Macrocyclic Squaramides: Anion Receptors with High Sulfate Binding Affinity and Selectivity in Aqueous Media

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2018 Aug 30

PMID 30155103

Citations 15

Authors

Lei Qin

Anna Hartley

Peter Turner

Robert B P Elmes

Katrina A Jolliffe

Affiliations

Soon will be listed here.

Abstract

A number of macrocyclic squaramide-containing receptors (MSQs) have been designed and synthesised and their interaction with a range of inorganic anions was studied in solution by H NMR spectroscopy and ESI-HRMS. The binding data revealed remarkable binding of sulfate in aqueous mixtures from 0.5 to 50% v/v HO/DMSO-. The larger [3]-MSQs were found to better match the size and shape of the sulfate ion than the [2]-MSQs, providing high affinity and selectivity for sulfate while other tetrahedral divalent anions such as selenate, phosphate species and chromate have substantially lower binding affinities. In mixtures of anions mimicking the composition of either nuclear waste or plasma, the [3]-MSQs were still able to bind sulfate ions with high affinity.

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References

Kuk Kim S, Lee J, Williams N, Lynch V, Hay B, Moyer B . Bipyrrole-strapped calix[4]pyrroles: strong anion receptors that extract the sulfate anion. J Am Chem Soc. 2014; 136(42):15079-85. DOI: 10.1021/ja5086996. View

Rodriguez-Docampo Z, Eugenieva-Ilieva E, Reyheller C, Belenguer A, Kubik S, Otto S . Dynamic combinatorial development of a neutral synthetic receptor that binds sulfate with nanomolar affinity in aqueous solution. Chem Commun (Camb). 2011; 47(35):9798-800. DOI: 10.1039/c1cc13451e. View

Zhou H, Zhao Y, Gao G, Li S, Lan J, You J . Highly selective fluorescent recognition of sulfate in water by two rigid tetrakisimidazolium macrocycles with peripheral chains. J Am Chem Soc. 2013; 135(40):14908-11. DOI: 10.1021/ja406638b. View

Langton M, Beer P . Sulfate-selective binding and sensing of a fluorescent [3]rotaxane host system. Chemistry. 2012; 18(45):14406-12. DOI: 10.1002/chem.201202204. View

Sessler J, Katayev E, Pantos G, Ustynyuk Y . Synthesis and study of a new diamidodipyrromethane macrocycle. An anion receptor with a high sulfate-to-nitrate binding selectivity. Chem Commun (Camb). 2004; (11):1276-7. DOI: 10.1039/b403665d. View

Murch S, MacDonald T, Walker-Smith J, Levin M, Lionetti P, Klein N . Disruption of sulphated glycosaminoglycans in intestinal inflammation. Lancet. 1993; 341(8847):711-4. DOI: 10.1016/0140-6736(93)90485-y. View

Bryantsev V, Hay B . Are C-H groups significant hydrogen bonding sites in anion receptors? Benzene complexes with Cl-, NO3-, and ClO4-. J Am Chem Soc. 2005; 127(23):8282-3. DOI: 10.1021/ja0518272. View

Ravikumar I, Ghosh P . Recognition and separation of sulfate anions. Chem Soc Rev. 2012; 41(8):3077-98. DOI: 10.1039/c2cs15293b. View

Olomu A, Vickers C, Waring R, Clements D, Babbs C, Warnes T . High incidence of poor sulfoxidation in patients with primary biliary cirrhosis. N Engl J Med. 1988; 318(17):1089-92. DOI: 10.1056/NEJM198804283181703. View

10.

Mateus P, Delgado R, Andre V, Duarte M . Sulfate recognition by a hexaaza cryptand receptor. Org Biomol Chem. 2014; 13(3):834-42. DOI: 10.1039/c4ob02027h. View

11.

Villalonga P, Fernandez de Mattos S, Ramis G, Obrador-Hevia A, Sampedro A, Rotger C . Cyclosquaramides as kinase inhibitors with anticancer activity. ChemMedChem. 2012; 7(8):1472-80. DOI: 10.1002/cmdc.201200157. View

12.

Custelcean R, Bonnesen P, Duncan N, Zhang X, Watson L, Van Berkel G . Urea-functionalized M4L6 cage receptors: anion-templated self-assembly and selective guest exchange in aqueous solutions. J Am Chem Soc. 2012; 134(20):8525-34. DOI: 10.1021/ja300677w. View

13.

Sommer F, Kubik S . Anion binding of a neutral bis(cyclopeptide) in water-methanol mixtures containing up to 95% water. Org Biomol Chem. 2014; 12(44):8851-60. DOI: 10.1039/c4ob01497a. View

14.

Nieuw Amerongen A, Bolscher J, Bloemena E, Veerman E . Sulfomucins in the human body. Biol Chem. 1998; 379(1):1-18. DOI: 10.1515/bchm.1998.379.1.1. View

15.

Schaly A, Belda R, Garcia-Espana E, Kubik S . Selective recognition of sulfate anions by a cyclopeptide-derived receptor in aqueous phosphate buffer. Org Lett. 2013; 15(24):6238-41. DOI: 10.1021/ol4030919. View

16.

Dungan V, Ngo H, Young P, Jolliffe K . High affinity sulfate binding in aqueous media by cyclic peptides with thiourea arms. Chem Commun (Camb). 2012; 49(3):264-6. DOI: 10.1039/c2cc37686e. View

17.

Li Y, Flood A . Pure C-H hydrogen bonding to chloride ions: a preorganized and rigid macrocyclic receptor. Angew Chem Int Ed Engl. 2008; 47(14):2649-52. DOI: 10.1002/anie.200704717. View

18.

Rostami A, Colin A, Li X, Chudzinski M, Lough A, Taylor M . N,N'-diarylsquaramides: general, high-yielding synthesis and applications in colorimetric anion sensing. J Org Chem. 2010; 75(12):3983-92. DOI: 10.1021/jo100104g. View

19.

Mintzer M, Grinstaff M . Biomedical applications of dendrimers: a tutorial. Chem Soc Rev. 2010; 40(1):173-90. DOI: 10.1039/b901839p. View

20.

Borman C, Custelcean R, Hay B, Bill N, Sessler J, Moyer B . Supramolecular organization of calix[4]pyrrole with a methyl-trialkylammonium anion exchanger leads to remarkable reversal of selectivity for sulfate extraction vs. nitrate. Chem Commun (Camb). 2011; 47(27):7611-3. DOI: 10.1039/c1cc12060c. View