Synchrotron-Based X-ray Fluorescence Imaging Elucidates Uranium Toxicokinetics in Daphnia magna.

A combination of synchrotron-based elemental analysis and acute toxicity tests was used to investigate the biodistribution and adverse effects in Daphnia magna exposed to uranium nanoparticle (UNP, 3-5 nm) suspensions or to uranium reference (Uref) solutions. Speciation analysis revealed similar size distributions between exposures, and toxicity tests showed comparable acute effects (UNP LC50: 402 µg L-1 [336-484], Uref LC50: 268 µg L-1 [229-315]). However, the uranium body burden was 3- to 5-fold greater in UNP-exposed daphnids, and analysis of survival as a function of body burden revealed a ∼5-fold higher specific toxicity from the Uref exposure. High-resolution X-ray fluorescence elemental maps of intact, whole daphnids from sublethal, acute exposures of both treatments revealed high uranium accumulation onto the gills (epipodites) as well as within the hepatic ceca and the intestinal lumen. Uranium uptake into the hemolymph circulatory system was inferred from signals observed in organs such as the heart and the maxillary gland. The substantial uptake in the maxillary gland and the associated nephridium suggests that these organs play a role in uranium removal from the hemolymph and subsequent excretion. Uranium was also observed associated with the embryos and the remnants of the chorion, suggesting uptake in the offspring. The identification of target organs and tissues is of major importance to the understanding of uranium and UNP toxicity and exposure characterization that should ultimately contribute to reducing uncertainties in related environmental impact and risk assessments.

On the Role of Cs4PbBr6 Phase in the Luminescence Performance of Bright CsPbBr3 Nanocrystals.

CsPbBr3 nanocrystals have been identified as a highly promising material for various optoelectronic applications. However, they tend to coexist with Cs4PbBr6 phase when the reaction conditions are not controlled carefully. It is therefore imperative to understand how the presence of this phase affects the luminescence performance of CsPbBr3 nanocrystals. We synthesized a mixed CsPbBr3-Cs4PbBr6 sample, and compared its photo- and radioluminescence properties, including timing characteristics, to the performance of pure CsPbBr3 nanocrystals. The possibility of energy transfer between the two phases was also explored. We demonstrated that the presence of Cs4PbBr6 causes significant drop in radioluminescence intensity of CsPbBr3 nanocrystals, which can limit possible future applications of Cs4PbBr6-CsPbBr3 mixtures or composites as scintillation detectors.

Scintillation Response Enhancement in Nanocrystalline Lead Halide Perovskite Thin Films on Scintillating Wafers.

Lead halide perovskite nanocrystals of the formula CsPbBr3 have recently been identified as potential time taggers in scintillating heterostructures for time-of-flight positron emission tomography (TOF-PET) imaging thanks to their ultrafast decay kinetics. This study investigates the potential of this material experimentally. We fabricated CsPbBr3 thin films on scintillating GGAG:Ce (Gd2.985Ce0.015Ga2.7Al2.3O12) wafer as a model structure for the future sampling detector geometry. We focused this study on the radioluminescence (RL) response of this composite material. We compare the results of two spin-coating methods, namely the static and the dynamic process, for the thin film preparation. We demonstrated enhanced RL intensity of both CsPbBr3 and GGAG:Ce scintillating constituents of a composite material. This synergic effect arises in both the RL spectra and decays, including decays in the short time window (50 ns). Consequently, this study confirms the applicability of CsPbBr3 nanocrystals as efficient time taggers for ultrafast timing applications, such as TOF-PET.

Primordial Radioactivity and Prebiotic Chemical Evolution: Effect of γ Radiation on Formamide-Based Synthesis.

Although the effect of ionizing radiation on prebiotic chemistry is often overlooked, primordial natural radioactivity might have been an important source of energy for various chemical transformations. Estimates of the abundances of short-lived radionuclides on early Earth suggest that the primordial intensity of endogenous terrestrial radioactivity was up to 4 × 103 times higher than it is today. Therefore, we assume that chemical substances in contact with radioactive rocks should therefore undergo radiolysis. The calculations are followed by research investigating the influence of ionizing γ radiation on basic prebiotic substances, including formamide mixed with various clays, which might have played the role of a catalyst and an agent that partially blocked radiation that was potentially destructive for the products. Our explorations of this effect have shown that the irradiation of formamide-clay mixtures at doses of ∼6 kGy produces significant amounts of urea (up to the maximal concentration of approximately 250 mg L-1), which plays a role in HCN-based prebiotic chemistry.

RADIOPROTECTIVE EFFECT OF HYDROXYL RADICAL SCAVENGERS ON PROKARYOTIC AND EUKARYOTIC CELLS UNDER VARIOUS GAMMA IRRADIATION CONDITIONS.

The influence of various hydroxyl radical scavengers such as methanol, ethanol and dimethyl sulfoxide on radiation sensitivity of prokaryotic cells (bacteria Escherichia coli) and eukaryotic cells (yeast Saccharomyces cerevisiae and V79 cells-Chinese hamster pulmonary fibroblasts) irradiated by 60Co gamma radiation was investigated. The dependence of radiation sensitivity on dose rate in range from 1.8 to 100 Gy h-1 was evaluated. Survival of cells irradiated by increasing dose rates was followed using clonogenic assay. Specific protective effect was found to be a nonmonotonous function of dose rate with typical maximum at the dose rate range from 50 to 55 Gy h-1 in all studied cell types.

ETHANOL AS A MODIFIER OF RADIATION SENSITIVITY OF LIVING CELLS AGAINST UV-C RADIATION.

The protection of Escherichia coli bacteria and the yeast Saccharomyces cerevisiae against UV-C radiation by ethanol was studied. It was found that the fraction of surviving cells increases with increasing ethanol concentration. The specific protection depends on the dose rate, concentration range of ethanol, and it is higher for yeast compared to the bacteria.

Core-shell ZnO:Ga-SiO2 nanocrystals: limiting particle agglomeration and increasing luminescence via surface defect passivation.

Heat treatment is needed to increase the luminescence intensity of ZnO:Ga particles, but it comes at the cost of higher particle agglomeration. Higher agglomeration results in low transparency of scintillating powder when embedded in a matrix and constitutes one of the biggest disadvantages, besides low light yield and low stopping power, of ZnO:Ga powder. Limiting ZnO:Ga particle size is therefore a key step in order to prepare highly luminescent and transparent composites with prospects for optical applications. In this work, SiO2 coating was successfully used to improve luminescence intensity or limitation of crystallite size growth during further annealing. Furthermore, ZnO:Ga and ZnO:Ga-SiO2 core-shells were embedded in a polystyrene matrix.

Ultrafast Zn(Cd,Mg)O:Ga nanoscintillators with luminescence tunable by band gap modulation.

Photo-induced synthesis was used for preparation of powder Zn(Cd,Mg)O:Ga scintillating nanocrystals featuring properties of solid solutions. Only ZnO phase was identified without any phase separation up to 10% of Cd after optimization of the preparation. Radioluminescence spectra show the exciton-related emission in UV spectral range with significant blue (ZnMgO:Ga) or red (ZnCdO:Ga) shifts. The emission wavelength is tunable by the Cd/Mg content. Defect-related emission is completely suppressed after treatment in reducing atmosphere. Photoluminescence and cathodoluminescence decays show extremely fast component. Subnanosecond decay together with band gap modulation make Zn(Cd,Mg)O:Ga good candidate for practical applications like X-ray induced photodynamic therapy (PDTX) or those requiring superfast timing.

Effects of irradiation conditions on the radiation sensitivity of microorganisms in the presence of OH-radical scavengers.

PURPOSE: The purpose of the paper was to investigate the protective effect of some scavengers of OH radicals (hydroxyl radicals) on the radiation sensitivity of bacteria (in some cases also yeast) under normoxic (in air) or hypoxic (suboxic) conditions and to compare the obtained results with those published earlier for the yeast, all in a wide interval of irradiation conditions. Another aim was to investigate a possible impact of the reaction order of the reaction between the scavengers and the OH radicals on the protection of the cells. MATERIALS AND METHODS: In order to study the protective effect of OH scavengers we used various concentrations of methanol and potassium formate (in some cases also ethanol) in isotonic salt solutions. These solutions containing living bacteria (Escherichia coli) or yeast (Saccharomyces cerevisiae) were irradiated with 60Co radiation using various doses and dose rates. Irradiation was performed in air, in some cases under the hypoxic conditions. The number of surviving cells was determined prior to and after irradiation in suspension with and without scavengers. The surviving fractions after irradiation with and without scavenger were evaluated. RESULTS: The surviving fraction of bacterial cells increases linearly with increasing concentration of both scavengers. The fraction of surviving cells does not increase with increasing concentration of the scavengers under suboxic conditions. The protective effect Ϭ increases linearly with increasing scavenging efficiency and this dependence is much sharper under normoxic conditions than under suboxic ones. The specific protection k is much higher for the methanol than for the potassium formate. CONCLUSIONS: The basic characteristics of the impact of scavengers of OH radicals on radiation sensitivity of both bacteria and yeast are the same in a wide interval of doses and dose rates. The specific protection effect is much higher under the normoxic conditions. This protective effect is inversely proportional to the rate constant of the reaction between the scavenger and the OH radicals. It seems to be obvious that the presence of oxygen during irradiation is a necessary condition for the protective action of the scavengers which may be partially controlled by some transport processes and may be connected with the radiation sensitivity of the cells. On the other hand, the change of the reaction order of the reaction of the scavenger with the OH radicals has turned out to be unimportant.

LuAG:Pr3+-porphyrin based nanohybrid system for singlet oxygen production: Toward the next generation of PDTX drugs.

A highly prospective drug for the X-ray induced photodynamic therapy (PDTX), LuAG:Pr3+@SiO2-PpIX nanocomposite, was successfully prepared by a three step process: photo-induced precipitation of the Lu3Al5O12:Pr3+ (LuAG:Pr3+) core, sol-gel technique for amorphous silica coating, and a biofunctionalization by attaching the protoporphyrin IX (PpIX) molecules. The synthesis procedure provides three-layer nanocomposite with uniform shells covering an intensely luminescent core. Room temperature radioluminescence (RT RL) spectra as well as photoluminescence (RT PL) steady-state and time resolved spectra of the material confirm the non-radiative energy transfer from the core Pr3+ ions to the PpIX outer layer. First, excitation of Pr3+ ions results in the red luminescence of PpIX. Second, the decay measurements exhibit clear evidence of mentioned non-radiative energy transfer (ET). The singlet oxygen generation in the system was demonstrated by the 3'-(p-aminophenyl) fluorescein (APF) chemical probe sensitive to the singlet oxygen presence. The RT PL spectra of an X-ray irradiated material with the APF probe manifest the formation of singlet oxygen due to which enhanced luminescence around 530 nm is observed. Quenching studies, using NaN3 as an 1O2 inhibitor, also confirm the presence of 1O2 in the system and rule out the parasitic reaction with OH radicals. To summarize, presented features of LuAG:Pr3+@SiO2-PpIX nanocomposite indicate its considerable potential for PDTX application.

At the crossroad of photochemistry and radiation chemistry: formation of hydroxyl radicals in diluted aqueous solutions exposed to ultraviolet radiation.

Formation yields of ˙OH radicals were precisely determined in aqueous solutions of coumarin-3-carboxylic acid and ferrous sulfate (i.e., Fricke dosimeter) exposed to 253.7 nm radiation delivered from a continuous source. Quantum yield of ˙OH radicals was determined as ∼0.08, i.e., roughly one out of twelve photons, efficiently absorbed in UV-illuminated solutions, produced one ˙OH radical. Energetically, a water molecule should undergo a correlated action of at least two 4.9 eV photons delivering enough energy for direct H-OH dissociation (5.0-5.4 eV). We suggest a mechanism based on an interaction of two water molecules, both in long-living triplet states. An intermolecular transfer of excitation energy provided a sufficient amount of energy for the dissociation of one water molecule into ˙OH and H˙ radicals. In an aqueous solution of phospholipids, quantum yields of hydroperoxides formed under these irradiation conditions decreased with total effectively absorbed energy (i.e. a dose), similar to the radiation chemical yields obtained during an exposure to ionizing radiation, such as gamma rays from radionuclide sources. Under 253.7 nm irradiation, one ˙OH radical causes a peroxidation of 34 phospholipid molecules. This implicates chain mechanism of the reaction.

Degradation of phospholipids under different types of irradiation and varying oxygen saturation.

The effects of different types of radiation on the formation of peroxide forms of 2-dioleoyl-sn-glycero-3-phosphocholine were studied under various conditions. For the irradiation, an aqueous solution of small unilamellar vesicles was prepared. Variations in parameters such as the dose rate and molecular oxygen saturation levels were evaluated. Our study suggests that the mechanism of the peroxides formation process remains unchanged under irradiation by accelerated electrons, gamma and accelerated protons. The values of radiation chemical yields of the peroxidic form depend on the type of radiation, dose rate, and the saturation of molecular oxygen. The level of oxygen saturation strongly affects the values of radiation chemical yields as well, as the dissolved oxygen is an important agent participating in peroxidation and it is a source of free radicals during the radiolysis. The values of radiation chemical yields strongly suggest that the mechanism of radiation-induced peroxidation of phosphatidylcholines does not proceed via chain reaction.

Preparation and luminescence properties of ZnO:Ga - polystyrene composite scintillator.

Highly luminescent ZnO:Ga-polystyrene composite (ZnO:Ga-PS) with ultrafast subnanosecond decay was prepared by homogeneous embedding the ZnO:Ga scintillating powder into the scintillating organic matrix. The powder was prepared by photo-induced precipitation with subsequent calcination in air and Ar/H2 atmospheres. The composite was subsequently prepared by mixing the ZnO:Ga powder into the polystyrene (10 wt% fraction of ZnO:Ga) and press compacted to the 1 mm thick pellet. Luminescent spectral and kinetic characteristics of ZnO:Ga were preserved. Radioluminescence spectra corresponded purely to the ZnO:Ga scintillating phase and emission of polystyrene at 300-350 nm was absent. These features suggest the presence of non-radiative energy transfer from polystyrene host towards the ZnO:Ga scintillating phase which is confirmed by the measurement of X-ray excited scintillation decay with picosecond time resolution. It shows an ultrafast rise time below the time resolution of the experiment (18 ps) and a single-exponential decay with the decay time around 500 ps.

Breaking DNA strands by extreme-ultraviolet laser pulses in vacuum.

Ionizing radiation induces a variety of DNA damages including single-strand breaks (SSBs), double-strand breaks (DSBs), abasic sites, modified sugars, and bases. Most theoretical and experimental studies have been focused on DNA strand scissions, in particular production of DNA double-strand breaks. DSBs have been proven to be a key damage at a molecular level responsible for the formation of chromosomal aberrations, leading often to cell death. We have studied the nature of DNA damage induced directly by the pulsed 46.9-nm (26.5 eV) radiation provided by an extreme ultraviolet (XUV) capillary-discharge Ne-like Ar laser (CDL). Doses up to 45 kGy were delivered with a repetition rate of 3 Hz. We studied the dependence of the yield of SSBs and DSBs of a simple model of DNA molecule (pBR322) on the CDL pulse fluence. Agarose gel electrophoresis method was used for determination of both SSB and DSB yields. The action cross sections of the single- and double-strand breaks of pBR322 plasmid DNA in solid state were determined. We observed an increase in the efficiency of strand-break induction in the supercoiled DNA as a function of laser pulse fluence. Results are compared to those acquired at synchrotron radiation facilities and other sources of extreme-ultraviolet and soft x-ray radiation.

Influence of various scavengers of •OH radicals on the radiation sensitivity of yeast and bacteria.

PURPOSE: To quantitatively investigate the influence of various •OH (hydroxyl radical) scavengers on the radiation sensitivity of yeast and bacteria, particularly to define the relationship between the protective effect of a scavenger and its •OH scavenging efficiency. MATERIALS AND METHODS: In order to study the protective effect of •OH scavengers we used various concentrations of four scavengers (methanol, potassium formate, ethanol and ascorbic acid) in isotonic salt solutions. These solutions containing live yeast (Saccharomyces cerevisiae) or bacteria (Escherichia coli) were irradiated with (60)Co isotope γ -radiation using two different doses and dose rates. The number of surviving cells was determined prior to and after irradiation both in suspension with and without scavengers. The surviving fractions after irradiation with and without the scavenger were evaluated. RESULTS AND CONCLUSIONS: The main results of the paper were: The surviving fraction increased approximately linearly within the measured interval with increasing concentration of the scavenger. The same dependences were found for the protecting effect depending on the scavenging efficiency. The slopes of these dependences (k) were found to be characteristic for each scavenger. The k value determined the degree in which the scavenging of •OH radicals participated in the protection of living cells. The protective effects of scavengers at the same scavenging efficiency were different and unique for each scavenger. No simple relation was found between the efficiency of scavenger k and the rate constant kOH of the reactions between scavengers and •OH radicals. Our results suggest that the studied scavengers effectively protected yeast and bacteria against ionizing radiation. Although the scavenging of •OH radicals seems to be important for protection of living cells, it is clearly not the only process on which the protection is based.

Radiation formation of colloidal silver particles in aqueous systems.

This paper reports on the formation of silver nanoparticles initiated by gamma and UV radiation in various aqueous solutions. Inorganic precursors were used for radiation and/or photochemical reduction of Ag(+) ions to a metallic form. The influence of various parameters on the nucleation and formation of colloid particles was studied. Attention was also focused on the composition of the irradiated solution. Aliphatic alcohols were used as scavengers of OH radicals and other oxidizing species. The influence of the stabilizers on the formation and stability of the nanoparticles was studied.