Structure-Activity Optimization of Luminescent Tb-doped LaF3 Nanoparticles.

A series of Tb-doped LaF3 nanoparticles (NPs) was prepared by systematically varying the Tb doping rate from 0 to 100%. The elemental composition was confirmed by inductively coupled plasma atomic emission spectroscopy (ICP-AES) analysis, and the size, morphology, and crystal structure were determined in the solid state by transmission electron microscopy and X-ray diffractometry, while the size and ζ-potential of the NPs in solution were studied by dynamic light scattering, Taylor dispersion analysis, and laser Doppler electrophoresis. While the crystal structure appears to be hexagonal for a doping rate of up to 70%, an admixture of hexagonal and orthorhombic phases is observed for 80 and 90% Tb contents with a pure orthorhombic phase being obtained for TbF3. The spectroscopic properties of the NPs were studied for bare NPs and in the presence of dipicolinic acid as a surface-capping antenna ligand in solution. The coverage of the NPs by the ligand resulted in an increase in the luminescence lifetime of the emitting Tb centers, as a consequence of a better protection toward luminescence quenching from water molecules, as well as a large improvement in the brightness of the NPs. Taking into account the various parameters, a doping rate of 40% Tb was shown to be the best compromise for the development of such NPs for bioanalytical applications.

Inter-annual variation of physiological traits between urban and forest great tits.

Urbanization is characterized by rapid environmental changes such as an increase in building surface, in pollution, or a decrease in invertebrate abundance. For many bird species, morphological and physiological differences have been observed between urban and rural individuals that seem to reflect a negative impact of urban life on the health and fitness of individuals. Studies on passerine birds also showed important differences between populations and species in their responses to the urban environment. We propose to test physiological differences between urban and forest individuals over 3 years to understand whether the observed patterns are constant or subject to variations across years. For this purpose, we assessed the health parameters of adults and fledgling of great tits, Parus major, living in an urban and in a forest site in the Eurometropole of Strasbourg, for three years. Bird health was estimated with morphological parameters (body condition and size) and also with physiological parameters (oxidative status and telomere length). Our results showed lower body condition of urban fledglings regardless of the year, but no site effects on telomere length. On the contrary, for adult breeders, urban individuals had longer telomeres than forest ones except for one year which coincide with bad weather conditions during reproduction where no difference was detected. Urban birds also had higher antioxidant capacity whatever the years. These results suggest that cities act as a filter in which only good quality individuals survive and achieve successful reproduction regardless of year, whereas in the forest the selection occurs only during harsh weather years.

Development of Cu(ii)-specific peptide shuttles capable of preventing Cu-amyloid beta toxicity and importing bioavailable Cu into cells.

Copper (Cu) in its ionic forms is an essential element for mammals and its homeostasis is tightly controlled. Accordingly, Cu-dyshomeostasis can be lethal as is the case in the well-established genetic Wilson's and Menkes diseases. In Alzheimer's disease (AD), Cu-accumulation occurs in amyloid plaques, where it is bound to the amyloid-beta peptide (Aß). In vitro, Cu-Aß is competent to catalyze the production of reactive oxygen species (ROS) in the presence of ascorbate under aerobic conditions, and hence Cu-Aß is believed to contribute to the oxidative stress in AD. Several molecules that can recover extracellular Cu from Aß and transport it back into cells with beneficial effects in cell culture and transgenic AD models were identified. However, all the Cu-shuttles currently available are not satisfactory due to various potential limitations including ion selectivity and toxicity. Hence, we designed a novel peptide-based Cu shuttle with the following properties: (i) it contains a Cu(ii)-binding motif that is very selective to Cu(ii) over all other essential metal ions; (ii) it is tagged with a fluorophore sensitive to Cu(ii)-binding and release; (iii) it is made of a peptide platform, which is very versatile to add new functions. The work presented here reports on the characterization of AKH-αR5W4NBD, which is able to transport Cu ions selectively into PC12 cells and the imported Cu appeared bioavailable, likely via reductive release induced by glutathione. Moreover, AKH-αR5W4NBD was able to withdraw Cu from the Aß1-16 peptide and consequently inhibited the Cu-Aß based reactive oxygen species production and related cell toxicity. Hence, AKH-αR5W4NBD could be a valuable new tool for Cu-transport into cells and suitable for mechanistic studies in cell culture, with potential applications in restoring Cu-homeostasis in Cu-related diseases such as AD.

Consequences of trace metal cocktail exposure in zebra finch (Taeniopygia guttata) and effect of calcium supplementation.

Trace metal elements are significant stressors in urban areas. Their harmful effects on physiological parameters are demonstrated, but current laboratory studies are not representative of wild chronic exposure to a trace metal cocktail. Calcium can reduce the accumulation and toxicity of several metals, but soil acidification in cities leads to a decrease in bioavailability of this element. The objective of this study was to investigate the accumulation and toxicity of a trace metal cocktail representative of urban exposure on passerine birds, and test the importance of calcium availability on these toxic effects. We exposed zebra finches (Taeniopygia guttata) to a cocktail of seven metals and one metalloid in drinking water, with or without calcium supplementation. We monitored the concentration of metals in the blood and feathers, and their effects on oxidative status and telomere length. The metal cocktail led to higher concentration of all elements in the feathers, and of arsenic and lead in the blood. Birds with a higher concentration of cadmium, arsenic and lead in the feathers had shorter telomeres, but no impact of the cocktail was detected on oxidative status. Birds of the 'calcium' group and the 'calcium and metal' group accumulated higher concentrations of zinc, chromium and nickel in feathers. The 'calcium and metal' group also accumulated lower concentrations of arsenic and lead in feathers compared to the 'metal' group. Our results suggest that chronic exposure to a cocktail of metals at low concentrations has deleterious effects on birds, which can be limited through calcium intake.

Sodium arsenite effect on Vitis vinifera L. Physiology.

Sodium arsenite (NaAsO2) was especially used as a dormant spray to control grapevine trunk diseases (GTDs) in European vineyards until 2003 when it was banned. It was an efficient product but it was banned due to high risk for human health and the environment. Now, as one of the consequences with climatic changes, GTDs threaten the sustainability of vineyards since no similar and efficacious sprays are presently available to reduce the impact of GTDs. Research efforts were devoted to identify other active ingredients and biological control agents but they remained limited in term of efficacy. New solutions might follow from a better understanding of the modes of action of sodium arsenite which are currently lacking, specially its impact on grapevine physiology. For this study, grafted plants cv. Tempranillo were sprayed by sodium arsenite at the end of the winter. During the vegetative period, the impact on plant physiology was studied by measurement of the photosynthetic activity, the vine growth and development, and some defense responses. Our results showed that arsenic was translocated throughout the vine with an increasing gradient from the leaves to the root system, that photosynthesis was firstly reduced and then stimulated, and that plant tolerance responses were induced especially antioxidant system. The activation of grapevine defense responses by sodium arsenite could be a complementary action to fight fungal pathogens in addition to the fungicide effect.

The PvdRT-OpmQ efflux pump controls the metal selectivity of the iron uptake pathway mediated by the siderophore pyoverdine in Pseudomonas aeruginosa.

Pyoverdine (PVD) is the major siderophore produced by Pseudomonas aeruginosa for iron acquisition. PvdRT-OpmQ is an ATP-dependent efflux pump involved in the secretion of newly synthesized pyoverdine (PVD) and of PVD that has transported and released its iron into the bacterium from the periplasm into the extracellular medium. This iron uptake pathway also involves an outer membrane transporter, FpvA, for PVD-Fe uptake from the extracellular medium into the periplasm. In binding assays, FpvA bound PVD in complex with many different metals, with affinities from 2.9 nM for PVD-Fe to 13 µM for PVD-Al. Uptake assays with various FpvA and PvdRT-OpmQ mutants, monitored by inductively coupled plasma-atomic emission spectrometry (ICP-AES) for metal detection, and by fluorescence for PVD detection, showed that both metals and PVD accumulated in P. aeruginosa, due to the uptake of these compounds via the FpvA/PVD pathway. Higher levels of accumulation were observed in the absence of PvdRT-OpmQ expression. Thus, FpvA has a broad metal specificity for both the binding and uptake of PVD-metal complexes, and the PvdRT-OpmQ efflux pump exports unwanted metals complexed with PVD from the bacterium. This study provides the first evidence of efflux pump involvement in the export of unwanted siderophore-metal complexes and insight into the molecular mechanisms involved controlling the metal selectivity of siderophore-mediated iron uptake pathways.