Irradiation Effects on Polymer-Grafted Gold Nanoparticles for Cancer Therapy.

In the context of cancer treatment, gold nanoparticles (AuNPs) are considered as very promising radiosensitizers. Here, well-defined polymer-grafted AuNPs were synthesized and studied under gamma irradiation to better understand the involved radiosensitizing mechanisms. First, various water-soluble and well-defined thiol-functionalized homopolymers and copolymers were obtained through atom transfer radical polymerization. They were then used as ligands in the one-step synthesis of AuNPs, which resulted in stable hybrid metal-polymer nanoparticles. Second, these nano-objects were irradiated in solution by γ rays at different doses. Structures were fully characterized through size exclusion chromatography, small-angle X-ray scattering, and small-angle neutron scattering measurements, prior to and after irradiation. We were thus able to quantify and to localize radiation impacts onto the grafted polymers, revealing the production sites of reactive species around AuNPs. Both external and near-surface scissions were observed. Interestingly, the ratio between these two effects was found to vary according to the nature of polymer ligands. Medium-range and long-distance dose enhancements could not be identified from the calculated scission yields, but several mechanisms were considered to explain high yields found for near-surface scissions. Then cytotoxicity was shown to be equivalent for both nonirradiated and irradiated polymer-grafted NPs, which suggested that released polymer fragments were nontoxic. Finally, the potential to add bioactive molecules such as anticancer drugs has been explored by grafting doxorubicin onto the polymer corona. This may lead to nano-objects combining both radiosensitization and chemotherapy effects. This work is the first one to study in details the impact of radiation on radiosensitizing nano-objects combining physical, chemical, and biological analyses.

Sediment Quality and Potential Toxicity Assessment in Two Open/Semiclosed Mediterranean Sea Areas: A Case Study of Sfax Coast (Tunisia).

The Gulf of Gabès (southeastern Tunisia), characterized by the abundance of halieutic resources, is nowadays facing strong anthropogenic pressures. This paper aims to assess and compare metallic pollution in two open/semiclosed areas bordering the coastline of Sfax (a part of the Gulf). The first area covers the outlet zone of many anthropogenic effluents of urban Sfax, whereas the second area, located at a distance of 15 km from the first one, was selected as being representative of numerous semiclosed areas bordering the Gulf that have served for harvesting clams. Spatial distribution of selected heavy metals (Cd, Pb, Zn, Cu, and Fe) coupled with chemometric approaches (enrichment factor, contamination degree, mean-ERM-quotients, and cluster analysis) were used as tools for the assessment of metallic pollution. The obtained results showed that metallic pollution is higher in the semiclosed area despite the absence of neighboring anthropogenic sources, probably because of the relative importance of both autochthonous organic matter and biota. The computed potential ecotoxicity demonstrated moderately high values in this area, testifying to a menaced biota that is prone to more affecting hazards if significant active measures are not taken.

Assessment of sediment quality in the Mediterranean Sea-Boughrara lagoon exchange areas (southeastern Tunisia): GIS approach-based chemometric methods.

Concentrations of selected heavy metals (Cd, Pb, Zn, Cu, Mn, and Fe) in surface sediments from 66 sites in both northern and eastern Mediterranean Sea-Boughrara lagoon exchange areas (southeastern Tunisia) were studied in order to understand current metal contamination due to the urbanization and economic development of nearby several coastal regions of the Gulf of Gabès. Multiple approaches were applied for the sediment quality assessment. These approaches were based on GIS coupled with chemometric methods (enrichment factors, geoaccumulation index, principal component analysis, and cluster analysis). Enrichment factors and principal component analysis revealed two distinct groups of metals. The first group corresponded to Fe and Mn derived from natural sources, and the second group contained Cd, Pb, Zn, and Cu originated from man-made sources. For these latter metals, cluster analysis showed two distinct distributions in the selected areas. They were attributed to temporal and spatial variations of contaminant sources input. The geoaccumulation index (I (geo)) values explained that only Cd, Pb, and Cu can be considered as moderate to extreme pollutants in the studied sediments.

Heavy metal concentrations in the surface marine sediments of Sfax Coast, Tunisia.

Sixty-seven surface marine sediment samples in the <63 µm fraction collected from the coast of Sfax (Tunisia) were analyzed by inductively coupled plasma-atomic emission spectrometry for seven heavy metals (Pb, Ni, Cu, Cr, Zn, Cd, and Fe). Metal concentrations were compared with natural values, marine sediment quality standards, and also with other results concerning sediments from several Mediterranean coasts. The study of their spatial distributions refined by complementary approaches including principal component analysis, enrichment factors, and geoaccumulation index showed a significant impact of multiple anthropogenic sources. These included industrial sources and municipal discharges of the urban Sfax and also non-controlled discharges in rural zones close to the coastline. Moderate pollution of sediments, especially by Pb, Zn, and Ni, was shown to exist in localized sites. Besides, it was shown that other sites, slightly to highly enriched in terms of Cu, Cr, and Cd, are characterized by a quality of sediments varying from unpolluted to moderately polluted.