Guest Binding with Sulfated Cyclodextrins: Does the Size of Cavity Matter?

Abstract

Sulfated cyclodextrins have recently emerged as potential candidates for producing host-induced guest aggregation with properties better than p-sulfonatocalixarenes that have previously shown numerous applications involving the phenomena of host-induced guest aggregation. In the class of sulfated cyclodextrins (SCD), sulfated β-cyclodextrin (β-SCD) remains the most extensively investigated host molecule. Although it is assumed that the host-induced guest aggregation is predominantly an outcome of interaction of the guest molecule with the charges on the exterior of SCD cavity, it has not been deciphered whether the variation in the cavity size will make a difference in the efficiency of host-induced guest-aggregation process. In this investigation, we present a systematic study of host-induced guest aggregation of a cationic molecular rotor dye, Thioflavin T (ThT) with three different sulfated cyclodextrin molecules, α-SCD, β-SCD and γ-SCD, which differ in their cavity size, using steady-state emission, ground-state absorption and time-resolved emission measurements. The obtained photophysical properties of ThT, upon interaction with different SCD molecules, indicate that the binding strength of ThT with different SCD molecules correlate with the cavity size of the host molecule, giving rise to the strongest complexation of ThT with the largest host molecule (γ-SCD). The binding affinity of ThT towards different host molecules has been supported by molecular docking calculations. The results obtained are further supported with the temperature and ionic strength dependent studies performed on the host-guest complex. Our results indicate that for host-induced guest aggregation, involving oppositely charged molecules, the size of the cavity also plays a crucial role beside the charge density on the exterior of host cavity.

Chiral Recognition of D/L-Ribose by Visual and SERS Assessments

“…β-CD is composed of seven D-glucose molecules, and the outer surface of a β-CD appears like a truncated cone; the inner cavity resembles a conical hourglass because of the inward protrusion of the glycosidic oxygens [ 21 ]. It is found that many molecules can be embedded into the guest-binding cavity of cyclodextrin to form complexes [ 30 ], like quinine [ 31 ], polychlorinated biphenyls (PCBs) [ 32 ], and thioflavin-T [ 33 ]. The glycosidic oxygen and hydroxyl groups of glucose molecules in CD can also provide hydrogen bonds [ 21 ].…”