Das Gopal, Matile Stefan
Department of Organic Chemistry, University of Geneva, CH-1211 Geneva, Switzerland.
Proc Natl Acad Sci U S A. 2002 Apr 16;99(8):5183-8. doi: 10.1073/pnas.022547899. Epub 2002 Mar 12.
Design, synthesis, and study of a synthetic barrel-stave supramolecule with p-octiphenyl "staves," beta-sheet "hoops," and hydrophobic exterior as well as internal carboxylate clusters are reported. Ion transport experiments indicate the formation of transmembrane pores at 5 < pH < 7 with nanomolar activity. Blockage of dye efflux from spherical bilayers by external Mg(OAc)(2) and internal 8-aminonaphthalene-1,3,6-trisulfonate is suggestive for weakly cooperative (n = 1.16) formation of aspartate-Mg(2+)-8-aminonaphthalene-1,3,6-trisulfonate complexes within the barrel-stave supramolecule (K(D) = 2.9 mM). Corroborative evidence from structural studies by circular dichroism spectroscopy is provided and discussed with emphasis of the importance of internal charge repulsion for pore formation and future applications toward binding and catalysis within supramolecular synthetic pores.
报道了一种合成桶板超分子的设计、合成及研究，该超分子具有对辛基苯基“桶板”、β-折叠“箍”、疏水外部以及内部羧酸盐簇。离子传输实验表明，在5 < pH < 7时形成了具有纳摩尔活性的跨膜孔。外部Mg(OAc)₂和内部8-氨基萘-1,3,6-三磺酸盐对球形双层膜中染料流出的阻断表明，桶板超分子内天冬氨酸-Mg²⁺-8-氨基萘-1,3,6-三磺酸盐络合物形成弱协同作用（n = 1.16）（解离常数K(D) = 2.9 mM）。提供了圆二色光谱结构研究的佐证证据，并进行了讨论，强调了内部电荷排斥对孔形成的重要性以及超分子合成孔在结合和催化方面的未来应用。
