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The solution-state interactions of plutonium and berkelium with the octadentate chelator 3,4,3-LI(1,2-HOPO) (343-HOPO) were investigated and characterized by X-ray absorption spectroscopy, which revealed in situ reductive decomposition of the tetravalent species of both actinide metals to yield Pu(III) and Bk(III) coordination complexes. X-ray absorption near-edge structure (XANES) measurements were the first indication of in situ synchrotron redox chemistry as the Pu threshold and white-line position energies for Pu-343-HOPO were in good agreement with known diagnostic Pu(III) species, whereas Bk-343-HOPO results were found to mirror the XANES behavior of Bk(III)-DTPA. Extended X-ray absorption fine structure results revealed An-OHOPO bond distances of 2.498 (5) and 2.415 (2) Å for Pu and Bk, respectively, which match well with bond distances obtained for trivalent actinides and 343-HOPO via density functional theory calculations. Pu(III)- and Bk(III)-343-HOPO data also provide initial insight into actinide periodicity as they can be compared with previous results with Am(III)-, Cm(III)-, Cf(III)-, and Es(III)-343-HOPO, which indicate there is likely an increase in 5f covalency and heterogeneity across the actinide series.

Background: The use of standardised assessment tools is a fundamental aspect of good clinical practice. However, to our knowledge, no study has documented the use of standardised assessment tools in physiotherapy in French-speaking sub-Saharan Africa. Objectives: Documenting the use of standardised outcome measures in physiotherapy in French-speaking sub-Saharan Africa. Method: Our cross-sectional survey used an online self-questionnaire on facilitators and barriers to the use of standardised outcome measures, distributed to physiotherapists in French-speaking sub-Saharan Africa. Results: A total of 241 physiotherapists working in French-speaking sub-Saharan Africa responded to the survey. The most represented countries were Benin (36.9%), Cameroon (14.1%), and Burkina Faso (10.8%). Although 99% of participants reported using standardised outcome measures, only 27% of the respondents used them systematically (all the time). The most reported facilitators included the recognition that standardised outcome measures help to determine whether treatment is effective, help to guide care, and improve communication with patients. The most significant barriers were the lack of time, unavailability of the standardised outcome measures, and non-sensitivity of measures to patients’ cultural and ethnic concerns. There was a higher proportion of use in the middle age group (30–40) (p = 0.02) and a lower proportion of use in physiotherapists simultaneously working in public and private sectors (p = 0.05). Conclusion: Standardised outcome measures are still not widely used by physiotherapists in French-speaking sub-Saharan Africa. Clinical implications: The perceived barriers and facilitators could help to develop strategies to improve the systematic use of outcome measures in French-speaking sub-Saharan Africa.

Transplutonium actinides are among the heaviest elements whose macroscale chemical properties can be experimentally tested. Being scarce and hazardous, their chemistry is rather unexplored, and they have traditionally been considered a rather homogeneous group, with most of their characteristics extrapolated from lanthanide surrogates. Newly emerged applications for these elements, combined with their persistent presence in nuclear waste, however, call for a better understanding of their behavior in complex living systems. In this work, we explored the biodistribution and excretion profiles of four transplutonium actinides (248Cm, 249Bk, 249Cf and 253Es) in a small animal model, and evaluated their in vivo sequestration and decorporation by two therapeutic chelators, diethylenetriamine pentaacetic acid and 3,4,3-LI(1,2-HOPO). Notably, the organ deposition patterns of those transplutonium actinides were element-dependent, particularly in the liver and skeleton, where lower atomic number radionuclides showed up to 7-fold larger liver/skeleton accumulation ratios. Nevertheless, the metal content in multiple organs was significantly decreased for all tested actinides, particularly in the liver, after administering the therapeutic agent 3,4,3-LI(1,2-HOPO) post-contamination. Lastly, the systematic comparison of the radionuclide biodistributions showed discernibly element-dependent organ depositions, which may provide insights into design rules for new bio-inspired chelating systems with high sequestration and separation performance.

Due to their rarity and radioactive nature, comparatively little is known about the actinides, particularly those with atomic numbers higher than that of plutonium, and their compounds. In this work, we describe how transmission electron microscopy can provide comprehensive, safe, and cost-effective characterization using only single nanogram amounts of highly-radioactive, solid compounds. Chlorides of the rare elements berkelium and californium are dropcast and then converted in situ to oxides using the electron beam. The f-band occupancies are probed using electron energy loss spectroscopy and an unexpectedly weak spin-orbit-coupling is identified for berkelium. In contrast, californium follows a jj coupling scheme. These results have important implications for the chemistries of these elements and solidify the status of californium as a transitional element in the actinide series.

The solution-state interactions between octadentate hydroxypyridinone (HOPO) and catecholamide (CAM) chelating ligands and uranium were investigated and characterized by UV-visible spectrophotometry and X-ray absorption spectroscopy (XAS), as well as electrochemically via spectroelectrochemistry (SEC) and cyclic voltammetry (CV) measurements. Depending on the selected chelator, we demonstrate the controlled ability to bind and stabilize UIV, generating with 3,4,3-LI(1,2-HOPO), a tetravalent uranium complex that is practically inert toward oxidation or hydrolysis in acidic, aqueous solution. At physiological pH values, we are also able to bind and stabilize UIV to a lesser extent, as evidenced by the mix of UIV and UVI complexes observed via XAS. CV and SEC measurements confirmed that the UIV complex formed with 3,4,3-LI(1,2-HOPO) is redox inert in acidic media, and UVI ions can be reduced, likely proceeding via a two-electron reduction process.

Separation of lanthanides (Ln) from actinides (An) is unanimously challenging in reprocessing used nuclear fuel despite of much dedicated efforts over the past several decades. The TALSPEAK process is the current reference method in the United States for Ln3+/An3+ separation but suffers from several limitations, such as a narrow working pH window (3.5-4.0), costly pH buffers, and slow extraction kinetics. Studies aiming at improving TALSPEAK have so far focused on polyaminocarboxylates hold-back reagents. Here, a new class of water-soluble ligands comprising hydroxypyridinone metal-binding units are evaluated for Ln3+/An3+ separation. The model octadentate chelator 3,4,3-LI(1,2-HOPO) (abbreviated as HOPO) was used in combination with several industry-relevant organic extractants to separate Gd from four transplutonium elements (Am, Cm, Bk, and Cf). Cyanex 301 GN and HDEHP worked best in combination with HOPO, whereas HEH[EHP], Cyanex 572, and ACORGA M5640 did not yield practical Ln3+/An3+ separation. Separation factors between Gd3+ and Am3+ reach about 50 with the HOPO/Cyanex 301 GN system and 30 with the HOPO/HDEHP system. The results using HDEHP (SFGd/Am = 30, SFGd/Cm = 8.5, and SFGd/Cf = 773) are high enough for industrial applications, and the proposed system works at pH values as low as 1.5, which simplifies the process by eliminating the need for pH buffers. In contrast to previously proposed methods, the HOPO-based process is also highly selective at separating Bk from Ln3+ (SFGd/Bk = 273) owing to in situ, spontaneous oxidation of Bk(III) to Bk(IV) by HOPO. The optimal pH in the case of HOPO/Cyanex 301 GN is 3.6 (SFAm/Gd = 50, SFCm/Gd = 23, SFBk/Gd = 1.4, and SFCf/Gd = 3.2), but this system has the advantage of extracting An ions into the organic phase while keeping Ln ions in the aqueous phase, which is opposite to the conventional TALSPEAK process. This study represents the first optimization of a TALSPEAK-like Ln/An separation method using a HOPO chelator and paves the avenue for further developments of analytical science and reprocessing of used nuclear fuel.

The octadentate siderophore analog 3,4,3-LI(1,2-HOPO), denoted 343-HOPO hereafter, is known to have high affinity for both trivalent and tetravalent lanthanide and actinide cations. Here we extend its coordination chemistry to the rare-earth cations Sc3+ and Y3+ and characterize fundamental metal-chelator binding interactions in solution via UV-Vis spectrophotometry, nuclear magnetic resonance spectroscopy, and spectrofluorimetric metal-competition titrations, as well as in the solid-state via single crystal X-ray diffraction. Sc3+ and Y3+ binding with 343-HOPO is found to be robust, with both high thermodynamic stability and fast room temperature radiolabeling, indicating that 343-HOPO is likely a promising chelator for in vivo applications with both metals. As a proof of concept, we prepared a 86Y-343-HOPO complex for in vivo PET imaging, and the results presented herein highlight the potential of 343-HOPO chelated trivalent metal cations for therapeutic and theranostic applications.

Current methods for metal chelation are generally based on multidentate organic ligands, which are generated through cumbersome multistep synthetic processes that lack flexibility for systematically varying metal-binding motifs. Octadentate ligands incorporating hydroxypyridinone or catecholamide binding moieties onto a spermine scaffold are known to display some of the highest affinities towards f-elements. Enhancing binding affinity for specific lanthanide or actinide ions however, necessitates ligand architectures that allow for modular and high throughput synthesis. Here we introduce a high-throughput combinatorial library of 16 tetrameric N-substituted glycine oligomers (peptoids) containing hydroxypyridinone or catecholamide chelating units linked via an ethylenediamine bridge and, for comparison, we also synthesized the corresponding mixed ligands derived from the spermine scaffold: 3,4,3-LI(1,2-HOPO)2(CAM)2 and 3,4,3-LI(CAM)2(1,2-HOPO)2. Coordination-based luminescence studies were carried out with Eu3+ and Tb3+ to begin probing the properties of the new ligand architecture and revealed higher sensitization efficiency with the spermine scaffold as well as different spectroscopic features among the structural peptoid isomers. Solution thermodynamic properties of selected ligands revealed different coordination properties between the spermine and peptoid analogues with Eu3+ stability constants log β 110 ranging from 28.88 ± 3.45 to 43.97 ± 0.49. The general synthetic strategy presented here paves the way for precision design of new specific and versatile ligands, with a variety of applications tailored towards the use of f-elements, including separations, optical device optimization, and pharmaceutical development.

Metal ion separations are critical to numerous fields, including nuclear medicine, waste recycling, space exploration, and fundamental research. Nonetheless, operational conditions and performance are limited, imposing compromises between recovery, purity, and cost. Siderophore-inspired ligands show unprecedented charge-based selectivity and compatibility with harsh industry conditions, affording excellent separation efficiency, robustness and process control. Here, we successfully demonstrate a general separation strategy on three distinct systems, for Ac, Pu, and Bk purification. Separation factors (SF) obtained with model compound 3,4,3-LI(1,2-HOPO) are orders of magnitude higher than with any other ligand currently employed: 106 between Ac and relevant metal impurities, and over 108 for redox-free Pu purification against uranyl ions and trivalent actinides or fission products. Finally, a one-step separation method (SF > 3 × 106 and radiopurity > 99.999%) enables the isolation of Bk from adjacent actinides and fission products. The proposed approach offers a paradigm change for the production of strategic elements.

The solution-state interactions of plutonium and berkelium with the octadentate chelator 3,4,3-LI(1,2-HOPO) (343-HOPO) were investigated and characterized by X-ray absorption spectroscopy, which revealed in situ reductive decomposition of the tetravalent species of both actinide metals to yield Pu(III) and Bk(III) coordination complexes. X-ray absorption near-edge structure (XANES) measurements were the first indication of in situ synchrotron redox chemistry as the Pu threshold and white-line position energies for Pu-343-HOPO were in good agreement with known diagnostic Pu(III) species, whereas Bk-343-HOPO results were found to mirror the XANES behavior of Bk(III)-DTPA. Extended X-ray absorption fine structure results revealed An—OHOPO bond distances of 2.498 (5) and 2.415 (2) Å for Pu and Bk, respectively, which match well with bond distances obtained for trivalent actinides and 343-HOPO via density functional theory calculations. Pu(III)- and Bk(III)-343-HOPO data also provide initial insight into actinide periodicity as they can be compared with previous results with Am(III)-, Cm(III)-, Cf(III)-, and Es(III)-343-HOPO, which indicate there is likely an increase in 5f covalency and heterogeneity across the actinide series.

The solution chemistry of a chelator developed for 227Th targeted alpha therapy was probed. The compound of interest is an octadentate ligand comprising four N-methyl-3-hydroxy-pyridine-2-one metal-binding units, two tertiary amine groups, and one carboxylate arm appended for bioconjugation. The seven p Ka values of the ligand and the stability constants of complexes formed with Th(IV), Hf(IV), Zr(IV), Gd(III), Eu(III), Al(III), and Fe(III) were determined. The ligand exhibits extreme thermodynamic selectivity toward tetravalent metal ions with a ca. 20 orders of magnitude difference between the formation constant of the Th(IV) species formed at physiological pH, namely [ThL]-, and that of its Eu(III) analogue. Likewise, log β110 values of 41.7 ± 0.3 and 26.9 ± 0.3 (T = 25 °C) were measured for [ThL]- and [FeIIIL]2-, respectively, highlighting the high affinity and selectivity of the ligand for Th ions over potentially competing endogenous metals. Single crystal X-ray analysis of the Fe(III) complex revealed a dinuclear 2:2 metal:chelator complex crystallizing in the space group P1̅. The formation of this dimeric species is likely favored by several intramolecular hydrogen bonds and the protonation state of the chelator in acidic media. LIII edge EXAFS data on the Th(IV) complexes of both the ligand and a monoclonal antibody conjugate revealed the expected mononuclear 1:1 metal:chelator coordination environment. This was also confirmed by high resolution mass spectrometry. Finally, kinetic experiments demonstrated that labeling the bioconjugated ligand with Th(IV) could be achieved and completed after 1 h at room temperature, reinforcing the high suitability of this chelator for 227Th targeted alpha therapy.

In order to reveal subtle differences between the solution chemistries of trivalent 4f and 5f elements, the physicochemical and photophysical properties of europium(iii), terbium(iii) and curium(iii) complexes formed with a 7-methoxy-coumarin appended 1,4,7,10-tetraazadodecane-1,4,7-triacid (DO3A) ligand were studied. All three complexes were found to be kinetically inert and exhibit stability constants similar to their 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) equivalents. The Cm(iii) and Eu(iii) complexes feature strong sensitised emission, while the triplet energy of the coumarin prohibits efficient sensitisation of the Tb(iii) analogue. The data presented here indicate significant differences in perturbation of the sensitising chromophore photophysics between the 4f and 5f elements. In contrast, the size of the metal center appears to not be a determining factor for the physicochemical properties of these kinetically inert Eu(iii), Tb(iii), and Cm(iii) complexes.

The hydroxypyridinone ligand 3,4,3-LI(1,2-HOPO) is a promising agent for biological decorporation of radionuclides, and allows spectroscopic detection of many lanthanide (Ln) and actinide (An) species via sensitized luminescence. Despite the manifest uses of this ligand, the structural and thermodynamic properties of its complexes across the An series remain understudied. Theoretical investigations of the binding of An(III) and An(IV) ions, from actinium to einsteinium, by the 3,4,3-LI(1,2-HOPO) ligand, as well as experimental extended X-ray absorption fine structure (EXAFS) studies on the trivalent americium, curium, and californium complexes were employed to address the resulting structures, thermodynamic parameters, redox properties, and corresponding electronic configurations. An(IV) ions were found to form much stronger complexes than An(III) ions, consistent with experimental measurements. Complexation of both An(III) and An(IV) ions generally becomes more favorable for heavier actinides, reflecting increased energy degeneracy driven covalency and concomitant orbital mixing between the 5f orbitals of the An ions and the π orbitals of the ligand. Notably, the ability of this ligand to either accept or donate electron density as needed from its pyridine rings is found to be key to its extraordinary stability across the actinide series.

In order to reveal subtle differences between the solution chemistries of trivalent 4f and 5f elements, the physicochemical and photophysical properties of europium(iii), terbium(iii) and curium(iii) complexes formed with a 7-methoxy-coumarin appended 1,4,7,10-tetraazadodecane-1,4,7-triacid (DO3A) ligand were studied. All three complexes were found to be kinetically inert and exhibit stability constants similar to their 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) equivalents. The Cm(iii) and Eu(iii) complexes feature strong sensitised emission, while the triplet energy of the coumarin prohibits efficient sensitisation of the Tb(iii) analogue. The data presented here indicate significant differences in perturbation of the sensitising chromophore photophysics between the 4f and 5f elements. In contrast, the size of the metal center appears to not be a determining factor for the physicochemical properties of these kinetically inert Eu(iii), Tb(iii), and Cm(iii) complexes.

The chemistry of trivalent transplutonium ions (Am3+ , Cm3+ , Bk3+ , Cf3+ , Es3+ …) is usually perceived as monotonic and paralleling that of the trivalent lanthanide series. Herein, we present the first extended X-ray absorption fine structure (EXAFS) study performed on a series of aqueous heavy actinide chelates, extending past Cm. The results obtained on diethylenetriaminepentaacetic acid (DTPA) complexes of trivalent Am, Cm, Bk, and Cf show a break to much shorter metal-oxygen nearest-neighbor bond lengths in the case of Cf3+ . Corroborating those results, density functional theory calculations, extended to Es3+ , suggest that the shorter Cf-O and Es-O bonds could arise from the departure of the coordinated water molecule and contraction of the ligand around the metal relative to the other [MIII DTPA(H2 O)]2- (M=Am, Cm, Bk) complexes. Taken together, these experimental and theoretical results demonstrate inhomogeneity within the trivalent transplutonium series that has been insinuated and debated in recent years, and that may also be leveraged for future nuclear waste reprocessing technologies.

The chemistry of trivalent transplutonium ions (Am3+ , Cm3+ , Bk3+ , Cf3+ , Es3+ …) is usually perceived as monotonic and paralleling that of the trivalent lanthanide series. Herein, we present the first extended X-ray absorption fine structure (EXAFS) study performed on a series of aqueous heavy actinide chelates, extending past Cm. The results obtained on diethylenetriaminepentaacetic acid (DTPA) complexes of trivalent Am, Cm, Bk, and Cf show a break to much shorter metal-oxygen nearest-neighbor bond lengths in the case of Cf3+ . Corroborating those results, density functional theory calculations, extended to Es3+ , suggest that the shorter Cf-O and Es-O bonds could arise from the departure of the coordinated water molecule and contraction of the ligand around the metal relative to the other [MIII DTPA(H2 O)]2- (M=Am, Cm, Bk) complexes. Taken together, these experimental and theoretical results demonstrate inhomogeneity within the trivalent transplutonium series that has been insinuated and debated in recent years, and that may also be leveraged for future nuclear waste reprocessing technologies.

Several MRI contrast agent clinical formulations are now known to leave deposits of the heavy metal gadolinium in the brain, bones, and other organs of patients. This persistent biological accumulation of gadolinium has been recently recognized as a deleterious outcome in patients administered Gd-based contrast agents (GBCAs) for MRI, prompting the European Medicines Agency to recommend discontinuing the use of over half of the GBCAs currently approved for clinical applications. To address this problem, we find that the orally-available metal decorporation agent 3,4,3-LI(1,2-HOPO) demonstrates superior efficacy at chelating and removing Gd from the body compared to diethylenetriaminepentaacetic acid, a ligand commonly used in the United States in the GBCA Gadopentetate (Magnevist). Using the radiotracer 153Gd to obtain precise biodistribution data, the results herein, supported by speciation simulations, suggest that the prophylactic or post-hoc therapeutic use of 3,4,3-LI(1,2-HOPO) may provide a means to mitigate Gd retention in patients requiring contrast-enhanced MRI.

The toxicity of heavy metals such as lead (Pb), cadmium (Cd) and tin (Sn) has long been known but accidental exposures of large populations to these elements remain unfortunately a topical issue. Chelating agents against Pb, Cd, or Sn poisoning are still limited to classical ligands such as ethylenediamine tetraacetic acid (EDTA). Here, we evaluate the ability of 3,4,3-LI(1,2-HOPO) (L4-), an octadentate ligand currently under evaluation for actinide decorporation, to bind Pb, Cd and Sn metal ions in aqueous solutions. This ligand forms 1:1 complexes with Pb(ii), Cd(ii) and Sn(iv) as well as bimetallic 2:1 species with Pb(ii) and Cd(ii), all of which were characterized by high resolution mass spectrometry and spectrophotometric titrations. The 3,4,3-LI(1,2-HOPO) ligand exhibits an extreme affinity for Sn(iv) ions (logβ110 > 40), with the complex remaining stable from highly acidic conditions to alkaline media (from 3 M HCl to pH 8). Single crystals of the neutral complex [SnIV3,4,3-LI(1,2-HOPO)·3H2O] were obtained and its structure determined, revealing a chiral conformation. Although not initially designed for hexacoordinated metals such as Pb(ii) and Cd(ii), the octadentate ligand shows promise for the in vitro or in vivo sequestration of toxic heavy metals, as evidenced by decorporation experiments performed in mice contaminated with 210Pb(ii) and treated with either EDTA or 3,4,3-LI(1,2-HOPO).

An innovative process was developed for the leaching of niobium- and rare earth elements-bearing pyrochlores ores and the subsequent separation of Nb from the REE. Compared to the conventional Nb hydrometallurgical methods, the proposed leaching process is based on a triphasic system: H2SO4(aq)-SO2(g)-activated carbon/ore. The implementation of this leaching step allows the selective dissolution of the non-valuable phases while significantly reducing the H2SO4 consumption. The results obtained in continuous operation, at the pilot scale, show a reduction of the sulfur consumption by 48% when compared to the classical H2SO4 pasting-roasting process. The presence of activated carbon, at concentration as low as 0.4% (w/w), was found to considerably fasten the dissolution reactions and allows optimizing the SO2 utilization to a nearly quantitative rate. The triphasic leaching also affords concentrating the Nb stream which decreases the energy consumption of the down-stream operations and especially for the subsequent Nb-REE-bearing pyrochlores roasting step. The process was optimized at the laboratory scale and then tested in continuous operation for 15 days at a flow of 15 kg h−1 of dry equivalent of non-magnetic Nb-REE pyrochlore ore from the Gabonese Mabounié deposit and the equivalent of 8.25 kg h−1 of H2SO4 and 0.15 kg h−1 of activated carbon.

Marine Barral,1,* Julie Martin,1,* Emmanuelle Carre,2 Audrey Janoly-Dumenil,3– 5 Florence Ranchon,2,4,6 Stéphanie Parat,2 Catherine Rioufol,2,4,6 Sylvain Goutelle,4,7,8 Laurent Bourguignon,4,7,8 Teddy Novais,4,9,10 Sebastien Doh,11 Matthieu Malatray,12 Philippe Chaudier,13 Jerome Gauthier,14 Christine Pivot,3 Christelle Mouchoux,4,9,15 Delphine Hoegy1,4,5 On behalf of 5P Study Group1Pharmacie, Hospices Civils de Lyon, Lyon, France; 2Pharmacie Hôpital Lyon Sud, Hospices Civils de Lyon, Pierre-Bénite, France; 3Pharmacie Hôpital Edouard Herriot, Hospices Civils de Lyon, Lyon, France; 4Institut des Sciences Pharmaceutiques et Biologiques, Univ Claude Bernard Lyon 1, Univ Lyon 1, Lyon, France; 5 6-EA 4129 P2S Parcours Santé Systémique- Univ Claude Bernard Lyon 1, Univ Lyon 1, Lyon, France; 6EA3738, CICLY Centre pour l’Innovation en cancérologie de Lyon, Univ Claude Bernard Lyon 1, Univ Lyon 1, Lyon, France; 7Pharmacie Hôpital Pierre Garraud, Hospices Civils de Lyon, Lyon, France; 8CNRS, UMR 5558, Laboratoire de Biométrie et Biologie Évolutive, Villeurbanne, France; 9Pharmacie Hôpital des Charpennes, Hospices Civils de Lyon, Villeurbanne, France; 10Université Claude Bernard Lyon 1, Research on Healthcare Performance (RESHAPE), INSERM U1290, Lyon, France; 11Service de Gériatrie Hôpital Edouard Herriot, Hospices Civils de Lyon, Lyon, France; 12Service de Chirurgie Orthopédique Hôpital Edouard Herriot, Hospices Civils de Lyon, Lyon, France; 13Service de Chirurgie Orthopédique Hôpital Lyon Sud, Hospices Civils de Lyon, Pierre-Bénite, France; 14Service d’anesthésie et réanimation Hôpital Lyon Sud, Hospices Civils de Lyon, Pierre-Bénite, France; 15Lyon Neuroscience Research Center, INSERM U1028, CNRS UMR5292, Lyon, France*These authors contributed equally to this work.Correspondence: Delphine HoegyHôpital Edouard Herriot, Groupement Hospitalier Centre, Hospices Civils de Lyon, 5 Place d’Arsonval, Lyon, 69003, FranceTel +33 4 72 11 91 82Fax +33 4 72 11 78 76Email delphine.hoegy@chu-lyon.frBackground: A new model was developed for integrating a personalised clinical pharmacy programme (5P project) into the orthogeriatric care pathway.Objective: To secure the therapeutic care of orthogeriatric patients.Design and Setting: Prospective descriptive study in a multisite teaching hospital from June 2019 to January 2020.Subjects: Patients aged ≥ 75 years admitted for hip fracture.Methods: A prescription review was performed for all patients at inclusion. Other clinical pharmacy activities (additional prescription review, pharmaceutical interviews, medication reconciliation) were dedicated to “high-risk” patients. Potential medication errors (ME), either pharmaceutical interventions (PI) or unintentional discrepancies (UID), were recorded. The potential clinical impact of PI was evaluated by a pluriprofessional expert panel using a validated tool.Results: In the 455 patients included, 955 potential ME were detected, that is ≥ 1 potential ME for 324/455 (71%) patients. In acute care, 561 PI were formulated during prescription review for 440/455 (97%) patients and 348/561 (62%) were accepted by physicians. Medication reconciliation was performed for 213 patients, 316 UID were identified. In rehabilitation units, a second prescription review was performed for 112/122 (92%) “high-risk” patients, leading to 61 PI. The clinical impact was evaluated for 519/622 (83%) PI. A consensus was obtained for 310/519 (60%) PI: 147/310 (47%) were rated as having minor clinical impact, 138/310 (45%) moderate, 22/310 (7%) major, 2/310 (0.6%) vital, and 1/310 (0.3%) null.Conclusion: The 5P project secured the orthogeriatric care pathway by detecting a great number of potential ME, including PI mostly considered as having a significant clinical impact.Keywords: hip fracture, frail elderly, pharmaceutical services, medication errors, clinical relevance

Recent efforts to activate the strong uranium-oxygen bonds in the dioxo uranyl cation have been limited to single oxo-group activation through either uranyl reduction and functionalization in solution, or by collision induced dissociation (CID) in the gas-phase, using mass spectrometry (MS). Here, we report and investigate the surprising double activation of uranyl by an organic ligand, 3,4,3-LI(CAM), leading to the formation of a formal U6+ chelate in the gas-phase. The cleavage of both uranyl oxo bonds was experimentally evidenced by CID, using deuterium and 18O isotopic substitutions, and by infrared multiple photon dissociation (IRMPD) spectroscopy. Density functional theory (DFT) computations predict that the overall reaction requires only 132 kJ/mol, with the first oxygen activation entailing about 107 kJ/mol. Combined with analysis of similar, but unreactive ligands, these results shed light on the chelation-driven mechanism of uranyl oxo bond cleavage, demonstrating its dependence on the presence of ligand hydroxyl protons available for direct interactions with the uranyl oxygens.

Berkelium (Bk) has been predicted to be the only transplutonium element able to exhibit both +III and +IV oxidation states in solution, but evidence of a stable oxidized Bk chelate has so far remained elusive. Here we describe the stabilization of the heaviest 4+ ion of the periodic table, under mild aqueous conditions, using a siderophore derivative. The resulting Bk(IV) complex exhibits luminescence via sensitization through an intramolecular antenna effect. This neutral Bk(IV) coordination compound is not sequestered by the protein siderocalin-a mammalian metal transporter-in contrast to the negatively charged species obtained with neighbouring trivalent actinides americium, curium and californium (Cf). The corresponding Cf(III)-ligand-protein ternary adduct was characterized by X-ray diffraction analysis. Combined with theoretical predictions, these data add significant insight to the field of transplutonium chemistry, and may lead to innovative Bk separation and purification processes.

Solvent extraction of Nb(v) from alkaline aqueous media using quaternary ammonium solutions, especially Aliquat® 336 diluted in an aliphatic diluent, was investigated. The hexaniobate ions (HxNb6O19x-8) were extracted into the organic phase with very high yields at room temperature and within a few minutes, affording easy access to organic solutions of hexaniobates. Several parameters were found to influence the extraction of HxNb6O19x-8 including the nature and concentration of alkali cations, confirming subtle effects previously described for polyoxoniobates such as ion-pairing with alkali ions. The extraction of HxNb6O19x-8 with Aliquat® 336 is also influenced if competing anions are present in the aqueous phase (NO3-, Cl-, C2O42-, SO42- and CO32-) and varies with the pH mainly due to the competitive extraction of hydroxide ions at high pH. The co-extraction of sodium ions with HxNb6O19x-8 was observed as well as the co-extraction of water molecules, suggesting a self-association of the extractant. The proposed liquid-liquid extraction generic system paves the way for innovative niobium (and potentially tantalum) hydrometallurgical processes and it may also afford more direct routes for exploring the chemistry of hexaniobates in organic solvents.

Solvent extraction of Nb(v) from alkaline aqueous media using quaternary ammonium solutions, especially Aliquat® 336 diluted in an aliphatic diluent, was investigated. The hexaniobate ions (HxNb6O19x-8) were extracted into the organic phase with very high yields at room temperature and within a few minutes, affording easy access to organic solutions of hexaniobates. Several parameters were found to influence the extraction of HxNb6O19x-8 including the nature and concentration of alkali cations, confirming subtle effects previously described for polyoxoniobates such as ion-pairing with alkali ions. The extraction of HxNb6O19x-8 with Aliquat® 336 is also influenced if competing anions are present in the aqueous phase (NO3-, Cl-, C2O42-, SO42- and CO32-) and varies with the pH mainly due to the competitive extraction of hydroxide ions at high pH. The co-extraction of sodium ions with HxNb6O19x-8 was observed as well as the co-extraction of water molecules, suggesting a self-association of the extractant. The proposed liquid-liquid extraction generic system paves the way for innovative niobium (and potentially tantalum) hydrometallurgical processes and it may also afford more direct routes for exploring the chemistry of hexaniobates in organic solvents.

Leveraging microgram-level techniques, we here present the first transplutonium bis-pentatungstate complex: NaCs8Cm(W5O18)2·14H2O (CmW5). Single crystal XRD, Raman, and fluorescence characterization show significant differences relative to analogous lanthanide compounds. The study reveals the unsuspected impact of counterions on fluorescence and vibrational modes of the curium complex and its lanthanide counterparts. [ABSTRACT FROM AUTHOR]

Leveraging microgram-level techniques, we here present the first transplutonium bis-pentatungstate complex: NaCs8Cm(W5O18)2·14H2O (CmW5). Single crystal XRD, Raman, and fluorescence characterization show significant differences relative to analogous lanthanide compounds. The study reveals the unsuspected impact of counterions on fluorescence and vibrational modes of the curium complex and its lanthanide counterparts. [ABSTRACT FROM AUTHOR]

The obtention and study of actinide elements is challenging due to various factors including their radioactivity and scarcity. Herein, the authors characterize the atomic and electronic structure of Am, Cm, Bk, and Cf compounds using a transmission electron microscopy-based workflow that only requires nanogram amounts of the actinide element.