1. Chapter 4. Synthetic Receptors for Small Organic and Inorganic Anions Stefan Kubik Fachbereich Chemie - Organische Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Straße, D-67663 Kaiserslautern, Germany Email: kubik@chemie.uni-kl.de Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

2. Table 1 Ionic radii, enthalpies of solvation, Gibbs energies of solvation, and pK a values of selected inorganic anions. a. Relative amount of the anion in water at pH 7.4 based on its pK a value. Other species present under these conditions are the protonated and/or deprotonated forms of the anion; b. not available. Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

3. Figure 4.1 Typical Hofmeister series for a selection of common inorganic anions. Note that the order depends on the experiment used to determine the anion effect, on the counterion, and on concentration, so that anions can sometimes exchange position in this series. Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

4. Chart 4.1 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

5. Chart 4.2 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

6. Chart 4.3 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

7. Chart 4.4 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

8. Chart 4.5 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

9. Chart 4.6 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

10. Chart 4.7 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

11. Chart 4.8 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

12. Chart 4.9 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

13. Chart 4.10 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

14. Chart 4.11 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

15. Chart 4.12 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

16. Chart 4.13 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

17. Figure 4.2 Electrostatic potential surfaces of the four halides fluoride, chloride, bromide and iodide. Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

18. Figure 4.3 Binding arrangement of a chloride anion inside the narrowest pore region of the chloride ion channel from S. typhimurium (left) and schematic representation of the underlying interactions (right). The picture was generated by using VMD from the structure deposited in the RCSB Protein Data Bank (code 1KPL). Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

19. Figure 4.4 Examples of prodigiosins. Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

20. Chart 4.14 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

21. Chart 4.15 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

22. Figure 4.5 Calculated structures of the sandwich type iodide complexes of receptors 4.35 (left) and 4.36, and crystal structure of the corresponding complex of 4.37 (right). Calculations were performed by the author by using Spartan 10 and the MMFF force-field. Hydrogen atoms except those on the NH groups are omitted for reasons of clarity. Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

23. Chart 4.16 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

24. Chart 4.17 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

25. Figure 4.6 Electrostatic potential surfaces of the azide and the cyanide anion. Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

26. Figure 4.7 Coordination of the cyanide anion to the heme a 3 and Cu B centers of bovine cytochrome c oxidase (left) and schematic representation of the underlying interactions (right). The picture was generated by using VMD from the structure deposited in the RCSB Protein Data Bank (code 3AG4). Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

27. Chart 4.18 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

28. Chart 4.19 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

29. Figure 4.8 Electrostatic potential surfaces of the nitrate, carbonate, and acetate anion. Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

30. Figure 4.9 Arrangement of L-N-(hydroxyaminocarbonyl)phenylalanine inside the binding site of carboxypeptidase A (left) and schematic representation of the underlying interactions (right). The picture was generated by using VMD from the structure deposited in the RCSB Protein Data Bank (code 1HEE). Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

31. Chart 4.20 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

32. Chart 4.21 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

33. Chart 4.22 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

34. Chart 4.23 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

35. Chart 4.24 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

36. Chart 4.25 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

37. Chart 4.26 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

38. Figure 4.10 Electrostatic potential surfaces of the sulfate, phosphate, arsenate, and perchlorate anion. Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

39. Figure 4.11 Binding arrangement of a hydrogenphosphate anion inside the binding site of the phosphate-binding protein (PBP) (left) and schematic representation of the underlying interactions (right). The picture was generated by using VMD from the structure deposited in the RCSB Protein Data Bank (code 1IXH). Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

40. Figure 4.12 Binding arrangement of a sulfate anion inside the binding site of the sulfate-binding protein (SBP) from Salmonella typhimurium (left) and schematic representation of the underlying interactions (right). The picture was generated by using VMD from the structure deposited in the RCSB Protein Data Bank (code 1SBP). Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

41. Chart 4.27 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

42. Chart 4.28 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

43. Chart 4.29 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

44. Chart 4.30 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

45. Chart 4.31 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

46. Chart 4.32 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015

47. Chart 4.33 Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015