Raisins and Currants as Conventional Nutraceuticals in Italian Market: Natural Occurrence of Ochratoxin A

The healthy consumers make a strong pressure to natural products that can prevent the chronic diseases and improve the general health status, and therefore an important aspect that have to be considered is the safe level of the nutraceuticals. This study reports the occurrence of Ochratoxin A (OTA) and associated fungal contamination in 35 samples of dried vine fruits imported in the European community potentially used for the development of new nutraceutical supplements. High pressure liquid chromatography analysis identified 18 samples as contaminated by OTA with an average level of 2.6 μg/kg. OTA was measured in 4 samples of currants (mean value of 6.6 μg/kg) and 13 samples of raisins (mean value of 1.4 μg/kg). In one sample of currants and one of raisins from Turkey OTA exceeded the limits set by European Commission of 10 μg/kg, being contaminated with 12.61 and 15.99 μg/kg, respectively. All the positive samples were confirmed by Orbitrap Q Exactive through their molecular weight and the corresponding fragmentation. The worldwide consumption of dried vine fruits contributed to OTA exposure in several group of consumers. In particular, considering the potential nutraceutical approach, this consumption may be represent a severe risk for healthy consumers that consider these products like healthy and salutistic for their contents in antioxidants, flavonoids, and polyphenols. Data reported in this study confirmed the need to regularly monitor mycotoxin levels in these food products and optimize the process of fruits drying in order to reduce the development of toxigenic molds.     

Unveiling the controversial mechanism of reversible Na storage in TiO2 nanotube arrays: Amorphous versus anatase TiO2

Due to their inherent safety,low cost,and structural stability,TiO2 nanostructures represent a suitable choice as anode materials in sodium-ion batteries.In the recent years,various hypotheses have been proposed regarding the actual mechanism of the reversible insertion of sodium ions in the TiO2 structure,and previous reports are often controversial in this respect.Interestingly,when tested as binder-and conducting additive-free electrodes in laboratory-scale sodium cells,amorphous and crystalline (anatase) TiO2 nanotubular arrays obtained by simple anodic oxidation exhibit peculiar and intrinsically different electrochemical responses.In particular,after the initial electrochemical activation,anatase TiO2 shows excellent rate capability and very stable long-term cycling performance with larger specific capacities,and thus a clearly superior response compared with the amorphous counterpart.To obtain deeper insight,the present materials are thoroughly characterized by scanning electron microscopy and ex situ X-ray diffraction,and the insertion of sodium ions in the TiO2 bulk phases is systematically modeled by density functional theory calculations.The present results may contribute to the development of more systematic screening approaches to identify suitable active materials for highly efficient sodium-based energy storage systems.     

Galloflavin (CAS 568-80-9): a novel inhibitor of lactate dehydrogenase

One of the most prominent alterations in cancer cells is their strict dependence on the glycolytic pathway for ATP generation. This observation led to the evaluation of glycolysis inhibitors as potential anticancer agents. The inhibition of lactate dehydrogenase (LDH) is a promising way to inhibit tumor cell glucose metabolism without affecting the energetic balance of normal tissues. However, the success of this approach depends chiefly on the availability of inhibitors that display good selectivity. We identified a compound (galloflavin, CAS 568‐80‐9) which, in contrast to other inhibitors of human LDH, hinders both the A and B isoforms of the enzyme. To determine the mechanism of action, we collected LDH‐A and ‐B inhibition data in competition reactions with pyruvate or NADH and evaluated the results using software for enzyme kinetics analysis. We found that galloflavin inhibits both human LDH isoforms by preferentially binding the free enzyme, without competing with the substrate or cofactor. The calculated K_i values for pyruvate were 5.46 μM (LDH‐A) and 15.06 μM (LDH‐B). In cultured tumor cells, galloflavin blocked aerobic glycolysis at micromolar concentrations, did not interfere with cell respiration, and induced cell death by triggering apoptosis. To our knowledge, the inhibition of LDH is, to date, the only biochemical effect described for galloflavin. Because galloflavin is not commercially available, we also describe herein a procedure for its synthesis and report its first full chemical characterization.     

Indoor air quality in schools of a highly polluted south Mediterranean area

This study aimed at surveying lower secondary schools in southern Italy, in a highly polluted area. A community close to an industrial area and three villages in rural areas was investigated. Indoor temperature, relative humidity (RH), gaseous pollutants (CO₂ and NO₂), selected biological pollutants in indoor dust, and the indoor/outdoor mass concentration and elemental composition of PM_2.5 were ascertained. Temperature and RH were within, or close to, the comfort range, while CO₂ frequently exceeded the threshold of 1000 ppm, indicating inadequate air exchange rate. In all the classrooms, median NO₂ levels were above the WHO threshold value. Dermatophagoides p. allergen concentration was below the sensitizing threshold, while high endotoxin levels were detected in the classrooms, suggesting schools may produce significant risks of endotoxin exposure. Concentration and solubility of PM_2.5 elements were used to identify the sources of indoor particles. Indoor concentration of most elements was higher than outdoors. Resuspension was responsible for the indoor increase in soil components. For elements from industrial emission (Cd, Co, Ni, Pb, Sb, Tl, V), the indoor concentration depended on penetration from the outside. For these elements, differences in rural vs industrial concentrations were found, suggesting industrial sources may influence indoor air quality nearby schools.     

Degradation of sulphur containing s-triazines during water chlorination

The reactions of four sulphur containing s-triazines (prometryne, terbutryne, ametryne and desmetryne) with hypochlorous acid (HClO) and chlorine dioxide (ClO₂) have been investigated using an 11 ppm/3 ppm oxidant/herbicide ratio. The main objective of the study was the identification of by-products. Additionally, to study the effect of oxidant concentration on the reaction rate, two more oxidant/herbicide ratios (3 ppm/3 ppb and 11 ppb/3 ppb) have been investigated only for prometryne. Oxidation reactions were monitored by high performance liquid chromatography (HPLC), while, the identification of by-products was initially carried out by low resolution HPLC-mass spectrometry (HPLC-MS) and confirmed by accurate mass measurement. Under the experimental conditions (T = 20°C, pH = 8, reaction TIME = 48 h), the results indicate that all the investigated triazines react in the same way with each oxidant. The reactions with HClO occur much faster than those with ClO₂ and give rise to three identified oxidation by-products: the sulfoxide, the sulfone and the sulfone's hydrolysis product. The reactions with ClO₂, instead, give rise to a sole oxidation by-product: the sulfoxide. With both oxidants, as expected, the lower the oxidant concentration the slower the oxidation rate.

Based on the obtained results, a general pathway for the oxidation of sulphur containing s-triazines is proposed.     

Photodegradation of Anthracene and Benzo[a]anthracene in Polar and Apolar Media: New Pathways of Photodegradation

The photochemical reactions of anthracene and benzo[a]anthracene polycyclic aromatic hydrocarbons (PAHs) in polar and apolar solvents (cyclohexane and water/acetonitrile) were studied using spectroscopic and chromatographic techniques. These homogenous photolysis experiments are used as simplified models to compare PAHs photochemistry in water and oil (or oil films). Moreover, these processes were to some extent used as model in literature in order to study those occurring on particulate matter and aerosol surfaces. In both media, new photochemical reaction products were found. Generally, the reaction rate in the polar medium is faster than that in the apolar medium, and the photodegradation quantum yields increase with increasing polarity of the medium. HPLC-absorption/emission analysis confirmed the literature reports that mainly oxygenated photoproducts, such as PAH-hydroxides, were formed. The novelty of this article is that GC-MS data revealed the presence of new photoproducts that have not yet been described. This simplified model system allowed us to characterize the product distribution, thus simplifying the interpretation of the photodegradation mechanism. The identification of new photofragmentation paths, originating by irradiation of primary PAH photoproducts, may suggest an innovative way of remediation triggered by light.