Extraction and transport of sulfate using macrocyclic squaramide receptors

Abstract

The selective extraction of the hydrophilic sulfate ion from water is highly challenging because the high free energy of hydration of this ion makes it more difficult to extract than less hydrophilic ions such as chloride and nitrate. Lipophilic macrocyclic squaramide receptors 1 and 2 were synthesized. Receptor 2 efficiently extracted sulfate from aqueous sodium sulfate solutions into a chloroform phase, via exchange with nitrate ions, overcoming the Hofmeister bias. The resulting 2·SO₄²⁻ complex was readily recycled through precipitation of BaSO₄. Transport of sulfate across a bulk chloroform membrane by 2 was demonstrated across a wide pH range (pH 3.2–9.4) and in the presence of high concentrations of competing anions (chloride, nitrate and dihydrogenphosphate), opening the door to the use of 2 for the selective removal of sulfate from water across a range of applications.

---

Introduction

The development of selective receptors capable of extracting sulfate from aqueous solution is of significant interest because of the important roles this anion plays in biological, environmental and industrial processes.¹ The removal of sulfate from aqueous solution is of particular importance in oil production and desalination processes where sulfate ions contribute to the formation of scale that clogs pipes and fouls membranes.^2–4 It is also of relevance in the nuclear industry where sulfate interferes with the vitrification process required for safe long-term storage of nuclear waste, primarily as a result of the low solubility of sulfate in borosilicate glass.^5–7 Precipitation of BaSO₄ is frequently used to remove sulfate from solution, but this approach is problematic in removing sulfate from nuclear waste as a result of the co-precipitation of radioactive ²²⁸Ra/²²⁶Ra and ⁹⁰Sr ions forming Ba(Ra)SO₄ and Ra(Sr)SO₄.^8–10 Therefore, it has been proposed that the selective extraction of sulfate from nitrate rich solutions by liquid–liquid extraction (LLE) using synthetic receptors could have significant benefits for nuclear waste remediation.¹¹

Despite the need to selectively extract sulfate from aqueous media, several key challenges have hindered the development of selective sulfate extraction agents. Sulfate has a very high hydration energy (ΔG_hyd = −1080 kJ mol⁻¹),¹² which poses a dual challenge for selective extraction of this anion from aqueous solution. Firstly, to extract sulfate from an aqueous phase into an organic phase, a receptor needs to bind sulfate with high affinity to compensate for the large dehydration energy. Secondly, if other anions such as nitrate, are present in high concentrations and are less strongly hydrated (ΔG_hyd = −306 kJ mol⁻¹)¹² than sulfate, these are easier to extract from aqueous solution than sulfate (commonly referred to as Hofmeister bias) reducing sulfate extraction efficiency. To overcome this bias and allow sulfate extraction in the presence of less hydrophilic anions, receptors must have excellent selectivity for sulfate. A further important challenge lies in the release of sulfate following extraction to allow facile recycling of the receptors and enable commercially viable industrial processes.¹¹

While a number of receptors for selective sulfate recognition have recently been reported,^13–25 there are relatively few examples of suitable receptors that overcome the Hofmeister bias to allow LLE of sulfate.^26–33 Sessler and co-workers have successfully employed calix[n]pyrroles to extract sulfate into organic media in the presence of methyltrialkylammonium ions.^26–28 Wu and co-workers have demonstrated that a tripodal hexaurea receptor is capable of extraction of sulfate ions into chloroform solution in the presence of TBACl and that the sulfate can be back-extracted with aqueous barium chloride to regenerate the receptor as a chloride complex.³⁰ Moyer and coworkers have demonstrated that a simple diiminoguanidinium extractant demonstrates very high sulfate selectivity and compatibility with aliphatic solvents commonly used in LLE processes.³¹ More recently, Romanski and coworkers have demonstrated that a ditopic receptor extracts potassium sulfate from aqueous solution.³³ In related work, the transport of sulfate across a bilayer membrane has been shown to be facilitated by tripodal thioureas.¹⁷ However, receptors that can transport sulfate across a bulk liquid membrane to facilitate receptor recycling for real-world applications of sulfate extraction remain unexplored.

We have recently reported the use of macrocyclic squaramides as highly selective sulfate receptors with strong affinity for this anion in aqueous mixtures³⁴ and reasoned that these macrocycles could be readily modified with aliphatic chains to solubilize them in organic solvents without altering their sulfate binding affinity, thereby enabling efficient and selective LLE of sulfate ions and their transport across a bulk liquid membrane. We now demonstrate that suitably functionalized macrocyclic squaramides are able to extract sulfate from aqueous solutions of sodium sulfate across a wide pH range (pH 3.2–9) and are capable of sulfate–nitrate exchange, overcoming the Hofmeister bias. We also show for the first time that dynamic sulfate transport can be achieved across a bulk liquid membrane in the presence of competing anions, demonstrating efficient receptor recyclability.

Results and discussion

The structures of macrocyclic squaramides (MSQs) 1 and 2 are based on our previously reported sulfate selective receptor 3 (Chart 1). In concurrent work,³⁵ we have demonstrated that replacing the benzene spacers in 3 with pyridines provides increased sulfate binding affinity, particularly at low pH where protonation of the pyridine units can occur, without reducing the selectivity that these macrocycles display for sulfate. We therefore chose to use isonicotinamide derived macrocycles in this work. We reasoned that it should be possible to functionalize this macrocyclic core with aliphatic chains to solubilize the macrocycle in organic solvents without impacting the demonstrated high sulfate binding affinity and selectivity of the macrocyclic core.

Chart 1 Structures of the MSQs 1–3.

Synthesis

The synthesis of macrocycles 1 and 2 followed similar procedures to those described previously for the synthesis of MSQs (Scheme 1).³⁴ Briefly, basic hydrolysis of methyl 2,6-bis(azido)isonicotinate^36,37 was followed immediately by reaction of the resulting carboxylic acid with either dioctylamine or dioctadecylamine in the presence of carbodiimide (CDI) to give diazides 4 and 5, respectively. Staudinger reduction of 4 and 5 to form the corresponding diamines 6 and 7 was followed by reaction with two equivalents of diethyl squarate to give disquarates 8 and 9, respectively. Following mono-Boc protection of diamines 6 and 7, the so-formed amines 10 and 11 were immediately reacted with 0.5 equivalents of diethyl squarate in ethanol to give the diisonicotinamide squaramides 12 and 13. Deprotection of compound 12 upon treatment with trifluoroacetic acid and subsequent reaction of diamine 14 with the corresponding disquarate 8 in ethanol provided the desired [3]MSQ 1 in 56% yield over the two steps. In contrast, attempts to condense diamine 15 with disquarate 9 under the same conditions were unsuccessful. However, in a mixed solvent system of EtOH/toluene/hexane (10 : 45 : 45 v/v/v) to ensure the solubility of all starting materials and reduce the aggregation of the long alkyl chains,^38,399 and 15 were successfully condensed in the presence of one equivalent of TBAH₂PO₄ to form [3]MSQ 2 in 58% yield. We found that dihydrogen phosphate was crucial for the formation of [3]MSQ 2; the addition of a range of other anions (Cl⁻, ClO₄⁻, I⁻, BF₄⁻, SO₄²⁻) did not lead to isolation of the desired product. In the absence of an anion or in the presence of anions such as ClO₄⁻, I⁻, BF₄⁻ that are known to only weakly coordinate to squaramides,^30,40,41 no reaction occurred. In the presence of Cl⁻ and SO₄²⁻, which bind to squaramides with relatively high affinities, mixtures of products were observed but all attempts to isolate desired macrocycle 2 (or other discrete species) from these reactions failed. We hypothesize that Cl⁻ and SO₄²⁻ may bind strongly to the reactants in the non-polar conditions used,^40–44 locking them into conformations that do not favour cyclisation, thus promoting the formation of linear oligomers, whereas the weaker binding to H₂PO₄⁻ allows interconversion of conformers to allow cyclisation to progress.

Scheme 1 Synthesis of the macrocyclic squaramide based receptors 1 and 2. Conditions: (i) Ph₃P, H₂O, THF, (6, 79%; 7, 85%); (ii) diethyl squarate, EtOH, RT, 16 h, (8, 82%; 9, 79%); (iii) Boc₂O, CH₂Cl₂, RT, 16 h, (10, 49%; 11, 62%); (iv) diethyl squarate, EtOH, RT, 16 h (12, 46%; 13, 60%); (v) TFA/CH₂Cl₂, RT, 2 h (14, quant.; 15, quant.); (vi) 8 + 14, EtOH, RT, 48 h, (1, 56%); (vii) 9 + 15, TBAH₂PO₄, EtOH/toluene/hexane 10/45/45 v/v/v, 60 °C, 48 h (2, 58%).

Sulfate extraction

We first established that appending alkyl chains to the MSQs did not impact their previously observed ability to bind with high affinity to sulfate ions.³⁴ In water-saturated CDCl₃, the signal attributable to the squaramide NH protons of MSQ 2 is too broad to observe and the signal for the benzylic protons occurs as a broad multiplet indicating the presence of multiple slowly interconverting conformers of the macrocycle.³⁴ Titration of TBA₂SO₄ into a solution of 2 in H₂O-saturated CDCl₃ led to a sharpening and downfield shift of the signal attributable to the squaramide NH with the appearance of a new signal at δ 9.50 ppm after the addition of 1 equiv. of SO₄²⁻ that further sharpened into a triplet on addition of excess SO₄²⁻ (Fig. S25†). A sharpening and upfield shift of the signal attributable to the aromatic protons, together with a sharpening and downfield shift of the signal attributable to the benzylic protons were also observed. This indicates the formation of a 2·SO₄²⁻ complex in CDCl₃ with intermediate/slow exchange, suggesting strong binding (K_a > 10⁴ M⁻¹) under these conditions. Titration of TBANO₃ into a solution of 2 in H₂O-saturated CDCl₃ resulted in similar changes to the spectra, however the downfield shift of the signal attributable to the squaramide proton was significantly lower than that observed upon addition of sulfate, with this signal emerging at δ 8.16 ppm after addition of 1 equiv. of nitrate, again suggesting strong 1 : 1 binding (K_a > 10⁴ M⁻¹) under these conditions.

The ability of 1 and 2 to extract sulfate from aqueous solution using liquid–liquid extraction was next investigated by vigorously shaking an aqueous solution of TBA₂SO₄ (see ESI† for details) with a CDCl₃ solution of either 1 or 2 [45 mM] for 1 minute. The two layers were immediately separated and the organic phase analysed by ¹H NMR. For MSQ 1, ¹H NMR spectroscopy indicated that none of the MSQ remained in the organic phase. However, a precipitate formed in the aqueous layer and after filtration and redissolution in CDCl₃, analysis of the precipitate by ¹H NMR (Fig. S28†) indicated the presence of TBA⁺ and 1·SO₄ in a 2 : 1 ratio, as established through integration of the macrocycle and TBA⁺ signals, together with the chemical shift of the squaramide NH protons matching that observed in the titration experiments above. This indicates the formation of a TBA₂[1·SO₄] complex, confirming the 1 : 1 complexation stoichiometry and suggesting that, while 1 is capable of binding to SO₄²⁻ at an aqueous–organic interface, the resulting complex is not sufficiently soluble in CDCl₃ to extract the SO₄²⁻ into the organic phase.²⁹ In contrast, with the more lipophilic MSQ 2, analysis of the CDCl₃ phase after liquid–liquid extraction indicated that one equiv. of TBA₂SO₄ was extracted into the organic phase, as determined by comparison of the integrations of the signals attributable to the macrocycle and tetrabutylammonium counterion which gave a ratio of 2 TBA⁺ ions per macrocycle (Fig. S30 and S31†). Notably, 2 was capable of efficient sulfate extraction, even at sub-stoichiometric sulfate concentrations (Fig. S31†). However, the lipophilic tetrabutylammonium counter ions were required for efficient extraction to take place, as attempts to extract Na₂SO₄ under the same conditions were unsuccessful.

We next evaluated the ability of MSQ 2 to extract sulfate in the presence of nitrate ions using an anion metathesis approach in which aqueous solutions of Na₂SO₄ at either pH 3.2 or pH 7.4 were layered onto a solution of [3]MSQ 2 and 2.0 eq. TBANO₃ in CDCl₃ (pH of the aqueous phase was adjusted using conc. HNO₃). The two layers were vigorously shaken for 1 minute, then separated and the organic phases were analyzed using ¹H NMR (Fig. 1). The ¹H NMR signals corresponding to the 2·NO₃⁻ and 2·SO₄²⁻ complexes are clearly differentiated by the chemical shift of the NH signals and appeared independently in 1 : 10 and 3 : 10 ratios of 2·SO₄²⁻: 2·NO₃⁻ at pH 7.4 and pH 3.2, respectively. This indicates that there is slow exchange between the 2·NO₃⁻ and 2·SO₄²⁻ complexes under these conditions. We speculate that the relative higher proportion of 2·SO₄²⁻ formed under acidic conditions is due to the partial protonation of the pyridine units in the macrocycle at pH 3.2 as the pK_a of isonicotinamide is 3.3,⁴⁵ which results in increased sulfate binding affinity.³⁴ The 2·SO₄²⁻ complex in CDCl₃ was readily recycled to the nitrate complex upon washing with an aqueous solution of Ba(NO₃)₂ (Fig. 2d) as a result of the formation of a BaSO₄ precipitate (K_sp = 1.1 × 10⁻¹⁰, 25 °C).⁴⁶ These experiments demonstrate that MSQ 2 is capable of sulfate–nitrate exchange processes at an aqueous–organic interface, indicating that the excellent selectivity demonstrated by MSQ 2 for SO₄²⁻ overcomes the Hofmeister bias and eliminates the need for lipophilic counter ions in the aqueous phase.

Fig. 1 Partial ¹H NMR spectra (400 MHz) of a CDCl₃ solution of MSQ 2 (5 mM) and TBANO₃ (10 mM) after extraction of the following aqueous solutions: (a) blank (20 mM Tris buffer, pH 7.4); (b) 500 mM Na₂SO₄ in 20 mM Tris buffer, pH 7.4; (c) 500 mM Na₂SO₄ in 20 mM Tris buffer, pH 3.2, adjusted by addition of conc. HNO₃; (d) back extraction of solution (c) through washing with 100 mM aqueous Ba(NO₃)₂. Back extraction of solution (b) gave an identical spectrum.

Fig. 2 Illustration of U-tube transport experiment (TBA⁺ cations are omitted for clarity).

Sulfate transport across a bulk liquid membrane

We next investigated the ability of 2 to transport sulfate across a bulk chloroform membrane using classic Cram U-tube experiments (Fig. 2),^5,47–49 as proof of principle that the receptor is capable of the dynamic removal of sulfate from aqueous solution through an anion exchange mechanism. In initial experiments the aqueous source and receiving phases were buffered to pH 7.4 (20 mM Tris) with the source phase also containing 500 mM Na₂SO₄ and the bulk chloroform phase containing 10 mM 2. Sulfate concentrations in both the source and receiving phases were detected using a modified BaSO₄ gravimetric analysis method^50,51 in which the non-precipitated Ba²⁺ concentration was measured using inductively coupled plasma mass spectrometry (ICP-MS) after the formation of a BaSO₄ precipitate. The final sulfate concentrations in each experiment were also determined by ICP-MS by measuring the concentration of sulfide (Table S2†).^52,53 In the absence of any ion source in the organic phase, no transport was observed after 21 days (Fig. 3 and Table S2†), indicating that MSQ 2 is not capable of transporting Na₂SO₄ across a bulk liquid membrane. However, upon the addition of five equivalents, relative to the receptor, of TBANO₃ (tetraalkylammonium ions have previously been shown to facilitate sulfate extraction through formation of ion pair complexes²⁷) to the chloroform phase, a sulfate concentration of 15 mM (all data listed in Table S2†) was detected in the receiving phase after 21 days. No sulfate was detected in the receiving phase in the absence of receptor 2. These results indicate that 2 is capable of efficiently transporting the highly hydrophilic sulfate ion across a bulk liquid membrane with subsequent release into an aqueous phase via an anion exchange mechanism.

Fig. 3 Sulfate transport by 2 across a bulk chloroform membrane determined by the [SO₄²⁻] in the receiving phase. Conditions: (A) source phase 500 mM Na₂SO₄ in 20 mM Tris buffer (pH 7.4); receiving phase 20 mM Tris buffer (pH 7.4); organic phase 10 mM 2 in CHCl₃. (B) Source phase 500 mM Na₂SO₄ in 20 mM Tris buffer (pH 7.4); receiving phase 20 mM Tris buffer (pH 7.4); organic phase 10 mM 2 and 50 mM TBANO₃ in CHCl₃. (C) Source phase 500 mM Na₂SO₄ in 20 mM Tris buffer (pH 7.4); receiving phase 300 mM BaCl₂ in 20 mM Tris buffer (pH 7.4); organic phase 10 mM 2 and 50 mM TBANO₃ in CHCl₃. (D) Source phase 500 mM Na₂SO₄ in H₂O (pH 3.2, HNO₃); receiving phase 300 mM BaCl₂ in H₂O (pH 3.2, HNO₃); organic phase 10 mM 2 and 50 mM TBANO₃ in CHCl₃. (E) source phase 500 mM Na₂SO₄ in H₂O (pH 9.4, NaOH); receiving phase 300 mM BaCl₂ in H₂O (pH 9.4, NaOH); organic phase 10 mM 2 and 50 mM TBANO₃ in CHCl₃. (F) source phase 500 mM Na₂SO₄ in 20 mM Tris buffer (pH 7.4); receiving phase 300 mM BaCl₂ in 20 mM Tris buffer (pH 7.4); organic phase 50 mM TBANO₃ in CHCl₃.

In subsequent experiments, BaCl₂ was added to the receiving phase. We anticipated this would facilitate sulfate release though precipitation of BaSO₄, thereby removing sulfate from the receiving phase and increasing transport rates through Le Chatelier's principle. This resulted in a >2-fold increase in the amount of sulfate transported over the same time period. No change in transport rate was observed upon lowering the pH to 3.2, whereas increasing the pH to 9.4 resulted in a modest reduction in sulfate transport. This may be due to the reduced binding affinity of the isonicotinamide MSQ core at basic pH³⁵ or alternatively might be a result of increased competition from carbonate ions at this higher pH. There was no detectable change in the concentration of sodium ions in the source or receiving phases in any of the transport experiments confirming that, under these conditions, transport occurs via an anion metathesis process. Finally, we evaluated sulfate transport with a mixture of anions in the source phase that mimics that in nuclear waste (100 mM Na₂SO₄, 100 mM Na₂HPO₄, 500 mM NaNO₃, 500 mM NaCl, pH 7.4). Under these highly competitive conditions, 2 still exhibited sulfate transport, although the rate was diminished, reflecting the ability of 2 to bind strongly to other anions in chloroform (Table S5†). While we have previously established that water-soluble analogues of 2 and related macrocycles bind sulfate with higher affinity than other anions in polar solvents (such as 1 : 1 v/v DMSO/H₂O),^34,35 in relatively non-polar solvents such as chloroform, 2 binds to nitrate, chloride and sulfate with K_a > 10⁴ for all three ions. Since both transport and extraction experiments require binding to occur at the interface between the water and chloroform phases, our hypothesis is that the demonstrated higher affinity of the macrocyclic core of 2 for sulfate over other anions in aqueous media results in preferential binding of sulfate by 2 at the aqueous interface, leading to the observed extraction and transport behaviour.

Experimental

Synthesis of macrocycle 1

Compound 12 (76 mg, 0.07 mmol) was dissolved in a solution of TFA/CH₂Cl₂ (1 : 1 v/v, 3 mL) before the reaction mixture was stirred at room temperature for 2 hours and then concentrated under reduced pressure. The resulting oil was dissolved in EtOH (3 mL) then a solution of 8 (46 mg, 0.07 mmol) and Et₃N (0.5 mL) in EtOH (50 mL) was added and the resulting mixture was stirred at room temperature for 48 h. The solvent was then removed under reduced pressure to give a yellow oil. Subjection of this material to flash silica gel chromatography (5/95 v/v methanol/dichloromethane elution) and concentration of the appropriate fractions (R_f 0.3) gave the macrocycle 1 (57 mg, 56%) as a beige solid. Mp. 262–268 °C (decomp.); ¹H NMR (400 MHz, DMSO-d₆): 0.79–0.90 (m, 18H), 0.98–1.29 (m, 60H), 1.41 (s, 6H), 1.56 (s, 6H), 3.04 (s, 6H), 3.36 (s, 6H), 4.81 (s, 12H), 7.23 (s, 6H), 8.02 (br s, 6H); ¹³C NMR (100.6 MHz, DMSO-d₆): 14.3, 14.4, 22.4, 22.5, 26.3, 26.8, 27.4, 28.4, 28.9, 29.1, 29.2, 29.5, 31.6, 31.7, 44.5, 48.6, 118.2, 146.8, 158.2, 168.3, 183.3, 2 signals obscured or overlapping; HRMS (ESI, MeOH) calcd for C₈₄H₁₂₆N₁₂O₉Na [M + Na]⁺ 1447.9845, found 1447.9829; ν_max (film) per cm⁻¹: 3237 (broad), 2925, 2851, 1801, 1714, 1609.

Synthesis of macrocycle 2

Compound 13 (53 mg, 0.032 mmol) was dissolved in a solution of TFA/CH₂Cl₂ (1 : 1 v/v, 3 mL) and the reaction mixture was stirred at room temperature for 2 hours, then concentrated under reduced pressure. The solid was washed with 5% NaHCO₃ solution (5 mL) then dried under stream of N₂ (g). The resulting solid was dissolved in 20 mL toluene and then added to a solution of 9 (30 mg, 0.032 mmol) and TBAH₂PO₄ (10.8 mg, 0.032 mmol) in EtOH/toluene/hexane 10/45/45 v/v/v (500 mL) and stirred at 60 °C for 48 h. The solvent was then removed under reduced pressure to give a yellow solid. Subjection of this material to flash silica gel chromatography (1/99 to 5/95 v/v methanol/dichloromethane elution) and concentration of the appropriate fractions (R_f 0.3) gave compound 2 (42 mg, 58%) as a beige solid. Mp. 252–258 °C (decomp.); ¹H NMR (400 MHz, CDCl₃): 0.86 (t, J = 6.8 Hz, 18H), 0.98–1.41 (m, 180H), 1.38–1.55 (m, 6H), 1.55–1.69 (m, 6H), 3.08 (t, J = 7.7 Hz, 6H), 3.42 (t, J = 7.7 Hz, 4H), 4.9 (br s, 12H), 7.1 (s, 6H), 7.7 (br s, 6H); ¹³C NMR (100.6 MHz, CDCl₃): δ 189.29, 183.18, 177.99, 172.37, 168.08, 155.74, 147.20, 147.20, 118.25, 69.92, 48.98, 44.97, 31.92, 29.70, 29.65, 29.46, 29.41, 29.35, 29.19, 28.75, 27.46, 27.08, 26.68, 26.62, 22.68, 15.86, 14.10; HRMS (ESI, MeOH) calcd for C₁₄₄H₂₄₆N₁₂O₉H₂ [M + 2H]²⁺ 1144.9653, found 1144.9645; ν_max (film) per cm⁻¹: 3254 (broad), 2920, 2851, 1807, 1598, 1535, 1466.

Conclusions

In summary, we have shown that the neutral MSQ 2 can efficiently extract SO₄²⁻ from an aqueous Na₂SO₄ solution into organic solution, via an anion exchange mechanism with nitrate ions, overcoming the Hofmeister bias. This is attributed to the high binding affinity of 2 for sulfate ions. We have further successfully demonstrated that, assisted by a lipophilic cation, MSQ 2 can transport the highly hydrophilic sulfate ion across a bulk chloroform layer via an anion exchange mechanism with nitrate, allowing the extraction of sulfate from sodium sulfate solutions. Notably, receptor 2 is able to transport sulfate across a bulk chloroform membrane even when a complex mixture of anions is present and across a wide pH range (pH 3.2–9.4). Release of the sulfate from the receptor into the receiving phase is facilitated through precipitation of BaSO₄ thereby increasing the rate of sulfate transport. These results provide proof-of-principle that neutral receptors for the sulfate ion can be employed in the selective removal of sulfate from aqueous solution in a recyclable manner, overcoming one of the key limitations for the use of such receptors in real-world applications such as the removal of sulfate from nuclear waste.

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

This work was supported by an Australian Research Council Discovery Project grant (DP170100118).

Notes and references

1. I. Ravikumar and P. Ghosh, Chem. Soc. Rev., 2012, 41, 3077–3098.
2. M. S. H. Bader, Desalination, 2006, 201, 100–105.
3. K. M. Abdullaev, M. M. Agamaliev and D. A. Akhmedova, J. Water Chem. Techno., 2019, 41, 119–124.
4. L. F. Greenlee, D. F. Lawler, B. D. Freeman, B. Marrot and P. Moulin, Water Res., 2009, 43, 2317–2348.
5. B. A. Moyer and R. P. Singh, Fundam. Appl. Anion Sep., Springer, 2004.
6. E. A. Katayev, Y. A. Ustynyuk and J. L. Sessler, Coord. Chem. Rev., 2006, 250, 3004–3037.
7. R. K. Mishra, K. V. Sudarsan, P. Sengupta, R. K. Vatsa, A. K. Tyagi, C. P. Kaushik, D. Das and K. Raj, J. Am. Ceram. Soc., 2008, 91, 3903–3907.
8. T. Y. Zhang, K. Gregory, R. W. Hammack and R. D. Vidic, Environ. Sci. Technol., 2014, 48, 4596–4603.
9. P. Medley, P. Martin, A. Bollhöfer and D. Parry, Appl. Radiat. Isot., 2015, 95, 200–207.
10. F. Grandia, J. Merino and J. Bruno, Assessment of the radium–barium co-precipitation and its potential influence on the solubility of Ra in the near-field, Technical Report TR-08-07, Swedish Nuclear Fuel and Waste Management Co., Stockholm, 2008.
11. B. A. Moyer, R. Custelcean, B. P. Hay, J. L. Sessler, K. Bowman-James, V. W. Day and S. O. Kang, Inorg. Chem., 2013, 52, 3473–3490.
12. R. Custelcean and B. A. Moyer, Eur. J. Inorg. Chem., 2007, 2007, 1321–1340.
13. C. Jin, M. Zhang, L. Wu, Y. Guan, Y. Pan, J. Jiang, C. Lin and L. Wang, Chem. Commun., 2013, 49, 2025–2027.
14. R. B. P. Elmes, K. K. Y. Yuen and K. A. Jolliffe, Chem.–Eur. J., 2014, 20, 7373–7380.
15. H. Zhou, Y. Zhao, G. Gao, S. Li, J. Lan and J. You, J. Am. Chem. Soc., 2013, 135, 14908–14911.
16. V. J. Dungan, H. T. Ngo, P. G. Young and K. A. Jolliffe, Chem. Commun., 2013, 49, 264–266.
17. N. Busschaert, L. E. Karagiannidis, M. Wenzel, C. J. E. Haynes, N. J. Wells, P. G. Young, D. Makuc, J. Plavec, K. A. Jolliffe and P. A. Gale, Chem. Sci., 2014, 5, 1118–1127.
18. A. Schaly, R. Belda, E. Garcia-Espana and S. Kubik, Org. Lett., 2013, 15, 6238–6241.
19. Z. Rodriguez-Docampo, E. Eugenieva-Ilieva, C. Reyheller, A. M. Belenguer, S. Kubik and S. Otto, Chem. Commun., 2011, 47, 9798–9800.
20. J. L. Sessler, E. Katayev, G. D. Pantos and Y. A. Ustynyuk, Chem. Commun., 2004, 1276–1277.
21. P. A. Gale, J. R. Hiscock, C. Z. Jie, M. B. Hursthouse and M. E. Light, Chem. Sci., 2010, 1, 215–220.
22. C. Jia, Q. Q. Wang, R. A. Begum, V. W. Day and K. Bowman-James, Org. Biomol. Chem., 2015, 13, 6953–6957.
23. J. I. Kim, H. Juwarker, X. Liu, M. S. Lah and K. S. Jeong, Chem. Commun., 2010, 46, 764–766.
24. P. Mateus, R. Delgado, V. Andre and M. Teresa Duarte, Org. Biomol. Chem., 2015, 13, 834–842.
25. N. A. Tzioumis, K. K. Y. Yuen and K. A. Jolliffe, Supramol. Chem., 2018, 30, 667–673.
26. C. J. Fowler, T. J. Haverlock, B. A. Moyer, J. A. Shriver, D. E. Gross, M. Marquez, J. L. Sessler, M. A. Hossain and K. Bowman-James, J. Am. Chem. Soc., 2008, 130, 14386–14387.
27. C. J. Borman, R. Custelcean, B. P. Hay, N. L. Bill, J. L. Sessler and B. A. Moyer, Chem. Commun., 2011, 47, 7611–7613.
28. S. K. Kim, J. Lee, N. J. Williams, V. M. Lynch, B. P. Hay, B. A. Moyer and J. L. Sessler, J. Am. Chem. Soc., 2014, 136, 15079–15085.
29. L. R. Eller, M. Stępień, C. J. Fowler, J. T. Lee, J. L. Sessler and B. A. Moyer, J. Am. Chem. Soc., 2007, 129, 11020–11021.
30. C. Jia, B. Wu, S. Li, X. Huang, Q. Zhao, Q. S. Li and X. J. Yang, Angew. Chem., Int. Ed., 2011, 50, 486–490.
31. N. J. Williams, C. A. Seipp, K. A. Garrabrant, R. Custelcean, E. Holguin, J. K. Keum, R. J. Ellis and B. A. Moyer, Chem. Commun., 2018, 54, 10048–10051.
32. B. Akhuli, I. Ravikumar and P. Ghosh, Chem. Sci., 2012, 3, 1522–1530.
33. D. Jagleniec, L. Dobrzycki, M. Karbarz and J. Romanski, Chem. Sci., 2019, 10, 9542–9547.
34. L. Qin, A. Hartley, P. Turner, R. B. P. Elmes and K. A. Jolliffe, Chem. Sci., 2016, 7, 4563–4572.
35. L. Qin, J. R. Wright, J. D. E. Lane, S. N. Berry, R. B. P. Elmes and K. A. Jolliffe, Chem. Commun., 2019, 55, 12312–12315.
36. S. G. Gouin, M. Roger, N. Leygue, D. Deniaud, K. Julienne, E. Benoist, C. Picard, J. Kovensky and C. Galaup, Bioorg. Med. Chem. Lett., 2012, 22, 2684–2688.
37. L. Laurent, B. Hervé and B. Emilie, Novel rare earth element cryptates including a tetraazatriphenylene unit, WO 2010070232, 2008.
38. R. O. Dunn and M. O. Bagby, J. Am. Oil Chem. Soc., 1995, 72, 123–130.
39. R. O. Dunn and M. O. Bagby, J. Am. Oil Chem. Soc., 1994, 71, 101–108.
40. V. E. Zwicker, K. K. Yuen, D. G. Smith, J. Ho, L. Qin, P. Turner and K. A. Jolliffe, Chem.–Eur. J., 2018, 24, 1140–1150.
41. V. Amendola, G. Bergamaschi, M. Boiocchi, L. Fabbrizzi and M. Milani, Chem.–Eur. J., 2010, 16, 4368–4380.
42. V. Amendola, L. Fabbrizzi, L. Mosca and F. P. Schmidtchen, Chem.–Eur. J., 2011, 17, 5972–5981.
43. N. Busschaert, I. L. Kirby, S. Young, S. J. Coles, P. N. Horton, M. E. Light and P. A. Gale, Angew. Chem., Int. Ed., 2012, 51, 4426–4430.
44. R. B. Elmes, P. Turner and K. A. Jolliffe, Org. Lett., 2013, 15, 5638–5641.
45. J. L. Castro, J. F. Arenas, M. R. Lopez-Ramirez, J. Soto and J. C. Otero, J. Colloid Interface Sci., 2013, 396, 95–100.
46. C. C. Templeton, J. Chem. Eng. Data, 1960, 5, 514–516.
47. D. J. Cram, Angew. Chem., Int. Ed., 1988, 27, 1009–1020.
48. G. M. Ritcey, Tsinghua Sci. Technol., 2006, 11, 137–152.
49. G. M. Ritcey and A. W. Ashbrook, Solvent Extraction: Principle and Applications to Process Metallurgy, Part I, Elsevier, Amsterdam, 1984.
50. O. K. Galle and L. R. Hathaway, Appl. Spectrosc., 1975, 29, 518–519.
51. F. Torrades and M. Castellvi, Fresenius. J. Anal. Chem., 1994, 349, 734–737.
52. M. Colon, M. Iglesias, M. Hidalgo and J. L. Todoli, J. Anal. At. Spectrom., 2008, 23, 416–418.
53. P. R. Craddock, O. J. Rouxel, L. A. Ball and W. Bach, Chem. Geol., 2008, 253, 102–113.

---

Footnote

† Electronic supplementary information (ESI) available: Synthetic procedures and characterisation data for all new compounds; general methods and data for sulfate extraction and transport experiments. See DOI: 10.1039/c9sc04786g

---