A Molecular Oyster: A Neutral Anion Receptor Containing Two Cyclopeptide Subunits with a Remarkable Sulfate Affinity in Aqueous Solution

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Abstract

An artificial anion receptor is presented, in which two cyclohexapeptide subunits containing l-proline and 6-aminopicolinic acid subunits in an alternating sequence are connected via an adipinic acid spacer. This compound was devised to stabilize the 2:1 sandwich-type anion complexes that are observed when the two cyclopeptide moieties are not covalently connected and to obtain a 1:1 stoichiometry for these aggregates. Electrospray ionization mass spectrometry and NMR spectroscopic investigations showed that the bridged bis(cyclopeptide) does indeed form defined 1:1 complexes with halides, sulfate, and nitrate. ROESY NMR spectroscopy and molecular modeling allowed a structural assignment of the sulfate complex in solution. The stabilities of various anion complexes were determined by means of NMR titrations and isothermal titration microcalorimetry in 50% water/methanol. Both methods gave essentially the same quantitative results, namely stability constants that varied in the range 105-102 M-1 and decreased in the order SO42- > I- > Br- > Cl- > NO3-. This order was rationalized in terms of the size of the anions with the larger anions forming the more stable complexes because they better fit into the cavity of the host. The ability of sulfate to form stronger hydrogen bonds to the NH groups of the receptor, in addition to its slightly larger ionic radius with respect to iodide, causes the higher stability of the sulfate complex. No significant effect of the countercation on complex stability was observed. Furthermore, complex stability is enthalpically as well as entropically favored. A comparison of the iodide and sulfate complex stabilities of the ditopic receptor with those of a cyclopeptide that forms 1:1 anion complexes in solution showed that the presence of a second binding site increases complex stability by a factor of 100-350.

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