title: Biotinylated Cyclophane: Synthesis, Cyclophane-Avidin Conjugates, and Their Enhanced Guest-Binding Affinity.
abstract: Cationic and anionic cyclophanes bearing a biotin moiety were synthesized as a water-soluble host (1a and 1b, respectively). Both hosts 1a and 1b were found to strongly bind avidin with binding constants of 1.3 × 10(8) M(-1), as confirmed by surface plasmon resonance measurements. The present conjugate of 1a with avidin (1a-avidin) showed an enhanced guest binding affinity toward fluorescence guests such as TNS and 2,6-ANS. The K values of 1a-avidin conjugate with TNS and 2,6-ANS were ~19-fold larger than those of monocyclic cyclophane 1a with the identical guests. Favorable hydrophobic and electrostatic interactions between 1a-avidin and TNS were suggested by computer-aided molecular modeling calculations. Moreover, addition of excess biotin to the complexes of 1a-avidin with the guests resulted in dissociation of 1a-avidin to avidin and 1a having less guest-binding affinity. Conversely, such enhancements in the guest-binding affinity were not obviously observed for the conjugate of anionic 1b with avidin (1b-avidin) due to electrostatic repulsion between anionic 1b and anionic guests.
authors.affiliation: Department of Chemistry, Faculty of Science, Fukuoka University , Nanakuma 8-19-1, Fukuoka 814-0180, Japan.
authors.forename: Osamu
authors.initials: O
authors.lastname: Hayashida
authors.affiliation: Department of Chemistry, Faculty of Science, Fukuoka University , Nanakuma 8-19-1, Fukuoka 814-0180, Japan.
authors.forename: Miwa
authors.initials: M
authors.lastname: Kojima
authors.affiliation: Department of Chemistry, Faculty of Science, Fukuoka University , Nanakuma 8-19-1, Fukuoka 814-0180, Japan.
authors.forename: Shuhei
authors.initials: S
authors.lastname: Kusano
mesh_terms: D001360:Avidin / Q000138:chemical synthesis* / Q000737:chemistry; D001665:Binding Sites; D001710:Biotin / Q000138:chemical synthesis* / Q000737:chemistry; D019921:Biotinylation; D057927:Hydrophobic and Hydrophilic Interactions; D007477:Ions / Q000737:chemistry*; D007700:Kinetics; D008958:Models, Molecular; D011485:Protein Binding
chemical_list: D007477:Ions; D001360:Avidin; D001710:Biotin