIRS during ANI oxidation and polymer degradation. The formation of CO(2) during degradation is confirmed by differential electrochemical mass spectroscopy. To the best of our knowledge, this is the first evidence of the oxidation of a conducting polymer to CO(2) by electrochemical means. The relevance of the production of different intermediate species towards PANI fabrication and applications is discussed.

Probe beam deflection studies of nanostructured catalyst materials for fuel cells.

Probe beam deflection (PBD) techniques, both as cyclic voltadeflectometry (CVD) and chronodeflectometry (CD), were applied for the first time to the study of the electrochemistry of nanostructured Pt materials which are commonly used as electrocatalysts in fuel cells. The electrochemical surface reactions, including faradaic processes, double layer charging and specific anion adsorption were easily detected. Quantitative analysis of the chronodeflectometric data made possible to elucidate the dynamics of double layer charging in such materials and to determine the potential of zero charge (pzc) of the metal present either as a monolithic mesoporous material or as metal nanoparticles supported on carbon. The electro-oxidation of CO, adsorbed on nanostructured Pt, was also studied by CVD and CD being able to detect the formation of CO2 and H3O+ related with the nucleation and growth process which controls the rate of CO stripping. The interplay of Pt oxide formation and COad electrooxidation, both in potential and time, was detected indicating possible application of the technique to other electrocatalysts.