The importance of inversion disorder in the visible light induced persistent luminescence in Cr3+^{3+} doped AB2_2O4_4 (A = Zn or Mg and B = Ga or Al)

Cr$^{3+}$ doped spinel compounds AB$_2$O$_4$ with A=Zn, Mg and B=Ga, Al exhibit a long near infrared persistent luminescence when excited with UV or X-rays. In addition, persistent luminescence of ZnGa$_2$O$_4$ and to a lesser extent MgGa$_2$O$_4$, can also be induced by visible light excitation via $^4$A$_2$ $\rightarrow$ $^4$T$_2$ transition of Cr$^{3+}$, which makes these compounds suitable as biomarkers for in vivo optical imaging of small animals. We correlate this peculiar optical property with the presence of antisite defects, which are present in ZnGa$_2$O$_4$ and MgGa$_2$O$_4$. By using X-ray absorption fine structure (XAFS) spectroscopy, associated with electron paramagnetic resonance (EPR) and optical emission spectroscopy, it is shown that an increase in antisite defects concentration results in a decrease in the Cr-O bond length and the octahedral crystal field energy. A part of the defects are in the close environment of Cr$^{3+}$ ions, as shown by the increasing strain broadening of EPR and XAFS peaks observed upon increasing antisite disorder. It appears that ZnAl$_2$O$_4$, which exhibits the largest crystal field splitting of Cr$^{3+}$ and the smallest antisite disorder, does not show considerable persistent luminescence upon visible light excitation as compared to ZnGa$_2$O$_4$ and MgGa$_2$O$_4$. These results highlight the importance of Cr$^{3+}$ ions with neighboring antisite defects in the mechanism of persistent luminescence exhibited by Cr$^{3+}$ doped AB$_2$O$_4$ spinel compounds.Comment: 10 pages + supplementary (available on request

Electron Paramagnetic Resonance Study of a Photosynthetic Microbial Mat and Comparison with Archean Cherts

International audienceOrganic radicals in artificially carbonized biomass dominated by oxygenic and non-oxygenic photosynthetic bacteria, Microcoleus chthonoplastes-like and Chloroflexus-like bacteria respectively, were studied by Electron Paramagnetic Resonance (EPR) spectroscopy. The two bacteria species were sampled in mats from a hypersaline lake. They underwent accelerated ageing by cumulative thermal treatments to induce progressive carbonization of the biological material, mimicking the natural maturation of carbonaceous material of Archean age. For thermal treatments at temperatures higher than 620 °C, a drastic increase in the EPR linewidth is observed in the carbonaceous matter from oxygenic photosynthetic bacteria and not anoxygenic photosynthetic bacteria. This selective EPR linewidth broadening reflects the presence of a catalytic element inducing formation of radical aggregates, without affecting the molecular structure or the microstructure of the organic matter, as shown by Raman spectroscopy and Transmission Electron Microscopy. For comparison, we carried out an EPR study of organic radicals in silicified carbonaceous rocks (cherts) from various localities, of different ages (0.42 to 3.5 Gyr) and having undergone various degrees of metamorphism, i.e. various degrees of natural carbonization. EPR linewidth dispersion for the most primitive samples was quite significant, pointing to a selective dipolar broadening similar to that observed for carbonized bacteria. This surprising result merits further evaluation in the light of its potential use as a marker of past bacterial metabolisms, in particular oxygenic photosynthesis, in Archean cherts

Modifications structurales et défauts ponctuels paramagnétiques induits par irradiation électronique externe de la hollandite Ba1.16Al2.32Ti5.68O16

Des matrices BaxCsy (M,Ti)8O16 (x+y<2, M cation trivalent) de type hollandite, sont envisagées pour confiner spécifiquement le césium radioactif. Afin de simuler l'effet des rayonnements b, les modifications structurales et les défauts ponctuels paramagnétiques produits par irradiation électronique externe à température proche de l'ambiante d'une hollandite de composition simplifiée sans césium Ba1,16Al2,32Ti5,68O16 ont été étudiés par RPE et RMN. Des modifications ont été observées au niveau de l'environnement des cations Al3+ et Ti4+, résultant de la formation de lacunes d'oxygène et d'une augmentation du désordre dans les tunnels associée à des déplacements d'ions baryum. Des centres à électrons (Ti3+) et à trous électroniques (O2-) ont été observés. Ceux-ci sont relativement stables à température ambiante mais des recuits (traitements isochrones entre 50 et 800°C, traitements isothermes à 300°C) engendrent la formation d'autres défauts issus des défauts précédents correspondant à des ions Ti3+ de surface de type titanyl et des agrégats d'oxygène

Proto-Planetary Disk Chemistry Recorded by D-Rich Organic Radicals in Carbonaceous Chondrites

Insoluble organic matter (IOM) in primitive carbonaceous meteorites has preserved its chemical composition and isotopic heterogeneity since the solar system formed ~4.567 billion years ago. We have identified the carrier moieties of isotopically anomalous hydrogen in IOM isolated from the Orgueil carbonaceous chondrite. Data from high spatial resolution, quantitative isotopic NanoSIMS mapping of Orgueil IOM combined with data from electron paramagnetic resonance spectroscopy reveals that organic radicals hold all the deuterium excess (relative to the bulk IOM) in distinct, micrometer-sized, D-rich hotspots. Taken together with previous work, the results indicate that an isotopic exchange reaction took place between pre-existing organic compounds characterized by low D/H ratios and D-rich gaseous molecules, such as H_2D^+ or HD_2^+. This exchange reaction most likely took place in the diffuse outer regions of the proto-planetary disk around the young Sun, offering a model that reconciles meteoritic and cometary isotopic compositions of organic molecules

Photostimulation induced persistent luminescence in Y₃Al₂Ga₃O₁₂:Cr³⁺

Cr³⁺-activated Y₃Al₂Ga₃O₁₂ garnet (YAGG:Cr³⁺) persistent phosphor has been recently reported as a potential candidate material for in vivo imaging application. Temperature dependence of photoluminescence (PL) spectra and thermostimulated luminescence (TSL) glow curves with several conditions, especially photostimulation wavelength dependence, were carefully investigated with the perspective of deep trap utilization for long-term in vivo imaging. The PL spectrum showed typical Cr³⁺ emission due to ²E→⁴A₂ and transitions) does not suffer from temperature quenching up to 600 K. From the TSL glow curve measurements, it was found that the persistent luminescence cannot be activated by visible light excitation. However, photostimulation induced persistent luminescence by red to near-infrared light can be possible in this material

D’AGLAE à New AGLAE

Le développement de l’instrument et des méthodes d’analyse par faisceau d’ions appliquées aux problématiques patrimoniales est au cœur de l’activité de l’équipe AGLAE. Le projet New AGLAE a pour objectif de mettre à disposition des chercheurs une ligne de faisceau automatisée et en fonctionnement jour et nuit, ainsi qu’un nouveau système de détection PIXE, PIGE, RBS et IBIL capable d’effectuer de l’imagerie chimique systématique sur plusieurs centimètres carrés.The development of the instrument and the methodologies of ion beam analysis applied to Cultural Heritage issues is a major interest of the AGLAE team. The New AGLAE project aims at providing an automated beamline available night and day as well as a new PIXE, PIGE, RBS and IBIL detection system enabling systematic chemical imaging on several cm²

In vivo optical imaging with rare earth doped Ca₂Si₅N₈ persistent luminescence nanoparticles

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Halogénures de lanthane dopés cérium (des scintillateurs rapides pour l'imagerie médicale)

Ce travail concerne l étude de cristaux scintillateurs inorganiques découverts récemment : LaCl3:Ce3+ et LaBr3:Ce3+, caractérisés par une réponse rapide, un rendement lumineux élevé et une excellente résolution énergétique, et particulièrement intéressants pour l imagerie médicale. La forte hygroscopie de ces matériaux nécessite l adaptation des modes opératoires habituels pour la détermination des caractéristiques physico-chimiques.. La bonne compréhension du mécanisme de scintillation et de l effet des défauts présents dans le matériau permet d envisager des pistes pour l optimisation des performances du scintillateur. Dans ce sens, plusieurs techniques sont utilisées (RPE, radioluminescence, excitation laser, thermoluminescence,...). La connaissance des divers processus impliqués dans le mécanisme de scintillation conduit à prévoir l effet de la température et du taux de dopage sur les performances du scintillateur.PARIS-BIUSJ-Thèses (751052125) / SudocPARIS-BIUSJ-Physique recherche (751052113) / SudocSudocFranceF