Zelica Minniti

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.

Absorption of nitro-polycyclic aromatic hydrocarbons by biomembrane models: effect of the medium lipophilicity.

To demonstrate the relationship between the structure of nitro-polycyclic aromatic hydrocarbons and their effect on biomembranes, we have investigated the influence of three structurally different nitro-polycyclic aromatic hydrocarbons, 2-nitrofluorene, 2,7-dinitrofluorene and 3-nitrofluoranthene, on the thermotropic behavior of dimyristoylphosphatidylcholine multilamellar vesicles, used as biomembrane models, by means of differential scanning calorimetry. The obtained results indicate that the studied nitro-polycyclic aromatic hydrocarbons affected the thermotropic behavior of multilamellar vesicles to various extents, modifying the pretransition and the main phase transition peaks and shifting them to lower temperatures. The effect of the aqueous and lipophilic medium on the absorption process of these compounds by the biomembrane models has been also investigated revealing that the process is hindered by the aqueous medium but strongly allowed by the lipophilic medium.

The PAH and Nitro-PAH Concentration Profiles in Size-Segregated Urban Particulate Matter and Soil in Traffic-Related Sites in Catania, Italy

Polycyclic aromatic hydrocarbons (PAHs) and nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) were identified from both air particulate matter and soils. For air sampling, a six-stage cascade impactor was situated in an urban area (Catania, Italy) that is recognized for its high traffic volume. The soil samples were collected every 1.5 km from under the grass by the side of the median of a Catania road along its full length (8.2 km). HPLC in electrochemical-fluorescence detection mode was used for selective separation, identification and quantification of analytes in air and soil samples, providing both good selectivity and sensitivity. The seasonal trends, effects of urban traffic, and source profiles are discussed herein. Higher PM10 concentrations were observed for summer (43 μg m−3) in comparison to winter (24 μg m−3). Conversely, the PAHs contained in PM10 were higher in winter (0.48 ng m−3 for fluoranthene) than in summer (0.14 ng m−3 for fluoranthene). Analysis of the size-segregated urban particulate matter showed that the amount of PM0.5 (stage 6) was always higher than the amount of other particles (stages 1–5). Furthermore, the PM0.5 was always higher in summer (about 40%, m/m) than in winter (about 30%, m/m). Finally, the amounts of PAH and nitro-PAH in PM0.5 (stage 6) were always higher, by a maximum of one order of magnitude, than that of other particles (stages 1–5). This result is crucial because ultrafine particles have a tendency to move into the blood through the alveolar epithelial barrier. Moreover, the air and soil pollution levels agree with those found in other cities with similar levels of pollution. Supplemental materials are available for this article. Go to the publishers online edition of Polycyclic Aromatic Compounds to view the supplemental file.

Calorimetric evidence of interaction of brominated flame retardants with membrane model

The presence of polybrominated flame retardants in the environment seems to be increasing in the past decade. Considering the toxic effects of these pollutants, it is important evaluating the potential interaction with biological membranes for a risk assessment. In this study low and high brominated biphenyls and biphenyl ethers were used to investigate their interaction with biological membrane models constituted by liposomes, using differential scanning calorimetry (DSC) technique. The medium influence on membrane absorption was also assessed. The findings indicate that membrane interaction is controlled by compound structural characteristics. The membrane absorption is allowed by lipophilic medium; instead hydrophilic medium prevents membrane permeation.

Time-Dependent Absorption Evidence of Phenylurea-Derived Herbicides on Model Biomembranes: A DSC Study

Environmental Context. The need to improve the quality of agricultural cultivation and to control the weed growth of non-cultivated area has brought herbicides to wide-scale use. Unfortunately, these compounds have been proved to be toxic for many organisms, humans included. With an aim to a better knowledge of the mobility and fate of environmental pollutants, it becomes very important to have an exact knowledge of the role that the medium in which these products are dissolved or dispersed plays on the absorption of these products by biological membranes as a complement to information on the interaction between these compounds and cells. Abstract. Phenylurea derivatives are used as herbicides that inhibit photosynthesis. These materials enter plants via their roots and are employed for selective control of germinating grass and broad-leaved weeds in many crops as well as for total weed control of non-cultivated areas such as roads, railways, and parks. The study of the interaction between the herbicide and lipid membrane is interesting in assessing the relevance of the dispersing medium in the absorption processes. Differential scanning calorimetry (DSC), which detects the effect of foreign molecules on the phase transition from an ordered to a disordered lipid structure when submitted to heating, was employed to study such an interaction. Effects exerted by four phenylurea herbicides (difenoxuron, diuron, metoxuron, and linuron) on the thermotropic behavior of model membranes were here investigated. Aqueous dispersions of dimyristoylphosphatidylcholine (DMPC) were used as model membranes to study herbicide–membrane interactions. Experiments carried out by leaving herbicides, in a powdered form, in contact with DMPC-based multilamellar or unilamellar vesicles show that all the examined herbicides are able, but in different ways, to migrate through the aqueous medium and interact with model membranes. Experiments on herbicide-loaded liposomes in contact with empty ones indicate that the compounds are able to migrate from a loaded membrane to an empty one. The obtained data seem to validate the use of the DSC in demonstrating that bioactive and potentially toxic compounds not only to interact with biological membranes but also adsorb into a cell when dispersed in a lipophilic medium.