Highly Tunable 4-Phosphoryl Pyrazolone Receptors for Selective Rare-Earth Separation.

Highly selective rare-earth separation has become increasingly important due to the indispensable role of these elements in various cutting-edge technologies including clean energy. However, the similar physicochemical properties of rare-earth elements (REEs) render their separation very challenging, and the development of new selective receptors for these elements is potentially of very considerable economic and environmental importance. Herein, we report the development of a series of 4-phosphoryl pyrazolone receptors for the selective separation of trivalent lanthanum, europium, and ytterbium as the representatives of light, middle, and heavy REEs, respectively. X-ray crystallography studies were employed to obtain solid-state structures across 11 of the resulting complexes, allowing comparative structure-function relationships to be probed, including the effect of lanthanide contraction that occurs along the series from lanthanum to europium to ytterbium and which potentially provides a basis for REE ion separation. In addition, the influence of ligand structure and lipophilicity on lanthanide binding and selectivity was systematically investigated via n-octanol/water distribution and liquid-liquid extraction (LLE) studies. Corresponding stoichiometry relationships between solid and solution states were well established using slope analyses. The results provide new insights into some fundamental lanthanide coordination chemistry from a separation perspective and establish 4-phosphoryl pyrazolone derivatives as potential practical extraction reagents for the selective separation of REEs in the future.

Selective Separation of Lithium, Magnesium and Calcium using 4-Phosphoryl Pyrazolones as pH-Regulated Receptors.

Ensuring continuous and sustainable lithium supply requires the development of highly efficient separation processes such as LLE (liquid-liquid extraction) for both primary sources and certain waste streams. In this work, 4-phosphoryl pyrazolones are used in an efficient pH-controlled stepwise separation of Li+ from Ca2+ , Mg2+ , Na+ and K+ . The factors affecting LLE process, such as the substitution pattern of the extractant, diluent/water distribution, co-ligand, pH, and speciation of the metal complexes involved, were systematically investigated. The maximum extraction efficiency of Li+ at pH 6.0 was 94 % when Mg2+ and Ca2+ were previously separated at pH<5.0, proving that the separation of these ions is possible by simply modulating the pH of the aqueous phase. Our study points a way to separation of lithium from acid brine or from spent lithium ion battery leaching solutions, which supports the future supply of lithium in a more environmentally friendly and sustainable manner.

Surface ion-imprinted brewer's spent grain with low template loading for selective uranyl ions adsorption from simulated wastewater.

Efficient removal of uranyl ions from wastewater requires excellent selectivity of the adsorbents. Herein, we report a new strategy using a high monomer/template molar ratio of 500:1 to prepare surface ion-imprinted brewer's spent grain (IIP-BSG) for selective U(VI) removal using binary functional monomers (2-hydroxyethyl methacrylate and diethyl vinylphosphonate) with high site accessibility and easy template removal. IIP-BSG exhibits a maximum U(VI) adsorption capacity of 165.7 mg/g, a high selectivity toward U(VI) in the presence of an excess amount of Eu(III) (Eu/U molar ratio = 20), a good tolerance of salinity, and a high reusability. In addition, mechanism studies have revealed electrostatic interaction and a coordination of uranyl ions by carboxyl and phosphoryl groups, the predominant contribution of high-energy (specific) sites during selective adsorption, and internal mass transfer as the rate-controlling step of U(VI) adsorption. Furthermore, IIP-BSG shows great potentials to separate U(VI) from lanthanides in simulated nuclear wastewater (pH0 = 3.5) and selectively concentrate U(VI) from simulated mine water (pH0 = 7.1). This study proves that the ion-imprinting effect can be achieved using a very low template amount with reduced production cost and secondary pollution, which benefits large-scale promotion of the ion-imprinted materials for selective uranyl ions removal.

One-pot synthesis of brewer's spent grain-supported superabsorbent polymer for highly efficient uranium adsorption from wastewater.

High-efficient and fast adsorption of uranium is important to reduce the hazards caused by the uranium contamination of water environment due to the increased human activities. Herein, brewer's spent grain (BSG)-supported superabsorbent polymers (SAP) with different cross-linking densities are prepared as cheap and eco-friendly adsorbents for the first time via one-pot swelling and graft polymerization. A 7 wt% NaOH solution is used to swell BSG before grafting and subsequently neutralize the acrylic acid to control the reaction rate without producing alkaline wastewater. Compared with the traditional methods, swelling improves the grafting density and the utilization of raw materials due to the increased disorder degree of the BSG fibers. This results in the grafting of abundant carboxyl and amide groups onto the BSG backbone, forming a strongly hydrophilic polymer network of the BSG-SAP. Compared with the reference polymers without BSG, BSG-SAP presents higher adsorption capacity and enhanced reusability. The highly cross-linked BSG-SAP (BSG-SAP-H) shows an outstanding adsorption capacity of U(VI) (1465 mg/g at pH0 = 4.6), a fast adsorption rate (81% of equilibrium adsorption capacity in 15 min), and a high selectivity in the presence of competing ions. Adsorption mechanism studies reveal the involvement of amide groups, a bidentate binding structure between UO22+ and the carboxyl groups, and a cation exchange between Na+ and UO22+. More importantly, the adsorption capacity of BSG-SAP-H reaches 254.4 mg/g in the fixed-bed column experiment at a low initial concentration (c0(U) = 30 mg/L) and keeps 80% of the adsorption capacity after four cycles, indicating a great potential for uranium removal from wastewater. This work shows a suitable approach to explore the untreated biomass to prepare SAP with enhanced adsorption performance via a general and low-cost strategy.

Insights at the molecular level into the formation of oxo-bridged trinuclear uranyl complexes.

Reaction of 1,3,4,6-tetra-O-acetyl-N-(2-hydroxy)-naphthylidene glucosamine (HL(Ac)) with uranyl acetate in ethanol leads to formation of dinuclear [(UO2)2(L)2] (1). In a second step 1 is quantitatively transferred into the trinuclear oxo-bridged complex [(UO2)3(µ3-O)(L)3]2- (22-) via deprotonation and coordination of a water molecule. This transformation was followed by NMR and UV/Vis spectroscopy and it proved possible to selectively introduce 18O into the µ3-bridge.

4-Phosphoryl Pyrazolones for Highly Selective Lithium Separation from Alkali Metal Ions.

Effective receptors for the separation of Li+ from a mixture with other alkali metal ions under mild conditions remains an important challenge that could benefit from new approaches. In this study, it is demonstrated that the 4-phosphoryl pyrazolones, HL2 -HL4 , in the presence of the typical industrial organophosphorus co-ligands tributylphosphine oxide (TBPO), tributylphosphate (TBP) and trioctylphosphine oxide (TOPO), are able to selectively recognise and extract lithium ions from aqueous solution. Structural investigations in solution as well as in the solid state reveal the existence of a series of multinuclear Li+ complexes that include dimers (TBPO, TBP) as well as rarely observed trimers (TOPO) and represent the first clear evidence for the synergistic role of the co-ligands in the extraction process. Our findings are supported by detailed NMR, MS and extraction studies. Liquid-liquid extraction in the presence of TOPO revealed an unprecedented high Li+ extraction efficiency (78 %) for HL4 compared to the use of the industrially employed acylpyrazolone HL1 (15 %) and benzoyl-1,1,1-trifluoroacetone (52 %) extractants. In addition, a high selectivity for Li+ over Na+ , K+ and Cs+ under mild conditions (pH ∼8.2) confirms that HL2 -HL4 represent a new class of ligands that are very effective extractants for use in lithium separation.

Recycling of Brewer's Spent Grain as a Biosorbent by Nitro-Oxidation for Uranyl Ion Removal from Wastewater.

Developing biosorbents derived from agro-industrial biomass is considered as an economic and sustainable method for dealing with uranium-contaminated wastewater. The present study explores the feasibility of oxidizing a representative protein-rich biomass, brewer's spent grain (BSG), to an effective and reusable uranyl ion adsorbent to reduce the cost and waste generation during water treatment. The unique composition of BSG favors the oxidation process and yields in a high carboxyl group content (1.3 mmol/g) of the biosorbent. This makes BSG a cheap, sustainable, and suitable raw material independent from pre-treatment. The oxidized brewer's spent grain (OBSG) presents a high adsorption capacity of U(VI) of 297.3 mg/g (c 0(U) = 900 mg/L, pH = 4.7) and fast adsorption kinetics (1 h) compared with other biosorbents reported in the literature. Infrared spectra (Fourier transform infrared), 13C solid-state nuclear magnetic resonance spectra, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and thermogravimetric analysis were employed to characterize the biosorbents and reveal the adsorption mechanisms. The desorption and reusability of OBSG were tested for five cycles, resulting in a remaining adsorption of U(VI) of 100.3 mg/g and a desorption ratio of 89%. This study offers a viable and sustainable approach to convert agro-industrial waste into effective and reusable biosorbents for uranium removal from wastewater.

Saccharified Uranyl Ions: Self-Assembly of UO2 2+ into Trinuclear Anionic Complexes by the Coordination of Glucosamine-Derived Schiff Bases.

The reaction of UO2 (OAc)2 ⋅ 2H2 O with the biologically inspired ligand 2-salicylidene glucosamine (H2 L1 ) results in the formation of the anionic trinuclear uranyl complex [(UO2 )3 (µ3 -O)(L1 )3 ]2- (12- ), which was isolated in good yield as its Cs-salt, [Cs]2 1. Recrystallization of [Cs]2 1 in the presence of 18-crown-6 led to formation of a neutral ion pair of type [M(18-crown-6)]2 1, which was also obtained for the alkali metal ions Rb+ and K+ (M=Cs, Rb, K). The related ligand, 2-(2-hydroxy-1-naphthylidene) glucosamine (H2 L2 ) in a similar procedure with Cs+ gave the corresponding complex [Cs(18-crown-6)]2 [(UO2 )3 (µ3 -O)(L2 )3 ([Cs(18-crown-6)]2 2). From X-ray investigations, the [(UO2 )3 O(Ln )3 ]2- anion (n=1, 2) in each complex is a discrete trinuclear uranyl species that coordinates to the alkali metal ion via three uranyl oxygen atoms. The coordination behavior of H2 L1 and H2 L2 towards UO2 2+ was investigated by NMR, UV/Vis spectroscopy and mass spectrometry, revealing the in situ formation of the 12- and 22- dianions in solution.

Recovering valuable metals from spent hydrodesulfurization catalyst via blank roasting and alkaline leaching.

Spent hydrodesulfurization (HDS) catalysts, containing considerable amount of pollutants and metals including vanadium (V), molybdenum (Mo), aluminum (Al), and nickel (Ni), are considered as hazardous wastes which will result in not only ecosystem damage but also squandering resource. Herein, a process featuring blank roasting-alkaline leaching is proposed to recover spent HDS catalyst. During roasting, low-valence compounds convert to high-valence oxides which can be leached out by NaOH solution. Afterwards, leaching solution is subjected to crystallization to separate metals. The results show that for samples roasted at 650 °C, 97% V, 96% Mo, and 88% Al are leached out at optimal condition; for samples roasted at 1000 °C, selective leaching of 91% V and 96% Mo respectively, are realized, with negligible Al being dissolved. NiO is insoluble in strong alkali leaving in residue. The advantages of this process are that first, the leaching of V, Mo, and Al can be manipulated by controlling roasting conditions, providing flexible process design. Second, leaching solution can be fully recycled. Finally, mild leaching condition and clean separation of V, Mo, and Al is achieved, proving fundamental information for peer researches to facilitate their future research on the development of more efficient and cleaner technologies.

Coordination of trivalent lanthanum and cerium, and tetravalent cerium and actinides (An = Th(IV), U(IV), Np(IV)) by a 4-phosphoryl 1H-pyrazol-5-olate ligand in solution and the solid state.

Structural investigations of three actinide(iv) 4-phosphoryl 1H-pyrazol-5-olate complexes (An = Th(iv), U(iv), Np(iv)) and their cerium(iv) analogue display the same metal coordination in the solid state. The mononuclear complexes show the metal centre in a square antiprismatic coordination geometry composed by the two O-donor atoms of four deprotonated ligands. Detailed solid state analysis of the U(iv) complex shows that dependent on the solvent used altered arrangements are observable, resulting in a change in the coordination polyhedron of the U(iv) metal centre to bi-capped trigonal prismatic. Further, single crystal analyses of the La(iii) and Ce(iii) complexes show that the ligand can also act as a neutral ligand by protonation of the pyrazolyl moiety. All complexes were comprehensively characterized by NMR, IR and Raman spectroscopy. A single resonance in each of the 31P NMR spectra for the La(iii), Ce(iii), Ce(iv), Th(iv) and Np(iv) complex indicates the formation of highly symmetric complex species in solution. Extended X-ray absorption fine structure (EXAFS) investigations provide evidence for the same local structure of the U(iv) and Np(iv) complex in toluene solution, confirming the observations made in the solid state.

Mild hydrothermally treated brewer's spent grain for efficient removal of uranyl and rare earth metal ions.

The increasing concerns on uranium and rare earth metal ion pollution in the environment require sustainable strategies to remove them from wastewater. The present study reports an eco-friendly approach to convert a kind of protein-rich biomass, brewer's spent grain (BSG), into effective biosorbents for uranyl and rare earth metal ions. The employed method reduces the energy consumption by performing the hydrothermal treatment at a significantly lower temperature (150 °C) than conventional hydrothermal carbonization. In addition, with the aid of the Maillard reaction between carbohydrates and proteins forming melanoidins, further activation processes are not required. Treatment at 150 °C for 16 h results in an altered biosorbent (ABSG) with increased content of carboxyl groups (1.46 mmol g-1) and a maximum adsorption capacity for La3+, Eu3+, Yb3+ (pH = 5.7) and UO2 2+ (pH = 4.7) of 38, 68, 46 and 221 mg g-1, respectively. Various characterization methods such as FT-IR, 13C CP/MAS NMR, SEM-EDX and STA-GC-MS analysis were performed to characterize the obtained material and to disclose the adsorption mechanisms. Aside from oxygen-containing functional groups, nitrogen-containing functional groups also contribute to the adsorption. These results strongly indicate that mild hydrothermal treatment of BSG could be applied as a greener, low-cost method to produce effective adsorbents for uranyl and rare earth metal ion removal.

Piperazine linked salicylaldoxime and salicylaldimine-based dicopper(ii) receptors for anions.

The syntheses and single crystal X-ray analyses of five strapped salicylaldoxime/salicylaldimine based dicopper(ii) receptors utilising a new piperazine linker are described. The complexes form 2 + 2 metallocycles and the molecular structures of all four complexes possess a small internal cavity with the utilisation of a short piperazine linker. The molecular structures of complexes [Cu2(L(4) - H)(L(4) - 2H) ⊂ DMF]BF4·DMF, and [Cu2(L(4) - H)2Br]Br·1.25DMSO·H2O·MeOH, show that intramolecular H-bonding interactions due to the presence of -OH (oxime moiety) groups lead to a Pacman-like cleft arrangement of the two metal coordinating subunits in the metallo-macrocycle. The geometrical constraints brought about by this constrained cleft make the receptor coordinate strongly to a bromide anion involving both metal centres as evidenced by whereas in the larger tetrafluroborate anion is excluded. Absence of the oxime moiety around the metal coordination site of the ligand as demonstrated in the complexes [Cu2(L(5))2BF4](BF4)3, and [Cu2(L(5))2Br]Br3·2MeOH, resulted in less constrained dicopper(ii) helicate forms. For these complexes no anion size discrimination was observed. The addition of pyridine solvent to a slightly modified piperazine-linked ligand produces an expanded 3 + 3 tube-like tricopper complex [Cu3(L(4a) - H)3Py3](BF4)2·(MeOH)3·PF6·(H2O)3, , with two coordinated pyridine molecules occupying the newly formed cavity.

Accurate method to quantify binding in supramolecular chemistry.

An approach for accurate and comparable measurement of host-guest binding affinities is introduced whereby differences in binding strength (ΔlogKass values) are measured between two host molecules toward a particular guest under identical solvent conditions. Measuring differences instead of absolute values enables obtaining highly accurate results, because many of the uncertainty sources (the solvation/association state of the guest in solution, deviations in solvent composition, etc.) cancel out. As a proof of concept, this method was applied to the measurement of the binding strength of 28 synthetic anion receptors toward acetate in acetonitrile containing 0.5% water. The receptors included differently substituted indolocarbazoles, ureas, thioureas, and some others. Possible deprotonation of more acidic receptors of each compound class by acetate was checked by measuring their acidities (ΔpKa values) relative to acetic acid in the same solvent. A self-consistent (consistency standard deviation 0.04 log units) binding affinity scale ranging for around 2.7 log units was constructed from the results. Absolute logKass values were found by anchoring the scale to the absolute logKass values of two receptor molecules, determined independently by direct measurements. This new approach is expected to find use in accurate quantification of a wide range of binding processes relevant to supramolecular chemistry.

Benzimidazole-based anion receptors: tautomeric switching and selectivity.

Tautomeric switching is observed in a series of benzimidazole-based anion receptors upon addition of basic anions. An N-methylbenzimidazole based receptor selectively interacts with dihydrogen phosphate over a variety of other putative anionic guests via a combination of donated and accepted hydrogen bonds.

Anion receptor chemistry: highlights from 2010.

This critical review covers advances in anion complexation in the year 2010. The review covers both organic and inorganic systems and also highlights the applications to which anion receptors can be applied such as sensing, anion transport, control of molecular motion and gelation (179 references).

Structure-activity relationships in tripodal transmembrane anion transporters: the effect of fluorination.

A series of easy-to-make fluorinated tripodal anion transporters containing urea and thiourea groups have been prepared and their anion transport properties studied. Vesicle anion transport assays using ion-selective electrodes show that this class of compound is capable of transporting chloride through a lipid bilayer via a variety of mechanisms, including chloride/H(+) cotransport and chloride/nitrate, chloride/bicarbonate, and to a lesser extent an unusual chloride/sulfate antiport process. Calculations indicate that increasing the degree of fluorination of the tripodal transmembrane transporters increases the lipophilicity of the transporter and this is shown to be the major contributing factor in the superior transport activity of the fluorinated compounds, with a maximum transport rate achieved for clog P = 8. The most active transporter 5 contained a urea functionality appended with a 3,5-bis(trifluoromethyl)phenyl group and was able to mediate transmembrane chloride transport at receptor to lipid ratios as low as 1:250000. Proton NMR titration and single crystal X-ray diffraction revealed the ability of the tripodal receptors to bind different anions with varying affinities in a 1:1 or 2:1 stoichiometry in solution and in the solid state. We also provide evidence that the most potent anion transporters are able to induce apoptosis in human cancer cells by using a selection of in vitro viability and fluorescence assays.

Thiourea isosteres as anion receptors and transmembrane transporters.

Compounds containing cyanoguanidine and 3-amino-1,2,4-benzothiadiazine-1,1-dioxide have been studied as anion receptors and transporters. Significant affinity for oxo-anions was observed in organic solution and the receptors were found to function as transmembrane chloride/nitrate antiporters with transport rates enhanced in the presence of valinomycin-K(+) complex.

A bis-salicylaldoximato-copper(II) receptor for selective sulfate uptake.

The preferential uptake of sulfate over the industrially important anions, chloride and nitrate and structurally similar dihydrogen phosphate has been achieved in aqueous media with a dicopper salicylaldoxime complex.

Zwitterionic dicopper helicates: anion encapsulation and binding studies.

The synthesis and spectroscopic studies of a dicopper(II) double helicate capable of binding anions is described. X-Ray crystallographic analysis of three anion variations of the complex have shown that the helicate is capable of accommodating anions with an approximate volume of 0.09 nm(3) and smaller. ESI-MS revealed that the supramolecular complexes retain the 2 : 2 ligand : metal cluster in solution. Spectrometric analysis has shown the complex is capable of binding anions in a 1 : 1 ratio of helicate to anion, in the order SO(4)(2-) > HPO(4)(2-) > ClO(4)(-) approximately BF(4)(-) approximately NO(3)(-). We demonstrate that coordination to the metal centre, H-bonding and electrostatic interactions all play a role in encapsulating the anions.

Anion-induced contraction of helical receptors.

Uptake of a tetrafluoroborate anion into the centre of a dicopper bis-salicylaldoxime complex causes a major contraction of the cavity and an increase in helicity.