Synthesis of a Novel Anthraquinone Diamino-Bridged Bis(β-cyclodextrin) and Its Cooperative Binding toward Guest Molecules

Abstract

A novel anthraquinone diamino-bridged bis(<TEX>$\beta$</TEX> -cyclodextrin) 2 was synthesized. The inclusion complexation behaviors of the native <TEX>$\beta$</TEX> -cyclodextrin 1 and the novel bis(<TEX>$\beta$</TEX> -cyclodextrin) 2 with guests, such as acridine red (AR), neutral red (NR), ammonium 8-anilino-1-naphthalenesulfonate (ANS), sodium 2-(p-toluidinyl) naphthalenesulfonate (TNS) and rhodamine B (RhB) were investigation by fluorescence, circular dichroism and 2D NMR spectroscopy. The spectral titrations were performed in phosphate buffer (pH 7.20) at 25 <TEX>${^{\circ}C}$</TEX> to give the complex stability constants (Ks) and Gibbs free energy changes (−<TEX>${\Delta}G^0$</TEX>) for the stoichiometric 1:1 inclusion complexation of host 1 and 2 with guests. The results indicated that the novel bis(<TEX>$\beta$</TEX> -cyclodextrin) 2 greatly enhanced the original binding affinity of the native <TEX>$\beta$</TEX> -cyclodextrin 1. Typically, bis(<TEX>$\beta$</TEX> -cyclodextrin) 2 showed the highest binding constant towards ANS up to 34.8 times higher than that of 1. The 2D NMR spectra of bis(<TEX>$\beta$</TEX> -cyclodextrin) 2 with RhB and TNS were performed to confirm the binding mode. The increased binding affinity and molecular selectivity of guests by bis(<TEX>$\beta$</TEX> -cyclodextrin) 2 were discussed from the viewpoint of the size/shape-fit concept and multipoint recognition mechanism.