Actinyl Ions Research Articles

Shape-Selective Supramolecular Capsules for Actinide Precipitation and Separation.

Improving actinide separations is key to reducing barriers to medical and industrial actinide isotope production and to addressing the challenges associated with the reprocessing of spent nuclear fuel. Here, we report the first example of a supramolecular anion recognition process that can achieve this goal. We have designed a preorganized triamidoarene receptor that induces quantitative precipitation of the early actinides Th(IV), Np(IV), and Pu(IV) from industrially relevant conditions through the formation of self-assembled hydrogen-bonded capsules. Selectivity over the later An(III) elements is shown through modulation of the nitric acid concentration, and no precipitation of actinyl or transition-metal ions occurs. The Np, Pu, and Am precipitates were characterized structurally by single-crystal X-ray diffraction and reveal shape specificity of the internal hydrogen-bonding array for the encapsulated hexanitratometalates. This work complements ion-exchange resins for 5f-element separations and illustrates the significant potential of supramolecular separation methods that target anionic actinide species.

Electrochemical/computational analysis and the derivation of Pourbaix diagrams of redox-active structural and adsorbed species in uranyl peroxide clusters (U60)

Electrochemical analysis of U60 nanoclusters (Li40K20[UO2(O2)(OH)]60(H2O)214) and their natural analog, the mineral studtite (UO2)O2(H2O)2·(H2O)2, was carried out using cyclic voltammetry with a powder microelectrode setup. Voltammetric analysis was supplemented by ab initio quantum mechanical modeling to understand the mechanism, thermodynamics, and structural changes during redox transition (with a semi-quantitative kinetics evaluation). This research aims to better understand the redox behavior and transport of dissolved and structural (incorporated) uranyl units in the environment. Further analysis is performed to determine if redox switching of actinyl ions in clusters can be performed while leaving the cluster intact or at what redox transition it disintegrates. Quantum-mechanical calculations were applied to approximate electrochemical peak potential shifts and add them to standard reduction potentials to more accurately assign peaks to specific redox transitions between different species. These peak potentials are calculated from oxidation state-dependent binding energies between different uranyl species either within or adsorbed to U60. This theoretical approach incorporates extensive error cancellation and serves to predict electrochemical redox potentials and identify the reaction taking place. Voltammograms of U60 in electrolyte solutions exhibit kinetically-inhibited coupled redox peaks assigned to the U(VI)/U(V) transition of cluster structural uranyl units at −0.34 V (vs. standard hydrogen electrode), indicative of U60 reduction from UO22+ to UO2+. The U(V)/U(IV) transition at −0.71 V is assigned to the subsequent U60 reduction of UO2+ to UO20. A method of observing these transitions in situ using synchrotron x-ray absorption spectroscopy was explored. Voltammetry, modeling, and peak analysis indicate a kinetically-inhibited two-step, one-e- (per step) reduction of U60 from U(VI) to U(V) to U(IV). Voltammetry and x-ray absorption spectroscopy measurements performed before and after exhaustive cycling and the highly stable nature of U60 provide evidence that clusters typically do not break apart upon reduction. Voltammograms of U60 collected in varied uranyl solutions are indicative of UO22+ adsorption to the cluster surface and its subsequent reduction at +0.24 V (U(VI)/U(V)) and −0.05 V (U(V)/U(IV)). For uranyl solutions in electrolyte, the two-step, one-e- (per step) reduction of U60 is superseded by uranyl adsorption from solution to the electrode surface with subsequent reduction via U(V) disproportionation. This study represents the sole electrochemical investigation of U60 in the literature and only the second of any uranyl peroxide nanocluster. It is also one of the first to use quantum–mechanical approaches in combination with existing solution-based standard reduction potentials to calculate Pourbaix (EH-pH) diagrams for adsorbed and structural species.

Evidence for Uranium(VI/V) Redox Supported by 2,2'-Bipyridyl-6,6'-dicarboxylate.

The 2,2'-bipyridyl-6,6'-dicarboxylate ligand (bdc) has been shown in prior work to effectively capture the uranyl(VI) ion, UO22+, from aqueous solutions. However, the redox properties of the uranyl complex of this ligand have not been addressed despite the relevance of uranium-centered reduction to the nuclear fuel cycle and the presence of a bipyridyl core in bdc, a motif long recognized for its ability to support redox chemistry. Here, the bdc complex of UO22+ (1-UO2) has been synthetically prepared and isolated under nonaqueous conditions for the study of its reductive chemical and electrochemical behavior. Spectrochemical titration data collected using decamethylcobaltocene (Cp*2Co) as the reductant demonstrate that 1e- reduction of 1-UO2 is accessible, and companion near-infrared and infrared spectroscopic data, along with theoretical findings from density functional theory, provide evidence that supports the accessibility of the U(V) oxidation state. Data obtained for control ruthenium complexes of bdc and related polypyridyl dicarboxylate ligands provide a counterpoint to these findings; ligand-centered reduction of bdc in these control compounds occurs at potentials more negative than those measured for reduction of 1-UO2, further supporting the generation of uranium(V) in 1-UO2. Taken together, these results underscore the usefulness of bdc as a ligand for actinyl ions and suggest that it could be useful for further studies of the reductive activation of these unique species.

Ion sieving in graphene oxide membrane enables efficient actinides/lanthanides separation

Separation of actinides from lanthanides is of great importance for the safe management of nuclear waste and sustainable development of nuclear energy, but it represents a huge challenge due to the chemical complexity of these f-elements. Herein, we report an efficient separation strategy based on ion sieving in graphene oxide membrane. In the presence of a strong oxidizing reagent, the actinides (U, Np, Pu, Am) in a nitric acid solution exist in the high valent and linear dioxo form of actinyl ions while the lanthanides (Ce, Nd, Eu, Gd, etc.) remain as trivalent/tetravalent spheric ions. A task-specific graphene oxide membrane with an interlayer nanochannel spacing between the sizes of hydrated actinyl ions and lanthanides ions is tailored and used as an ionic cut-off filter, which blocks the larger and linear actinyl ions but allows the smaller and spheric lanthanides ions to penetrate through, affording lanthanides/actinides separation factors up to ~400. This work realizes the group separation of actinides from lanthanides under highly acidic conditions by a simple ion sieving strategy and highlights the great potential of utilizing graphene oxide membrane for nuclear waste treatment.

Applying Two-Dimensional Correlation Spectroscopy and Principal Component Analysis to Understand How Temperature Affects the Neptunium(V) Absorption Spectrum

The visible-near infrared (Vis-NIR) electronic absorption spectrum of neptunium(V) (NpO2+) comprises numerous f-f electronic transitions with mostly undocumented temperature dependencies. The effect of temperature on the absorption spectrum of the pentavalent neptunyl dioxocation (NpO2+) is an important factor to consider with spectrophotometric applications but has often been overlooked. Optical Vis-NIR absorption spectra (400–1700 nm) of Np(V) (0.017–0.89 M) in 1 M nitric acid were evaluated with varying temperatures (T = 10–80 °C). The intensity, position, and overall shape of the bands were sensitive to interactions with the solvent and coordination environment. Numerous temperature-induced isosbestic points were identified resulting from dynamic, overlapping peak shifts. Spectral variations were characterized using principal component analysis (PCA) and 2D correlation spectroscopy (COS). 2D-COS revealed that the absorption band near 1095 nm likely consists of two bands centered near 1087 and 1096 nm, which cannot be explained by current computational methods. 2D-COS analysis also provided an unambiguous assignment of unresolved peaks in the visible region for comparison with computational predictions. PCA was used to identify nonlinearity in the spectral response at elevated Np(V) concentrations ≥ 0.5 M. This unique experimental data and interpretation will foster a deeper understanding of the absorption spectra for complex actinyl ions.

Advancing the Am Extractant Design through the Interplay among Planarity, Preorganization, and Substitution Effects.

Advancing the field of chemical separations is important for nearly every area of science and technology. Some of the most challenging separations are associated with the americium ion Am(III) for its extraction in the nuclear fuel cycle, 241Am production for industrial usage, and environmental cleanup efforts. Herein, we study a series of extractants, using first-principle calculations, to identify the electronic properties that preferentially influence Am(III) binding in separations. As the most used extractant family and because it affords a high degree of functionalization, the polypyridyl family of extractants is chosen to study the effects of the planarity of the structure, preorganization of coordinating atoms, and substitution of various functional groups. The actinyl ions are used as a structurally simplified surrogate model to quickly screen the most promising candidates that can separate these metal ions. The down-selected extractants are then tested for the Am(III)/Eu(III) system. Our results show that π interactions, especially those between the central terpyridine ring and Am(III), play a crucial role in separation. Adding an electron-donating group onto the terpyridine backbone increases the binding energies to Am(III) and stabilizes Am-terpyridine coordination. Increasing the planarity of the extractant increases the binding strength as well, although this effect is found to be rather weak. Preorganizing the coordinating atoms of an extractant to their binding configuration as in the bound metal complex speeds up the binding process and significantly improves the kinetics of the separation process. This conclusion is validated by the synthesized 1,2-dihydrodipyrido[4,3-b;5,6-b]acridine (13) extractant, a preorganized derivative of the terpyridine extractant, which we experimentally showed was four times more effective than terpyridine at separating Am3+ from Eu3+ (SFAm/Eu ∼ 23 ± 1).

The strong interaction of actinyl ions with fullerenol driven by multiple hydrogen bonds.

The removal of actinides from radioactive wastewater is an important subject with the continuous application of nuclear energy. All-electron density functional theory (DFT) calculations were carried out to understand the adsorption behaviors of actinyl ions on C60(OH)24 fullerenol in this work. The outer-sphere (OS) bonding mode is more stable than the inner-sphere one because of the formation of multiple hydrogen bonds in the OS mode. The actinyl(VI) ions can be more efficiently absorbed by fullerenol than actinyl(V) ones. The bonding nature of actinyl ions with C60(OH)24 was revealed by various electron density topological analyses. Multiple hydrogen bonds formed in the OS complexes show moderate bond strength with partial covalent nature and are responsible for their high stability. IR spectra were fingerprinted to distinguish the interaction modes of actinyl ions with C60(OH)24.

Piperazinyl-Based Diamide Ligand for Selective Precipitation of Actinyl (UO22+/PuO22+) Ions with Fast Kinetics.

A novel ligand N,N'-bis(N″,N″-diethyl carbamoyl) piperazine (BDECP), L1, is synthesized as a selective precipitant for hexavalent actinyl (UO22+ and PuO22+) ions from an aqueous nitric acid medium. The ligand BDECP forms an infinite one-dimensional coordination polymer with uranyl nitrate and behaves as a bridging bidentate neutral donor. There is an alternate repetition of [UO2(NO3)2] and BDECP units as evidenced by single-crystal X-ray diffraction. Uranyl ion (UO22+) can be precipitated in >99% yield from an aqueous nitric acid medium. L1 shows fast kinetics of precipitation of uranyl ion as compared to those of other reported ligands like N-alkyl pyrolidone and N-(1-adamantyl) acetamide. Avrami's coefficient, obtained from the Avrami-Erofe'ev equation, shows that the precipitation mechanism is controlled by the phase boundary and not governed by diffusion. Theoretical studies of the uranyl complex of L1 show that there is no thermodynamic preference for L1 as compared to other potential amide-based precipitants. The principal factors that govern the fast kinetics of precipitation are the aqueous solubility and higher charge density on the amide oxygen of L1.

Computational Study of Actinyl Ion Complexation with Dipyriamethyrin Macrocyclic Ligands.

Relativistic density functional theory has been employed to characterize [AnO2(L)]0/-1 complexes, where An = U, Np, Pu, and Am, and L is the recently reported hexa-aza porphyrin analogue, termed dipyriamethyrin, which contains six nitrogen donor atoms (four pyrrolic and two pyridine rings). Shorter axial (An═O) and longer equatorial (An-N) bond lengths are observed when going from AnVI to AnV. The actinide to pyrrole nitrogen bonds are shorter as compared to the bonds to the pyridine nitrogens; the former also play a dominant role in the formation of the actinyl (VI and V) complexes. Natural population analysis shows that the pyrrole nitrogen atoms in all the complexes carry higher negative charges than the pyridine nitrogens. Upon binding actinyl ions with the ligand a significant ligand-to-metal charge transfer takes place in all the actinyl (VI and V) complexes. The formation energy of the actinyl(VI,V) complexes in the gas-phase is found to decrease in the order of UO2L > PuO2L > NpO2L > AmO2L. This trend is consistent with results for the formation of complexes in dichloromethane solution. The calculated ΔG and ΔH values are negative for all the complexes. Energy decomposition analysis (EDA) indicates that the interactions between actinyl(V/VI) and ligand are mainly controlled by electrostatic components over covalent orbital interactions, and the covalent character gradually decreases from U to Am for both pentavalent and hexavalent actinyl complexes.

Decisive Role of 5f-Orbital Covalence in the Structure and Stability of Pentavalent Transuranic Oxo [M6O8] Clusters.

Actinide metal oxo clusters are of vital importance in actinide chemistry, as well as in environmental and materials sciences. They are ubiquitous in both aqueous and nonaqueous phases and play key roles in nuclear materials (e.g., nuclear fuel) and nuclear waste management. Despite their importance, our structural understanding of the actinide metal oxo clusters, particularly the transuranic ones, is very limited because of experimental challenges such as high radioactivity. Herein we report a systematic theoretical study on the structures and stabilities of seven actinide metal oxo-hydroxo clusters [AnIV6O4(OH)4L12] (1-An; An = Th-Cm; L = O2CH-) along with their group 4 (Ti, Zr, Hf, Rf) and lanthanide (Ce) counterparts [MIV6O4(OH)4L12] (1-M). The work shows the Td-symmetric structures of all of the 1-An/M clusters and suggests the positions of the -OH functional groups, which are experimentally challenging to determine. Furthermore, by removing six electrons from 1-An, we found that oxidation could happen on the AnIV metal ions, producing [AnV6O4(OH)4L12]6+ (2-An; An = Pa, U, Np), or on the O2- and OH- ligands, producing [AnIV6(O•-)4(OH•)2(OH)2L12]6+ (3-An; An = Pu, Am, Cm). On the basis of 2-An, we constructed a series of tetravalent and pentavalent actinide metal oxo clusters [AnIV6O14]4- (4-An) and [AnV6O14]2+ (5-An), which proves the feasibility of the highly important pentavalent actinyl clusters, demonstrates the f orbital's structure-directing role in the formation of linear [O≡AnV═O]+ actinyl ions, and expands the concept of actinyl-actinyl interaction into pentavalent transuranic actinyl clusters.

Spectroscopic Study on Aqueous Uranyl(VI) Complexes with Methoxy- and Methylbenzoates: Electronic and Steric Effects of the Substituents

Aqueous complexation of uranyl(VI) ions with methoxy- and methylbenzoates in 0.1 M NaClO4 solutions was studied by means of UV-vis absorption and Raman spectroscopy. The predominance of 1:1 complexation (uranyl to ligand) was verified for all uranyl carboxylates under acidic conditions (-log [H+] < 3.2), and absorption spectra, stability constants, and symmetric stretching frequencies of the uranyl group of the complexes were determined for the first time. For meta- and para-substituted benzoates, a linear free energy relationship (LFER) was observed between the equilibrium constants for the protonation (log βP) and uranyl complexation (log βU) reactions, and the electronic effects of the substituents were successfully described by the Hammett equation. In the case of ortho-substituted benzoates, the stability constant of uranyl 2-methoxybenzoate is slightly lower than the LFER trend, which is generally explained by the destabilization of cross-conjugation in the uranyl complex due to the steric hindrance between the reaction center and adjacent methoxy group. On the contrary, the stability constant of uranyl 2-methylbenzoate is comparable to the LFER trend, implying that the steric effect is relatively insignificant for the smaller methyl group. The utility of such thermodynamic correlations between the uranyl-substituted benzoates is useful for the molecular understanding and predictive modeling of chemical interactions between actinyl(VI) ions and various organic carboxyl groups.

The role of cations in uranyl nanocluster association: a molecular dynamics study.

Actinyl ions can self-assemble in aqueous solution to form closed cage clusters ranging from 1.5 to 4.0 nm in diameter. The self-assembly, stability, and behavior of the nanoclusters depend on the nature of the aqueous environment, such as the pH and cations present. In this work, a classical force field for [(UO2)20(O2)30]20- (U20) peroxide nanoclusters in aqueous solution was developed from quantum-mechanical calculations. Using molecular dynamics simulations, the preferred binding sites of six cations (Li+, Na+, K+, Rb+, Cs+, and Ca2+) to the nanocluster were determined. Replica exchange molecular dynamics was used to equilibrate the structure and determine the equilibrium distribution of cations and water with respect to the nanocluster cage. In addition, the free energy barriers associated with cations entering the cluster were computed. Finally, the association of two cages was investigated by computing the free energy as a function of intercage distance. The free energy profiles reveal that the nanoclusters prefer to be associated when neutralized with divalent cations, but do not associate when neutralized with monovalent cations. This could explain the formation of tertiary structures observed experimentally.

Gas Phase Hydrolysis and Oxo-Exchange of Actinide Dioxide Cations: Elucidating Intrinsic Chemistry from Protactinium to Einsteinium.

Gas-phase bimolecular reactions of metal cations with water provide insights into intrinsic characteristics of hydrolysis. For the actinide dioxide cations, actinyl(V) AnO2 + , melding of experiment and computation provides insights into trends for hydrolysis, as well as for oxo-exchange between actinyls and water that proceeds by a hydrolysis pathway. Here this line of inquiry is further extended into the actinide series with CCSD(T) computations of potential energy surfaces, for the reaction pathway for oxo-exchange through hydrolysis of nine actinyl(V) ions, from PaO2 + to EsO2 + . The computed surfaces are in accord with previous experimental results for oxo-exchange, and furthermore predict spontaneous exchange for CmO2 + , BkO2 + , CfO2 + and EsO2 + , but not for AmO2 + . Natural Bond Order analysis of the species involved in both hydrolysis and oxo-exchange reveals an inverse correlation between the barrier to hydrolysis and the charge on the actinide centre, q(An). Based on this correlation, it can be concluded that hydrolysis, and related phenomena such as oxo-exchange, become less favourable as the charge on the metal centre decreases. The new results provide a straightforward rationalization of trends across a wide swathe of the actinide series.

Determining the kinetics of discrete aqueous redox reaction sub-steps using computational methods: Application to reactions of plutonyl (PuO2+/2+) with Fe2+, Fe3+, and hydroxyl radical (•OH)

The solubility and mobility of actinides, such as plutonium, are highly-dependent on their oxidation state, with the penta- and hexavalent species forming soluble actinyl ions (for example, PuO2+/2+). While significant data exist on the equilibrium thermodynamics of these species, the kinetic datasets for actinide reactions are less robust. To understand these reactions in greater detail, this study assesses the degree to which different sub-steps affect the overall rate of an aqueous reaction. In this approach, reactions are broken into three steps: (1) the diffusion of reactants toward each other in solution to form an outer-sphere complex, (2) the transition from outer- to inner-sphere complex, and (3) the transfer of an electron. We address encounter frequency using collision theory and the last two steps using quantum-mechanical modeling to analyze the energy, as well as atomic charges and spins, as a function of distance between the two reactants. This approach is applied to the reactions of PuO22+ and PuO2+ hydrolysis species with Fe2+, Fe3+, and hydroxyl radical (•OH) at high pH. Regardless of the hydration treatment scheme or spin configuration (explicit vs. explicit with an implicit continuum model; ferromagnetic vs. antiferromagnetic), once species are within distances of 7.3 to 11.0 A, the formation of an outer-sphere complex is found to be energetically favorable. This process proceeds rapidly even at low, environmentally-relevant plutonyl concentrations. The half-life of plutonyl in the bulk solution (that is, that which has not yet formed an outer-sphere complex) is found to be From the quantum-mechanical calculations, changes in system energy versus reactant distance reveal the transition from outer- to inner-sphere complex, along with specific changes to the physical and electronic structure. The energy gain associated with hydrogen bonding between the first hydration spheres drives the reaction to form progressively interconnected complexes. In the models with Fe2+, charge and spin analysis confirms the formation of the inner-sphere complex is coincident with the reduction of Pu5+ and Pu6+. Since there is no change in angular (spin) momentum of the overall system when the spins of Fe and plutonyl assume opposite directions (antiferromagnetic case) during this redox process, such a spin configuration is more likely to further electron transfer. Overall, the derived kinetics of the conversion between different complex configurations indicate that collision and outer-to-inner sphere conversion of these reactions proceed quickly and are likely not rate-limiting for these systems. This methodology can provide insight into rate-limiting sub-processes and allow us to explore the redox behavior of Pu and other metals in greater detail. The computational scheme can now be reasonably extended to determine the kinetics of complex formation at mineral-solution interfaces and also combined with Marcus theory calculations to determine explicit electron transfer rates for complex-dependent redox processes.

A molecular dynamics investigation of actinyl-ligand speciation in aqueous solution.

Actinyl ions (AnO2n+), the form in which actinides are commonly found in aqueous solution, are important species in the nuclear fuel cycle. These ions can form stable complexes with ionic ligands such as OH-, NO3-, Cl-, and even other actinyl ions in the aqueous phase. Knowledge of the relative stabilities of these complexes is important for the efficient design of separation processes used in recycling. These complexes also play a major role in the formation of actinide nanoclusters. A quantitative treatment of the stability of these actinyl ion complexes is therefore warranted. In the present work, molecular dynamics (MD) simulations have been performed to calculate the potential of mean force (PMF) between two actinyl ions (UO22+ and NpO2+) and various ligands (F-, Cl-, OH-, NO3-, SO42-, CO32-, Na+, and H2O) in explicitly-modeled aqueous solution. Equilibrium constants were calculated from the PMFs, and are consistent with experimental trends. Dication actinyls show stronger affinity for anions compared to monocation actinyls, whereas the opposite is true for cation-cation interactions between actinyls. Finally, the dynamics of actinyl-ligand contact ion pair (CIP) dissociation were characterized by calculating rate constants from transition state theory. The transmission coefficient, a dynamical correction factor used to correct for reaction barrier recrossing, was calculated for each actinyl-ligand CIP dissociation event.

Complexation of Pu(vi) with N,N,N',N'-tetramethyl-3-oxa-glutar-amide (TMOGA) and related ligands: optical properties and coordination modes.

The complexation of hexavalent plutonyl Pu(vi) with N,N,N',N'-tetramethyl-3-oxa-glutar-amide (TMOGA) and its carboxylate analogs, N,N-dimethyl-3-oxa-glutaramic acid (DMOGA) and oxydiacetic acid (ODA), has been studied in 1.0 M NaClO4 by absorption spectrophotometry and density functional theory (DFT). Both 1 : 1 and 1 : 2 complexes of Pu(vi) with TMOGA, DMOGA and ODA have been identified and their stability constants were obtained and compared with those of hexavalent U(vi) and pentavalent Np(v). The resultant stability constants indicate that the ability of the three ligands to complex with Pu(vi) decreases in the order of ODA > DMOGA > TMOGA. While for one given ligand, the stability constants of both the 1 : 1 and 1 : 2 complexes decrease generally in the order U(vi) > Pu(vi) > Np(v). The trends of the complexation strength have been elucidated by the calculated Mulliken atomic charges of the central metal cations. Furthermore, the coordination modes of the Pu(vi) complexes with TMOGA, DMOGA and ODA have been illustrated by analyses of the optical features of the complexes as well as by DFT calculations. The results demonstrate that the 1 : 2 Pu(vi)/TMOGA complex is centrosymmetric, while the 1 : 2 complexes of Pu(vi) with DMOGA and ODA are non-centrosymmetric. Moreover, different coordination modes have been observed in actinyl complexes with the same ligand, suggesting the structurally similar actinyl ions (U(vi), Pu(vi) and Np(v)) could exhibit quite different coordination behavior due to the variation of cation size and electronic structure.

Enzymatic activity of the CaM-PDE1 system upon addition of actinyl ions

The threat of a dirty bomb which could cause internal contamination has been of major concern for the past decades. Because of their high chemical toxicity and their presence in the nuclear fuel cycle, uranium and neptunium are two actinides of high interest. Calmodulin (CaM) which is a ubiquitous protein present in all eukaryotic cells and is involved in calcium-dependent signaling pathways has a known affinity for uranyl and neptunyl ions. The impact of the complexation of these actinides on the physiological response of the protein remains, however, largely unknown. An isothermal titration calorimetry (ITC) was developed to monitor in vitro the enzymatic activity of the phosphodiesterase enzyme which is known to be activated by CaM and calcium. This approach showed that addition of actinyl ions (AnO2n+), uranyl (UO22+) and neptunyl (NpO2+), resulted in a decrease of the enzymatic activity, due to the formation of CaM-actinide complexes, which inhibit the enzyme and alter its interaction with the substrate by direct interaction. Results from dynamic light scattering rationalized this result by showing that the CaM-actinyl complexes adopted a specific conformation different from that of the CaM-Ca2+ complex. The effect of actinides could be reversed using a hydroxypyridonate actinide decorporation agent (5-LIO(Me-3,2-HOPO)) in the experimental medium demonstrating its capacity to efficiently bind the actinides and restore the calcium-dependent enzyme activation.

Revealing Disparate Chemistries of Protactinium and Uranium. Synthesis of the Molecular Uranium Tetroxide Anion, UO4.

The synthesis, reactivity, structures, and bonding in gas-phase binary and complex oxide anion molecules of protactinium and uranium have been studied by experiment and theory. The oxalate ions, AnVO2(C2O4)-, where An = Pa or U, are essentially actinyl ions, AnVO2+, coordinated by an oxalate dianion. Both react with water to yield the pentavalent hydroxides, AnVO(OH)2(C2O4)-. The chemistry of Pa and U becomes divergent for reactions that result in oxidation: whereas PaVI is inaccessible, UVI is very stable. The UVO2(C2O4)- complex exhibits a remarkable spontaneous exothermic replacement of the oxalate ligand by O2 to yield UO4- and two CO2 molecules. The structure of the uranium tetroxide anion is computed to correspond to distorted uranyl, UVIO22+, coordinated in the equatorial plane by two equivalent O atoms each having formal charges of -1.5 and U-O bond orders intermediate between single and double. The unreactive nature of PaVO2(C2O4)- toward O2 is a manifestation of the resistance toward oxidation of PaV, and clearly reveals the disparate chemistries of Pa and U. The uranium tetroxide anion, UO4-, reacts with water to yield UO5H2-. Infrared spectra obtained for UO5H2- confirm the computed lowest-energy structure, UO3(OH)2-.

Structural Environment and Stability of the Complexes Formed Between Calmodulin and Actinyl Ions.

Because of their presence in the nuclear fuel cycle, neptunium and uranium are two actinides of main interest in case of internal contamination. Complexation of U(VI) and Np(V) by the target protein calmodulin (CaM(WT)) was therefore studied herein. Both actinides have two axial oxygen atoms, which, charge aside, makes them very similar structurally wise. This work combines spectroscopy and theoretical density functional theory (DFT) calculations. Structural characterization was performed by extended X-ray absorption fine structure (EXAFS) at the L(III)-edge for each studied actinide. Models for the binding site of the protein were developed and then refined by using DFT to fit the obtained experimental EXAFS data. The effect of hydrolysis was also considered for both actinides (the uranyl experiment was performed at pH 3 and 6, while the neptunyl experiment was conducted at pH 7 and 9). The effect of the pH variation was apparent on the coordination sphere of the uranyl complexes, while the neptunyl complex characteristics remained stable under both studied conditions. The DFT calculations showed that at near physiological pH the complex formed by CaM(WT) with the neptunium ion is more stable than the one formed with uranyl.

Reanalysis of the Aqueous Spectrum of the Neptunyl(V) [NpO2(+)] Ion.

The actinyl ions, consisting of the dioxoactinde(VI) and dioxoactinide(V) ions, are unique in the periodic table. However, very few quantitative studies of the spectra of these ions have been performed. In this paper the analysis of the optical spectrum of the aqueous neptunyl(V) [NpO2(+)] ion in 1 M HClO4 is reexamined. The species in solution is assumed to be the linear NpO2(+) ion surrounded in the equatorial plane by five oxygen atoms from five H2O molecules. The neptunyl(V) ion has the 5f(2) open-shell configuration, and the low-lying optical transitions (up to ∼20 000 cm(-1)) observed are primarily from the two 5f electrons occupying the 5fφ and 5fδ orbitals. The conventional parametric theory used for f(n) systems is applied to these low-lying transitions utilizing the intensity calculations that Matiska et al.1 have performed for this ion and the data reported by Eisenstein and Pryce.2 Possible ratios for the Slater electrostatic repulsion parameters are obtained from the data for the isoelectronic ion U(4+) (5f(2)) in various host crystals. The results are consistent with earlier crystal field analyses of the 5f(1) neptunyl(VI) [NpO2(2+)] ion.