Complex formation of large-ring cyclodextrins (CDs) having DP21-32 with iodine in aqueous KI solution was studied by isothermal titration calorimetry (ITC). When the individual CD is shown, the term CD
n is used, where n represents the degree of polymerization. For CDs in the DP range of 21-32, the curves obtained for the titration of the CDs with iodine can be analyzed by a model assuming 1:2 complex formation with identical interacting sites. For the case of two identical interacting sites, the binding constants
K1 and
K2 (
K1 <
K2), defined relative to the progress of saturation, lie in the range 0.7 to 7.3×10
3M
-1 and 3.0 to 62.6×10
3M
-1, respectively. The values of Δ
H2 and
TΔ
S2 lie in the range -34.9 to -136.4kJ mol
-1 and -15.5 to -112.8kJ mol
-1, respectively. The largest values for -
TΔ
S2 obtained for a CD
26 can, in part, be attributed to a large decrease in conformational flexibility of the CD which occurs during complex formation. Based on ITC data, conformational changes in CD
26 which are induced as the results of the formation of a CD-iodine inclusion complex are discussed in terms of the recently reported crystal structure of CD
26.
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