Capture Instead of Release: Defect-Modulated Radionuclide Leaching Kinetics in Metal-Organic Frameworks.

Comparison of defect-controlled leaching-kinetics modulation of metal-organic frameworks (MOFs) and porous functionalized silica-based materials was performed on the example of a radionuclide and radionuclide surrogate for the first time, revealing an unprecedented readsorption phenomenon. On a series of zirconium-based MOFs as model systems, we demonstrated the ability to capture and retain >99% of the transuranic 241Am radionuclide after 1 week of storage. We report the possibility of tailoring radionuclide release kinetics in MOFs through framework defects as a function of postsynthetically installed organic ligands including cation-chelating crown ether-based linkers. Based on comprehensive analysis using spectroscopy (EXAFS, UV-vis, FTIR, and NMR), X-ray crystallography (single crystal and powder), and theoretical calculations (nine kinetics models and structure simulations), we demonstrated the synergy of radionuclide integration methods, topological restrictions, postsynthetic scaffold modification, and defect engineering. This combination is inaccessible in any other material and highlights the advantages of using well-defined frameworks for gaining fundamental knowledge necessary for the advancement of actinide-based material development, providing a pathway for addressing upcoming challenges in the nuclear waste administration sector.

Effects of Impregnated Amidophosphonate Ligand Concentration on the Uranium Extraction Behavior of Mesoporous Silica.

A series of solid-phase uranium extractants were prepared by post-synthesis impregnation of a mesoporous silica support previously functionalized with octyl chains by direct silanization. Five materials were synthesized with 0, 0.2, 0.3, 0.4 and 0.5 mmol of the amidophosphonate ligand DEHCEBP per gram of functionalized solid, and the effect of the ligand concentration on the uranium extraction efficiency and selectivity of the materials was investigated. Nitrogen adsorption-desorption data show that with increasing ligand loadings, the specific surface area and average pore volume decrease as the amidophosphonate ligand fills first the micropores and then the mesopores of the support. Acidic uranium solutions with a high sulfate content were used to replicate the conditions in ore treatment leaching solutions. Considering the extraction kinetics, the equilibration time was found to increase with the ligand concentration, which can be explained by the clogging of micropores and the multilayer arrangement of the DEHCEBP molecules in the materials with their highest ligand contents. The fact that the equilibrium ligand/uranium ratio is about 2 mol/mol regardless of the ligand concentration in the material suggests that all the ligand molecules remain accessible for extraction. The maximum uranium extraction capacities ranged from 30 mg∙g-1 at 0.2 mmol∙g-1 DEHCEBP to 54 mg∙g-1 in the material with 0.5 mmol∙g-1 DEHCEBP. These materials could therefore potentially be used as solid-phase uranium extractants in acidic solutions with high sulfate concentrations.

Bis-Catecholamide-Based Materials for Uranium Extraction.

This work reports the synthesis of formo-phenolic resins containing four catecholamide (CAM) moieties with admixture of phenol, catechol or resorcinol. These chelating resins have been developed to selectively extract U(VI) from seawater. This media is a challenging environment due to a pH around 8.2 and a large excess of alkaline and earth-alkaline cations. From the various sorption experiments investigated, the results indicate that the synthesized material exhibit good sorbent properties for U(VI) with uptake capacity about 50 mg/g for the more promising resins with a pronounced selectivity for uranium even under saline conditions. Thermodynamic and kinetic adsorption data were determined for the best resin (Langmuir adsorption model and pseudo-second order model).

Bis-Catecholamide-Based Materials for Uranium Extraction.

Invited for this month's cover is the collaborating group of Dr Guilhem Arrachart and Dr Stéphane Pellet-Rostaing at Institut de Chimie Séparative de Marcoule (ICSM). The cover picture shows a person going uranium fishing thanks to the use of bis-catecholamide materials. These materials have shown interesting performance for the recovery of uranium in saline environments such as seawater. More information can be found in the Research Article by G. Arrachart, S. Pellet-Rostaing, and co-workers.

Degradation mechanism of tributyl phosphate by UV/H2O2 treatment and parameters optimization towards the design of a pilot reactor.

While activated sludge treatment is currently the preferred process for the removal of tributyl phosphate (TBP) at the mg.L-1 level, it is well known that this recalcitrant molecule is incompletely degraded, stimulating research into alternative approaches, such as advanced oxidation. The aim of this study was to characterize the degradation mechanism of TBP during ultraviolet/H2O2 treatment using 31P NMR, ionic chromatography and total organic carbon analysis. The effects of initial pH, amount of oxidant and pollutant concentration were also assessed using an experimental design approach. The results of this parametric study show that ultraviolet/H2O2 photo-oxidation efficiently degrades TBP at concentrations up to 600 mg.L-1, with >90% phosphate release and up to 95% removal of total organic carbon within 1 h. The data also show that the main reaction intermediates are short carboxylic acids, resulting from the released alkyl groups, meaning that an interesting application of this process may be to rapidly pre-treat industrial effluent upstream of activated sludge reactors.

Solid lipid nanoparticles (SLNs) derived from para-acyl-calix[9]-arene: preparation and stability.

A study of the parameters relating to the preparation of para-acyl-calix[9]arene-based solid lipid nanoparticles (SLNs) has been undertaken. Dynamic light scattering and electron microscopy have shown that the particle size varies between 85 and 215 nm depending on the acyl chain length. Parameters, including the organic solvent, amphiphile concentration and the presence of a co-surfactant affect the size of the SLNs obtained significantly. In contrast, stirring speed and solution viscosity have no effect. The ionic strength of the suspension has been shown to affect SLN stability in a salt-dependent manner. Ultrasonic and ultraviolet and 80°C treatment of the SLN suspensions have no effect on the SLN stability. The SLNs are unstable with respect to freezing–defreezing cycles, but can be reconstituted using mono- or disaccharides as cryoprotectants. Importantly, the temporal stability of these suspensions in water has been shown to be superior to 6 months. With regard to protein interactions, no SLN aggregation was observed in the presence of human serum albumin, with formation of a monolayer of albumin on the surface of the SLNs. Encapsulation was shown using acridine as a fluorescent probe.

Structuring detergents for extracting and stabilizing functional membrane proteins.

BACKGROUND: Membrane proteins are privileged pharmaceutical targets for which the development of structure-based drug design is challenging. One underlying reason is the fact that detergents do not stabilize membrane domains as efficiently as natural lipids in membranes, often leading to a partial to complete loss of activity/stability during protein extraction and purification and preventing crystallization in an active conformation. METHODOLOGY/PRINCIPAL FINDINGS: Anionic calix[4]arene based detergents (C4Cn, n=1-12) were designed to structure the membrane domains through hydrophobic interactions and a network of salt bridges with the basic residues found at the cytosol-membrane interface of membrane proteins. These compounds behave as surfactants, forming micelles of 5-24 nm, with the critical micellar concentration (CMC) being as expected sensitive to pH ranging from 0.05 to 1.5 mM. Both by 1H NMR titration and Surface Tension titration experiments, the interaction of these molecules with the basic amino acids was confirmed. They extract membrane proteins from different origins behaving as mild detergents, leading to partial extraction in some cases. They also retain protein functionality, as shown for BmrA (Bacillus multidrug resistance ATP protein), a membrane multidrug-transporting ATPase, which is particularly sensitive to detergent extraction. These new detergents allow BmrA to bind daunorubicin with a Kd of 12 µM, a value similar to that observed after purification using dodecyl maltoside (DDM). They preserve the ATPase activity of BmrA (which resets the protein to its initial state after drug efflux) much more efficiently than SDS (sodium dodecyl sulphate), FC12 (Foscholine 12) or DDM. They also maintain in a functional state the C4Cn-extracted protein upon detergent exchange with FC12. Finally, they promote 3D-crystallization of the membrane protein. CONCLUSION/SIGNIFICANCE: These compounds seem promising to extract in a functional state membrane proteins obeying the positive inside rule. In that context, they may contribute to the membrane protein crystallization field.

Bisphosphonate sequestering agents. Synthesis and preliminary evaluation for in vitro and in vivo uranium(VI) chelation.

A library of bisphosphonate-based ligands was prepared using solution-phase parallel synthesis and tested for its uranium-binding properties. With the help of a screening method, based on a chromophoric complex displacement procedure, 23 dipodal and tripodal chelates bearing bisphosphonate chelating functions were found to display very high affinity for the uranyl ion and were selected for evaluation of their in vivo uranyl-removal efficacy. Among them, 11 ligands induced a huge modification of the uranyl biodistribution by deviating the metal from kidney and bones to liver. Among the other ligands, the most potent was the dipodal bisphosphonate 3C which reduced the retention of uranyl and increased its excretion by around 10% of the injected metal.