Kinetics of hydrogen bonds in aqueous solutions of cyclodextrin and its methyl-substituted forms

摘要

Molecular dynamics simulations of β-cyclodextrin (BCD) and its two methyl-substituted derivatives, namely, heptakis(2,6-di-O-methyl)-β- cyclodextrin (DIMEB) and heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin (TRIMEB) have been performed in aqueous solutions. Detailed analyses were carried out to investigate the effects of substitution on the kinetics of cyclodextrin-water and water-water hydrogen bonds formed by water present in the hydration layers around these macromolecules as well as those formed by water inside their cavities. It is observed that increased geometrical constraints due to substitution of the OH groups of the glucose rings of the BCD molecule result in rapid establishment of hydrogen bond breaking and reformation equilibria for DIMEB and TRIMEB. This has been found to be the microscopic origin of highly rigid arrangement of water around TRIMEB and inside its cavity, as against water in and around BCD and DIMEB.