Bioorganic chemistry à la baguette: studies on molecular recognition in biological systems using rigid-rod molecules.
Initial studies using rigid-rod molecules or "baguettes" to address bioorganic topics of current scientific concern are reported. It is illustrated how transmembrane oligo(p-phenylene)s as representative model rods can be tuned to recognize lipid bilayer membranes either by their thickness or polarization. The construction of otherwise problematic hydrogen-bonded chains along transmembrane rods yields "proton wires," which act by a mechanism that is central in bioenergetics but poorly explored by means of synthetic models. Another example focuses on multivalent ligands assembling rigid-rod cell-surface receptors into transmembrane dynamic arene arrays. The potassium transport mediated by these ligand-receptor complexes provides experimental support for the potential biological importances of the controversial cation-pi mechanism. More complex supramolecular architecture is portrayed in the first artificial beta-barrels. It is shown how programmed assembly of toroidal rigid-rod supramolecules in detergent-free water permits control of diameter of the chemical nature of their interior. Reversed rigid-rod beta-barrels are assembled to function as self-assembled ionophores, ion channel models, and transmembrane nanopores. The potential of future intratoroidal chemistry is exemplified by encapsulation and planarization of beta-carotene in water and the construction of transmembrane B-DNA at the center of a second-sphere host-guest complex à al baguette.
Matile
S
S
Department of Organic Chemistry, University of Geneva, Switzerland. stefan.matile@chiorg.unige.ch
D001555:Benzene Derivatives / Q000737:chemistry; D002462:Cell Membrane / Q000737:chemistry / Q000648:ultrastructure; D007473:Ion Channels / Q000378:metabolism*; D017136:Ion Transport; D007476:Ionophores / Q000737:chemistry*; D008024:Ligands; D008051:Lipid Bilayers / Q000378:metabolism*; D008968:Molecular Conformation; D015335:Molecular Probes / Q000737:chemistry*; D011956:Receptors, Cell Surface / Q000378:metabolism
D001555:Benzene Derivatives; D007473:Ion Channels; D007476:Ionophores; D008024:Ligands; D008051:Lipid Bilayers; D015335:Molecular Probes; D011956:Receptors, Cell Surface