Adjusting the binding thermodynamics, kinetics, and orientation of guests within large synthetic hydrophobic pockets.

ABSTRACT: Kinetic analysis of the host guest complexation of a large, open molecular basket and a highly complementary adamantoid guest reveals that for these types of systems a dissociative mechanism is in operation. Hence, the resident adamantyl guest must completely vacate the cavity before another guest molecule can move in to replace it. As a result of the rigid nature of the host, the energy barrier to this process is relatively high, about 16 kcal mol(-1) at room temperature. Modifying the cavity of the host by dangling either a methyl group or a hydroxyl group from the portal rim alters the thermodynamic binding profile of these hosts. (1)H NMR shift data analysis also reveals that these functional groups can adjust the orientation that monosubstituted guests adopt within the cavity. Additio

SUBMITTER: Gibb CL 

PROVIDER: S-EPMC122683 | biostudies-literature | 2002 Apr

REPOSITORIES: biostudies-literature