title: Solvent and guest isotope effects on complexation thermodynamics of alpha-, beta-, and 6-amino-6-deoxy-beta-cyclodextrins.
abstract: The stability constant (K), standard free energy (DeltaG degrees ), enthalpy (DeltaH degrees ), and entropy changes (TDeltaS degrees ) for the complexation of native alpha- and beta-cyclodextrins (CDs) and 6-amino-6-deoxy-beta-CD with more than 30 neutral, positively, and negatively charged guests, including seven fully or partially deuterated guests, have been determined in phosphate buffer solutions (pH/pD 6.9) of hydrogen oxide (H(2)O) or deuterium oxide (D(2)O) at 298.15 K by titration microcalorimetry. Upon complexation with these native and modified CDs, both nondeuterated and deuterated guests examined consistently exhibited higher affinities (by 5-20%) in D(2)O than in H(2)O. The quantitative affinity enhancement in D(2)O versus H(2)O directly correlates with the size and strength of the hydration shell around the charged/hydrophilic group of the guest. For that reason, negatively/positively charged guests, possessing a relatively large and strong hydration shell, afford smaller K(H2O)/K(D2O) ratios than those for neutral guests with a smaller and weaker hydration shell. Deuterated guests showed lower affinities (by 5-15%) than the relevant nondeuterated guests in both H(2)O and D(2)O, which is most likely ascribed to the lower ability of the C-D bond to produce induced dipoles and thus the reduced intracavity van der Waals interactions. The excellent enthalpy-entropy correlation obtained can be taken as evidence for the very limited conformational changes upon transfer of CD complexes from H(2)O to D(2)O.
authors.affiliation: Entropy Control Project, ICORP, JST, 4-6-3 Kamishinden, Toyonaka 560-0085, Japan.
authors.forename: Mikhail V
authors.initials: MV
authors.lastname: Rekharsky
authors.forename: Yoshihisa
authors.initials: Y
authors.lastname: Inoue
mesh_terms: D002151:Calorimetry; D003505:Cyclodextrins / Q000737:chemistry*; D003903:Deuterium; D017666:Deuterium Oxide / Q000737:chemistry; D006860:Hydrogen Bonding; D007700:Kinetics; D012997:Solvents; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
chemical_list: D003505:Cyclodextrins; D012997:Solvents; D014867:Water; D003903:Deuterium; D017666:Deuterium Oxide