Thorium Complexation with Aliphatic and Aromatic Hydroxycarboxylates: A Combined Experimental and Theoretical Study.

Hydroxycarboxylic acids, viz., α-hydroxyisobutyric acid (HIBA) and mandelic acid (MA), have been widely employed as eluents for inner transition metal separation studies. Both extractants have identical functional groups (OH and COOH) with different side-chains. Despite their similarities in binding motifs, they show different retention behaviors for thorium and uranium in liquid chromatography. To understand the mechanism behind the trend, a detailed study on the aqueous phase interaction of thorium with both extractants is carried out by speciation, spectroscopy, and density functional theory-based calculations. Potentiometric titration experiments are carried out to reveal the stability and species formed. Electrospray ionization mass spectrometry is performed to identify the formation of different species by Th with both HIBA and MA. It is seen that for Th-HIBA and Th-MA, the dominating species are ML3 and ML4, respectively. A similar pattern observed in potentiometric speciation analysis supports the tendency of Th to form higher stoichiometric species with MA than with HIBA. The difference in the dominating species thus helps in explaining the reversal in the retention behavior of uranium and thorium in the reverse-phase liquid chromatographic separation. The results obtained are corroborated with extended X-ray absorption fine structure spectroscopic measurements and density functional theory (DFT) calculations.

Additive energy functions have predictable landscape topologies.

Recent work [Mirth et al., J. Chem. Phys. 154, 114114 (2021)] has demonstrated that sublevelset persistent homology provides a compact representation of the complex features of an energy landscape in 3 N-dimensions. This includes information about all transition paths between local minima (connected by critical points of index ≥1) and allows for differentiation of energy landscapes that may appear similar when considering only the lowest energy pathways (as tracked by other representations, such as disconnectivity graphs, using index 1 critical points). Using the additive nature of the conformational potential energy landscape of n-alkanes, it became apparent that some topological features-such as the number of sublevelset persistence bars-could be proven. This work expands the notion of predictable energy landscape topology to any additive intramolecular energy function on a product space, including the number of sublevelset persistent bars as well as the birth and death times of these topological features. This amounts to a rigorous methodology to predict the relative energies of all topological features of the conformational energy landscape in 3N dimensions (without the need for dimensionality reduction). This approach is demonstrated for branched alkanes of varying complexity and connectivity patterns. More generally, this result explains how the sublevelset persistent homology of an additive energy landscape can be computed from the individual terms comprising that landscape.

Modulating Aggregation in Microemulsions: The Dispersion by Competitive Intermolecular Interaction Model.

A phenomenological model has been developed for the mechanism of action of phase modifiers as additives that control aggregation phenomena within water-in-oil emulsions. The "Dispersion by Competitive Intermolecular Interaction" model (DCI) explicitly considers the strength and prevalence of different intermolecular interactions that influence the molecular association of amphiphiles, the resulting distribution of aggregate size, and interaggregate interactions that influence phase phenomena. The existing "cosolvent" and "cosurfactant" association models, which describe the distribution of these amphiphiles within the solution, are re-examined in the context of intermolecular interactions. The different contributions of intermolecular interactions to the potential energy landscape of molecular association create distinct regimes within the DCI model that explain prior observations of cosolvent and cosurfactant behavior. The specific system under consideration, the N,N,N',N'-tetraoctyl diglycolamide amphiphile extractant with tributyl phosphate or dihexyl octanamide phase modifier additives, represents a new regime-labeled the polar disruption regime-where strong hydrogen bonding of the phase modifier with the polar-solutes disrupts the internal hydrogen bonding network of the polar micellar core, thereby decreasing aggregate size and narrowing the polydispersity in solution.

Role of O Substitution in Expanded Porphyrins on Uranyl Complexation: Orbital- and Density-Based Analyses.

Search for new U(VI) sequestering macrocyclic ligands is an important area of research due to manifold applications. Besides hard- or soft-donor-based ligands, mixed-donor ligands are also gaining popularity in achieving optimized performances. However, how the combination of hard-soft-donor centers alters the bonding interactions with U(VI) is still not well-understood. Moreover, a consensus is yet to be reached on the nature and role of underlying covalent interactions in mixed N,O-donor ligands. In this work, using the relativistic density functional theory (DFT), we attempted to address these intriguing issues by investigating the subtle change in bonding characteristics of the uranyl ion upon binding with an expanded porphyrin, viz. sapphyrin, with subsequent O substitutions at the cavity. The results obtained from a range of modern analysis tools suggest that in the O-substituted sapphyrin variants, UO22+ prefers to bind with N over O, and an increase in the number of O-donor sites at the cavity prompts UO22+ to have a better interaction with the rest of the N-donor-centers. Although O donors are involved in more numbers of mixed molecular orbitals, the variation in the amplitude of overlap and the better σ-donation ability favor N to have stronger bonding interactions with uranyl. Molecular orbital (MO) and density of states (DOS) analyses show favorable participation of U(d), and the involvement of U(f) orbitals in bonding is of a low extent but non-negligible. Although electrostatic interaction dominates at U-O/N bonds in the equatorial plane, the quantum theory of atoms in molecules descriptors, MO analysis, and overlap-integral calculations confirm the presence of underlying near-degeneracy-driven covalent interactions.

Achieving highly efficient and selective cesium extraction using 1,3-di-octyloxycalix[4]arene-crown-6 in n-octanol based solvent system: experimental and DFT investigation.

Due to the long half-life of 137Cs (t 1/2 ∼ 30 years), the selective extraction of cesium (Cs) from high level liquid waste is of paramount importance in the back end of the nuclear fuel cycle to avoid long term surveillance of high radiotoxic waste. As 1,3-di-octyloxycalix[4]arene-crown-6 (CC6) is suggested to be a promising candidate for selective Cs extraction, the improvement in the Cs extraction efficiency by CC6 has been investigated through the optimization of the effect of dielectric media on the extraction process. The effects of the feed acid (HNO3, HCl, and HClO4) and the composition of the diluents for the ligand in the organic phase on the extraction efficiency of Cs have been investigated systematically. In 100% n-octanol medium, Cs is found to form a 1 : 1 ion-pair complex with CC6 (0.03 M) providing a very high distribution ratio of D Cs ∼ 22, suggesting n-octanol as the most suitable diluent for Cs extraction. No significant interference of other relevant cations such as Na, Mg and Sr was observed on the D Cs value in the optimized solvent system. Density functional theory (DFT) based calculations have been carried out to elucidate the reason of ionic selectivity and enhanced Cs extraction efficiency of CC6 in the studied diluent systems. In addition to the ionic size-based selectivity of the crown-6 cavity, the polarity of the organic solvent system, the hydration energy of the ion, and the relative reorganization of CC6 upon complexation with Cs are understood to have roles in achieving the enhanced efficiency for the extraction of Cs by the CC6 extractant in nitrobenzene medium.

Periodic trends and complexation chemistry of tetravalent actinide ions with a potential actinide decorporation agent 5-LIO(Me-3,2-HOPO): A relativistic density functional theory exploration.

A relativistic density functional theory (DFT) study is reported which aims to understand the complexation chemistry of An4+ ions (An = Th, U, Np, and Pu) with a potential decorporation agent, 5-LIO(Me-3,2-HOPO). The calculations show that the periodic change of the metal binding free energy has an excellent correlation with the ionic radii and such change of ionic radii also leads to the structural modulation of actinide-ligand complexes. The calculated structural and binding parameters agree well with the available experimental data. Atomic charges derived from quantum theory of atoms in molecules (QTAIM) and natural bond order (NBO) analysis shows the major role of ligand-to-metal charge transfer in the stability of the complexes. Energy decomposition analysis, QTAIM, and electron localization function (ELF) predict that the actinide-ligand bond is dominantly ionic, but the contribution of orbital interaction is considerable and increases from Th4+ to Pu4+ . A decomposition of orbital contributions applying the extended transition state-natural orbital chemical valence method points out the significant π-donation from the oxygen donor centers to the electron-poor actinide ion. Molecular orbital analysis suggests an increasing trend of orbital mixing in the context of 5f orbital participation across the tetravalent An series (Th-Pu). However, the corresponding overlap integral is found to be smaller than in the case of 6d orbital participation. An analysis of the results from the aforementioned electronic structure methods indicates that such orbital participation possibly arises due to the energy matching of ligand and metal orbitals and carries the signature of near-degeneracy driven covalency.

Enhancing Actinide(III) over Lanthanide(III) Selectivity through Hard-by-Soft Donor Substitution: Exploitation and Implication of Near-Degeneracy-Driven Covalency.

Soft donor ligands often provide higher selectivity for actinides(III) over chemically similar lanthanides(III), e.g., in the AmIII-EuIII pair. Frequently, the origin of such selectivity is associated with an increased covalency in actinide-ligand bonding. However, the relationship between the degree of covalency and ion selectivity has yet to reach general consensus. Further, it is unclear whether the enhanced covalency leads to a thermodynamic stabilization of the complex or not. Using relativistic density functional theory, we have addressed these outstanding issues by analyzing the subtle change of metal-ligand interactions from a hard donor ligand to a mixed soft-hard one. The present comparative study on the structure of and binding in Am3+ and Eu3+ complexes with 3,4,3-LI(1,2-HOPO) (L) and its mixed-donor variant (LS) shows that the introduction of sulfur as a soft donor atom into the metal coordination sphere indeed infuses an Am3+ selectivity into the otherwise nonselective ligand L but also leads to a significant reduction of the metal-binding Gibbs free energies. Natural population analysis, charge decomposition analysis, and its extended version point to the critical role of ligand-to-metal charge transfer in the overall thermodynamic stability of the complexes. A detailed energy decomposition analysis combining the extended transition state with the natural orbitals chemical valence method reveals an enhancement of the covalency upon switching to the soft-hard donor ligand because of the different nature of the metal-ligand interaction. The ligand L predominantly binds the metal via π donation, whereas the ligand LS prefers σ donation. Molecular orbital and quantum theory of atoms in molecules analyses as well as a comparison to a simple model system show that the covalency occurs as a result of orbital mixing and is near-degeneracy-driven in nature. This enhanced covalency, however, fails to thermodynamically compensate for the loss of strong electrostatic interaction and thus does not lead to an additional stabilization of the metal-LS complexes.

Thorium decorporation efficacy of rationally-selected biocompatible compounds with relevance to human application.

During civil, nuclear or defense activities, internal contamination of actinides in humans and mitigation of their toxic impacts are of serious concern. Considering the health hazards of thorium (Th) internalization, an attempt was made to examine the potential of ten rationally-selected compounds/formulations to decorporate Th ions from physiological systems. The Th-induced hemolysis assay with human erythrocytes revealed good potential of tiron, silibin (SLB), phytic acid (PA) and Liv.52® (L52) for Th decorporation, in comparison to diethylenetriaminepentaacetic acid, an FDA-approved decorporation drug. This was further validated by decorporation experiments with relevant human cell models (erythrocytes and liver cells) and biological fluid (blood) under pre-/post-treatment conditions, using inductively coupled plasma mass spectrometry (ICP-MS) and transmission electron microscopy (TEM). Furthermore, density functional theory-based calculations and extended X-ray absorption fine structure (EXAFS) spectroscopy confirmed the formation of Th complex by these agents. Amongst the chosen biocompatible agents, tiron, SLB, PA and L52 hold promise to enhance Th decorporation for human application.

The coordination chemistry of lanthanide and actinide metal ions with hydroxypyridinone-based decorporation agents: orbital and density based analyses.

In the context of the mitigation of the biological effects of internal radionuclide contamination and for efficient decorporation, the design and development of efficient chelators for lanthanide and actinide metal ions has become a central issue. The pioneering work of Raymond and coworkers (Chem. Rev., 2003, 103, 4207-4282) led to the development of siderophore-related hydroxypyridinonate ligands for possible treatment of internalized radionuclides. However, the structure-function relationship of Ln/An bound to these ligands, particularly the bonding and coordination aspects are not clearly understood at the atomic level. Here, we have investigated the structure, binding and energetics of trivalent and tetravalent Ln/An (Sm3+, Eu3+, Am3+, Cm3+, Th4+, Pu4+) ions with spermine-based octadentate hydroxypyridinonate chelators, namely 3,4,3-LI(1,2-HOPO) and its 3,3,3 variant, using relativistic density functional theory (DFT). Furthermore, we have performed orbital and density based analyses to elucidate the nature of bonding in these complexes. In accordance with the experimental stability constant, we found the maximum binding free energy for An4+ (Pu4+, Th4+) as compared to trivalent metal ions. CDA and ECDA analyses along with orbital-based population analyses confirmed the higher ligand to metal charge transfer for An4+ than for trivalent metal ions. Furthermore, the aromaticity index analysis suggested the presence of crucial chelatoaromatic stabilization for all these metal ions with the maximum for An4+. QTAIM descriptors indicated that the binding of An/Ln with the hard oxygen donor of the ligands is of the donor-acceptor type but a higher degree of covalency exists for actinides as compared to lanthanides. Furthermore, QTAIM and molecular orbital analysis confirmed that such covalency is of the energy-driven type and strictly originates from the orbital mixing event of An-5f orbitals with the ligand orbitals.

Unusual intramolecular CHO hydrogen bonding interaction between a sterically bulky amide and uranyl oxygen.

The selective separation of toxic heavy metals such as uranyl can be accomplished using ligands with stereognostic hydrogen bonding interactions to the uranyl oxo group, as proposed by Raymond and co-workers (T. S. Franczyk, K. R. Czerwinski and K. N. Raymond, J. Am. Chem. Soc., 1992, 114, 8138-8146). Recently, several ligands possessing this weak interaction have been proposed involving the hydrogen bonding of NH and OH based moieties with uranyl oxygen. We herein report the structurally and spectroscopically characterized CHO hydrogen bonding using a sterically bulky amide based ligand. In conjunction with experiments, electronic structure calculations are carried out to understand the structure, binding and the strength of the CHO hydrogen bonding interactions. This weak interaction is mainly due to the steric effect caused by a bulky substituent around the donor group which has direct relevance in designing novel ligands in nuclear waste management processes. Although the kinetics are very slow, the ligand is also highly selective to uranyl in the presence of other interfering ions such as lanthanides.

Divalent ions are potential permeating blockers of the non-selective NaK ion channel: combined QM and MD based investigations.

The bacterial NaK ion channel is distinctly different from other known ion channels due to its inherent non-selective feature. One of the unexplored and rather interesting features is its ability to permeate divalent metal ions (such as Ca2+ and Ba2+) and not monovalent alkali metal ions. Several intriguing questions about the energetics and structural aspects still remain unanswered. For instance, what causes Ca2+ to permeate as well as block the selectivity filter (SF) of the NaK ion channel and act as a "permeating blocker"? How and at what energetic cost does another chemical congener, Sr2+, as well as Ba2+, a potent blocker of the K+ ion channel, permeate through the SF of the NaK ion channel? Finally, how do their translocation energetics differ from those of monovalent ions such as K+? Here, in an attempt to address these outstanding issues, we elucidate the structure, binding and selectivity of divalent ions (Ca2+, Sr2+ and Ba2+) as they permeate through the SF of the NaK ion channel using all-atom molecular dynamics simulations and density functional theory based calculations. We unveil mechanistic insight into this translocation event using well-tempered metadynamics simulations in a polarizable environment using the mean-field model of water and incorporating electronic continuum corrections for ions via charge rescaling. The results show that, akin to K+ coordination, Sr2+ and Ba2+ bind at the SF in a very similar fashion and remain octa-coordinated at all sites. Interestingly, differing from its local hydration structure, Ca2+ interacts with eight carbonyls to remain at the middle of the S3 site. Furthermore, the binding of divalent metals at SF binding sites is more favorable than the binding of K+. However, their permeation through the extracellular entrance faces a considerably higher energetic barrier compared to that for K+, which eventually manifests their inherent blocking feature.

Speciation of uranium-mandelic acid complexes using electrospray ionization mass spectrometry and density functional theory.

RATIONALE: Mandelic acid is a complexing agent employed for the liquid chromatographic separation of actinides. However, the types of species and the structural details of the uranyl-mandelate complexes are still unknown. Understanding the nature of these complex species would provide better insight into the mechanism of their separation in liquid chromatography. METHODS: Formation of different species of the uranyl ion (UO2 ) with mandelic acid was studied using electrospray ionization mass spectrometry (ESI-MS) with a quadrupole time-of-flight analyzer. The different species of uranyl nitrate with mandelic acid (MA) at ligand (L) to metal ratios in the range 1-10 were examined in both positive and negative ion modes. The stability of different species with the possible pathways of formation was scrutinized using density functional theory (DFT) calculations. RESULTS: In negative ion mode, nitrate-containing UO2 (MA)1 , UO2 (MA)2 and UO2 (MA)3 species were found in good abundance. In positive ion mode, under-coordinated uranyl-mandelate species, and solvated (S) species of types UO2 (MA)1 (S), UO2 (MA)1 (S)2 and UO2 (MA)2 (S), were observed whereas nitrate-containing species were absent. Interestingly, doubly and singly charged dimeric species were also identified in positive ion mode. The theoretically computed energetics of the various species are in close agreement with their experimentally observed intensities in ESI-MS. CONCLUSIONS: The most intense peak observed in ESI-MS, UO2 (MA)3 , was found to be the energetically most favorable amongst different UO2 (MA)n type species. Metal-ligand equilibria studied in the two modes yielded similar results. The combined experimental and quantum chemical investigations predict that T-shape complexes may be formed even in the gas phase. Copyright © 2016 John Wiley & Sons, Ltd.

Evaluation of an Ultrafast Molecular Rotor, Auramine O, as a Fluorescent Amyloid Marker.

Recently, Auramine O (AuO) has been projected as a fluorescent fibril sensor, and it has been claimed that AuO has an advantage over the most extensively utilized fibril marker, Thioflavin-T (ThT), owing to the presence of an additional large red-shifted emission band for AuO, which was observed exclusively for AuO in the presence of fibrillar media and not in protein or buffer media. As fibrils are very rich in ß-sheet structure, a fibril sensor should be more specific toward the ß-sheet structure so as to produce a large contrast between the fibril form and native protein form, for efficient detection and in vitro mechanistic studies of fibrillation. However, in this report, we show that AuO interacts significantly with the native form of bovine serum albumin (BSA), which is an all-α-helical protein and lacks the ß-sheet structure, which are the hallmarks of a fibrillar structure. This strong interaction of AuO with the native form of BSA leads to a large emission enhancement of AuO for the native protein itself, and leads to a low contrast between the BSA protein and its fibrils. More importantly, the large red-shifted emission band of AuO, reported in the presence of human insulin fibrils, and which was projected as its major advantage over ThT, is not observed in the presence of BSA fibrils as well as fibrils from other proteins, such as lysozyme, human serum albumin, and ß-lactoglobulin. Thus, our results provide information on the universal applicability of the distinctive and claimed-to-be-advantageous photophysical features reported for AuO in human insulin fibrils towards fibrils from other proteins. Time-resolved fluorescence measurements also support the proposition of a strong interaction of AuO with native BSA. Additionally, tryptophan emission of the protein has been explored to further elucidate the binding mechanism of AuO with native BSA. Evaluation of thermodynamic parameters revealed that the binding of AuO with native BSA involved positive enthalpy and entropy changes, suggesting dominant contributions from hydrophobic and electrostatic interactions toward the association of AuO with native BSA. Molecular docking calculations have been performed to identify the principal binding location of AuO in native BSA.

Asn47 and Phe114 modulate the inner sphere reorganization energies of type zero copper proteins.

The geometric structures and electron transfer properties of type 1 Cu proteins are reasonably understood at the molecular level (E. I. Solomon and R. G. Hadt, Coord. Chem. Rev., 2011, 255, 774-789, J. J. Warren, K. M. Lancaster, J. H. Richards and H. B. Gray, J. Inorg. Biochem., 2012, 115, 119-126). Much understanding of type 1 copper electron transfer reactivity has come from site directed mutagenesis studies. For example, artificial "type zero" Cu-centres constructed in cupredoxin-azurin have showcased the capacity of outer-sphere hydrogen bonding networks to enhance Cu II/I electron transfer reactivity. In this paper, we have elaborated on earlier kinetics and electronic structural studies of type zero Cu by calculating the inner sphere reorganization energies of type 1, type 2, and type zero Cu proteins using density functional theory (DFT). Although the choice of density functionals for copper systems is not straightforward, we have benchmarked the density functionals against the recently reported ESI-PES data for two synthetic copper models (S. Niu, D.-L. Huang, P. D. Dau, H.-T. Liu, L.-S. Wang and T. J. Ichiye, Chem. Theory Comput., 2014, 10, 1283). For the Cu proteins, our calculations predict that changes in the coordination number upon metal reduction lead to large inner sphere reorganization energies for type 2 Cu sites, whereas retention in the coordination number is observed for type zero Cu sites. These variations in the coordination number are modulated by the outer-sphere coordinating residues Asn47 and Phe114, which are involved in hydrogen bonding with the Asp112 side chain.

Selective recognition of uranyl ions from bulk of thorium(iv) and lanthanide(iii) ions by tetraalkyl urea: a combined experimental and quantum chemical study.

The selective separation of uranyl ions from an aqueous solution is one of the most important criteria for sustainable nuclear energy production. We report herein a known, but unexplored extractant, tetraalkyl urea, which shows supreme selectivity for uranium in the presence of interfering thorium and other lanthanide ions from a nitric acid medium. The structural characterization of the uranyl complex (UO2X2·2L, where X = NO3(-), Cl(-) and Br(-)) by IR, NMR and single crystal X-ray diffraction provides insight into the strong interaction between the uranyl ion and the ligand. The origin of this supreme selectivity for uranyl ions is further supported by electronic structure calculations. Uranyl binding with the extractant is thermodynamically more favourable when compared to thorium and the selectivity is achieved through a combination of electronic and steric effects.

Efficient Separation of Europium Over Americium Using Cucurbit-[5]-uril Supramolecule: A Relativistic DFT Based Investigation.

Achieving an efficient separation of chemically similar Am(3+)/Eu(3+) pair in high level liquid waste treatment is crucial for managing the long-term nuclear waste disposal issues. The use of sophisticated supramolecules in a rigid framework could be the next step toward solving the long-standing problem. Here, we have investigated the possibility of separating Am(3+)/Eu(3+) pair with cucurbit-[5]-uril (CB[5]), a macrocycle from the cucurbit-[n]-uril family, using relativistic density functional theory (DFT) based calculations. We have explored the structures, binding, and energetics of metal-CB[5] complexation processes with and without the presence of counterions. Our study reveals an excellent selectivity of Eu(3+) over Am(3+) with CB[5] (ion exchange free energy, ΔΔGAm/Eu > 10 kcal mol(-1)). Both metals bind with the carbonyl portals via µ(5) coordination arrangement with the further involvement of three external water molecules. The presence of counterions, particularly nitrate, inside the hydrophobic cavity of CB[5], induces a cooperative cation-anion binding, resulting in enhancement of metal binding at the host. The overall binding process is found to be entropy driven resembling the recent experimental observations (Rawat et al. Dalton Trans. 2015, 44, 4246-4258). The optimized structural parameters for Eu(3+)-CB[5] complexes are found to be in excellent agreement with the available experimental information. To rationalize the computed selectivity trend, electronic structures are further scrutinized using energy decomposition analysis (EDA), quantum theory of atom in molecules (QTAIM), Mülliken population analysis (MPA), Nalewajski-Mrojek (NM) bond order, and molecular orbital analyses. Strong electrostatic ion-dipole interaction along with efficient charge transfer between CB[5] and Eu(3+) outweighs the better degree of covalency between CB[5] and Am(3+) leading to superior selectivity of Eu(3+) over Am(3+).

Selectivity of a Singly Permeating Ion in Nonselective NaK Channel: Combined QM and MD Based Investigations.

Ion channels, such as potassium channels are known to discriminate ions to achieve remarkable selective transportation of K(+) over Na(+) through the membrane. The recently reported NaK ion channel, on the contrary, seems to be an exception, as it is observed to permeate most of the group IA alkali metal cations and hence is suggested to be nonselective in nature. However, does that correspond to a complete annihilation of selectivity inside the selectivity filter (SF) of the channel? What is the origin of such nonselectivity/selectivity, if any? The present computational study is an extensive multiscale modeling approach to find the probable answers to these intriguing questions. Here, we have used density functional theory (DFT) based calculations using a realistic truncated model of SF from the crystal structures of the NaK ion channel to evaluate the binding of various alkali metal ions (Na(+), K(+) and Cs(+)), free from "contamination" due to the absence any other "rivalry" cations, in its different binding sites. Among all of the possible binding sites, a vestibule is noticed to be nonselective and seen to act as a probable binding site only in the presence of multiple ions. Binding sites S3 and S4 are found to be selective for K(+) and Na(+), respectively. As an important observation, we find that calculations on oversimplified models using an isolated ion binding site may lead to an erroneous selectivity trend as it neglects the synergetics of consecutive binding sites on the final outcome. Energy decomposition analysis revealed ion-dipole electrostatics as the major contributing interaction in metal-bound binding sites. Our investigations find that although NaK is permeable to monovalent alkali metal ions, strongly "site specific" selectivity does exist at the three well-defined noncontiguous binding sites of the SF. Different important physicomechanical parameters (such as ligating environment, synergistic influence of binding sites, and topological constraints) are found to be the determining factor to induce the "site specific" selectivity of ions during translocation. Wherever possible, our computed results are compared with the available experimental findings. We finally conduct a detailed umbrella sampling-corrected metadynamics simulation in order to obtain an ion permeation free energy landscape within the SF that corroborates well with the "site specific" selectivity trend.

Elucidating the structures and cooperative binding mechanism of cesium salts to the multitopic ion-pair receptor through density functional theory calculations.

Designing new and innovative receptors for the selective binding of radionuclides is central to nuclear waste management processes. Recently, a new multi-topic ion-pair receptor was reported which binds a variety of cesium salts. Due to the large size of the receptor, quantum chemical calculations on the full ion-pair receptors are restricted, thus the binding mechanisms are not well understood at the molecular level. We have assessed the binding strengths of various cesium salts to the recently synthesized multi-topic ion-pair receptor molecule using density functional theory based calculations. Our calculations predict that the binding of cesium salts to the receptor predominantly occurs via the cooperative binding mechanism. Cesium and the anion synergistically assist each other to bind favorably inside the receptor. Energy decomposition analysis on the ion-pair complexes shows that the Cs salts are bound to the receptor mainly through electrostatic interactions with small contribution from covalent interactions for large ionic radius anions. Further, QTAIM analysis characterizes the importance of different inter-molecular interactions between the ions and the receptor inside the ion-pair complexes. The role of the crystallographic solvent molecule contributes significantly by ~10 kcal mol(-1) to the overall binding affinities which is quite significant. Further, unlike the recent molecular mechanics (MM) calculations, our calculated binding affinity trends for various Cs ion-pair complexes (CsF, CsCl and CsNO3) are now in excellent agreement with the experimental binding affinity trends.

Water-Mediated Differential Binding of Strontium and Cesium Cations in Fulvic Acid.

The migration of potentially harmful radionuclides, such as cesium ((137)Cs) and strontium ((90)Sr), in soil is governed by the chemical and biological reactivity of soil components. Soil organic matter (SOM) that can be modeled through fulvic acid (FA) is known to alter the mobility of radionuclide cations, Cs(+) and Sr(2+). Shedding light on the possible interaction mechanisms at the atomic level of these two ions with FA is thus vital to explain their transport behavior and for the design of new ligands for the efficient extraction of radionuclides. Here we have performed molecular dynamics, metadynamics simulations, and density-functional-theory-based calculations to understand the binding mechanism of Sr(2+) and Cs(+) cations with FA. Our studies predict that interaction of Cs(+) to FA is very weak as compared with Sr(2+). While the water-FA interaction is largely responsible for the weak binding of Cs(+) to FA, leading to the outer sphere complexation of the ion with FA, the interaction between Sr(2+) and FA is stronger and thus can surpass the existing secondary nonbonding interaction between coordinated waters and FA, leading to inner sphere complexation of the ion with FA. We also find that entropy plays a dominant role for Cs(+) binding to FA, whereas Sr(2+) binding is an enthalpy-driven process. Our predicted results are found to be in excellent agreement with the available experimental data on complexation of Cs(+) and Sr(2+) with SOM.

Effect of successive alkylation of N,N-dialkyl amides on the complexation behavior of uranium and thorium: solvent extraction, small angle neutron scattering, and computational studies.

The effect of successive alkylation of the Cα atom adjacent to the carbonyl group in N,N-dialkyl amides (i.e., di(2-ethylhexyl)acetamide (D2EHAA), di(2-ethylhexyl)propionamide (D2EHPRA), di(2-ethylhexyl)isobutyramide (D2EHIBA), and di(2-ethylhexyl)pivalamide (D2EHPVA)) on the extraction behavior of hexavalent uranium (U(VI)) and tetravalent thorium (Th(IV)) ions has been investigated. These studies show that the extraction of Th(IV) is significantly suppressed compared to that of U(VI) with increased branching at the Cα atom adjacent to the carbonyl group. Small angle neutron scattering (SANS) studies showed an increased aggregation tendency in the presence of nitric acid and metal ions. D2EHAA showed more aggregation compared to its branched homologues, which explains its capacity for higher extraction of metal ions. These experimental observations were further supported by density function theory calculations, which provided structural evidence of differential binding affinities of these extractants for uranyl cations. The complexation process is primarily controlled by steric and electronic effects. Quantum chemical calculations showed that local hardness and polarizability can be extremely useful inputs for designing novel extractants relevant to a nuclear fuel cycle.