Selective Modify Cyclodextrins And The Application Of Cyclodextrin Derivatives In Peroxalate Chemiluminesence

Cyclodextrins and their chemically modified derivatives are widely used in artificial enzymes, catalyze, drug carrier, etc. Cyclodextrins can be subjected to diverse modifications to give a wide variety of cyclodextrin derivatives, which could alter the conformation, size and the molecular selectivity of the guest molecular. Selective modified cyclodextrins is also difficult own to the numerous hydroxyl of it. In this thesis a facile method of synthesing mono- and per(2-sulfonyl)-β- cyclodextrins was afforded, and a series of dansyl modified cyclodextrins were synthesed which were subjected to the chmiluminesence reaction. A series of useful and creative results have been obtained. The major contents are as follows:1. The general aspect of the mothed of selective modifying cyclodextrin and their use in supramolecular chemistry.2. Afford a facile syntheses of mono- and per(2-sulfonyl)-β-cyclodextrinso Cs₂CO₃ was found to efficiently catalyze the reaction ofβ-cyclodextrin and N-tosylimidazole. This methodology has the advantage of a fast and clean reaction, facile manipulation and stable results for the monosulfonates.lt also ensured the first direct sulfonylation of all the 2-OHs.3. Efficient topological control in the syntheses of cappedγ-cyclodextrins. Modified one glucose unit(A) ofγ-cyclodextrin with N-dansyl-L-cysteine, in the precess of esteri-fition the flexible cysteine moiety can differentiate hydroxyl groups in clockwise -counterclockwise relationship led to the reaction of only 6^B-OH among many others, affording the corresponding lactone. The bulky dansyl group is supposed to display an important role in control the regio-selectivity.4. Four kinds, thirteen novel cyclodextrin derivatives, including mono-modifiedβ-cyclodextrin and -cyclodextrin on the different rims, imidazole and dansyl dimodifiedβ-cyclodextrin, capped cyclodextrin and bridgedγ-cyclodextrin, and their structures were characterized by NMR, MS.5. Chmiluminesence properties of the dansyl modified cyclodextrins were examined, the results show that 1:1 in inclusion complexes are formed for the 3-dansyl-β-cyclodextrin with TCPO. The influence of cyclodextrin on the fluorescence and the chemiexcitation were also examined. Campared with dansyl glycine, compound 3-dansyl-β-cyclodextrin showed 2 times enhancement of chemiexcitation. The conformation of cyclodextrin derivatives were elucidated by spectropolarimetric, and further explaination were also gived.