Cyclodextrin dimers as receptor molecules for steroid sensors.
The dansyl-modified dimer 9 complexes strongly with the steroidal bile salts. Relative to native beta-cyclodextrin, the binding of cholate (1a) and deoxycholate (1b) salts is especially enhanced. These steroids bind exclusively in a 1:1 fashion. For other bile salts (1c-1e) both 1:1 and 1:2 complexes were observed with stabilities similar to those of native beta-cyclodextrin. This indicates that only one cavity is used, with a small contribution from the second. The difference is attributed to the absence of a 12-hydroxy group in the second group of steroids. Comparison with a dimer that lacks the dansyl moiety (6) shows that this group especially hinders the cooperative binding of la and 1b. The smaller interference in the binding of the other steroids indicates that self-inclusion of the dansyl moiety hardly occurs. This weak self-inclusion is supported by fluorescence studies. The dansyl fluorescence of dimer 9 is less blue-shifted than that of other known dansyl-appended cyclodextrin derivatives; this is indicative of a more polar micro-environment. Addition of guests causes a change in fluorescence intensity.
de Jong
M R
MR
Laboratory of Supramolecular Chemistry and Technology, MESA+ Research Institute, University of Twente, Enschede, The Netherlands.
Engbersen
J F
JF
Huskens
J
J
Reinhoudt
D N
DN
D001647:Bile Acids and Salts / Q000737:chemistry; D047250:Calixarenes; D003505:Cyclodextrins / Q000737:chemistry*; D003619:Dansyl Compounds / Q000737:chemistry; D019281:Dimerization; D046911:Macromolecular Substances; D008968:Molecular Conformation; D012995:Solubility; D013050:Spectrometry, Fluorescence; D013256:Steroids / Q000737:chemistry*; D013816:Thermodynamics
D001647:Bile Acids and Salts; D003505:Cyclodextrins; D003619:Dansyl Compounds; D046911:Macromolecular Substances; D013256:Steroids; D047250:Calixarenes