Supplementary information for Synthetic Receptors for Biomolecules Design

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Chapter 3. Synthetic Receptors for Alkali Metal Cations George W. Gokel*a, b, c and Joseph W. Meisela, b a. Center for Nanoscience, b. Department of Chemistry and Biochemistry, c. Department of Biology, University of Missouri-St. Louis, 1 University Blvd. Saint Louis, MO 63121 USA *Email: gokelg@umsl. edu

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Chart 3. 1 Solid state structure of the polyether ionophore, monensin A, binding Na+.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Chart 3. 2 Partial structures of two biological ion channels showing: (A) Two Na+ binding sites in the Leu. T Na+-dependent pump (PDB code 2 A 65). (B) Four K+ binding sites in the Kcs. A K+ channel (PDB code 1 K 4 C). (Reproduced with permission from Science 2005, 310, 1461, © American Association for the Advancement of Science)

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 1 Coordination compounds and bidentate complexes

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 2 The chemistry leading to the first crown ethers.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 3 Solid state structure of dibenzo-18 -crown-6 binding K+ (CSD: BEBFAP).

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 4 Two-armed diaza-18 -crown-6 derivatives having three atom sidearms.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Table 3. 1 Homogeneous complexation constants and thermodynamic parameters determined in methanola, b.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 5 Binding constants determined in 100% methanol solution for 3 n-crown-n compounds where n = 4 – 8.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 6 Solid state structures of uncomplexed 12 -crown-4 (CSD: TOXCDP) and K+ ion complexed by 18 -crown-6 (CSD: KTHOXD).

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 7 Solid state structures of (12 C 4)2 • Na+ (CSD: BEYHES) and ( Aza-12 C 4)2 • Na+ (CSD: FEHDOL).

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 8 Solvent dependence of 18 -crown-6 • Na+ binding in methanol and water.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 9 Structures of [2. 1. 1]cryptand [3. 2. 2]cryptand.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 10 Solid state structure of [2. 2. 2]cryptand complexing KI.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 11 Left: a spherand. Center: a hemispherand. Right a crown-hemispherand.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 12 Macrocyclic compounds formed by acid-catalyzed, multiple condensations.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 13 Calixarene receptor molecules.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 14 K+ complexation by a calix-crown.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 15 Comparison of homogeneous binding and extractions constants with transport rate.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 16 Schematic representation of a liposome and a typical phospholipid.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 17 Redox-switched molecular receptors.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 18 Examples of host molecules that can be photo-switched.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 19 Relative NH 4+ binding strengths for 18 -membered ring macrocycles.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 20 Crown ether-derived colorimetric sensors: “chromoionophores”.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 21 Fluoroionophores based on crown ethers and calixarenes.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 22 Chemical structure of the cyclic peptide K+ carrier valinomycin.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 23 (Top) Single-armed carbon-pivot and nitrogen pivot lariat ethers. (Bottom) a two-armed or bibracchial nitrogen-pivot lariat ether.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 24 Solid state structure of 4, 13 -diaza-18 -crown-6 having two methoxyethyl side arms attached to nitrogen and binding KI.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Table 2 Sodium and potassium cation binding by lariat ethers expressed as log 10 KS. a

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 25 Bibracchial lariat ethers containing π-donor side arms.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 26 Solid state structures of phenyl (CSD: OCABEZ) and pentafluorobenzyl (CSD: OCACIE) side-armed bibracchial lariat ethers binding KI.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 27 Solid state structure of a calixarene • 2 Cs+ complex (CSD: RADBUT).

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 28 A ditopic receptor binding both Na+ and I- (CSD: IBUKUM).

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 29 An ion-conducting channel based on the cyclodextrin scaffold.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 30 Channel designs reported by Lehn (left) and by Fyles and their coworkers.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 31 The hydraphile channel concept.

Supplementary information for Synthetic Receptors for Biomolecules: Design Principles and Applications © The Royal Society of Chemistry 2015 Figure 3. 32 An array of synthetic amphiphiles that show channel-like function.