Research On Supramolecular Sensors For Recognition Of Sulfonic Compounds

Sulfonic compounds are widely employed in chemical industry, such as dye intermediates, slushing agents for concrete, catalysts and surfactants. And it got worldwide attention due to so many environmental issues and food safety issues caused. This confirmed that research on recognition of sulfonic compounds will be meaningful. As the raw materials of intermediates of naphthalene series,1-naphthalenesulfonic acid,2-naphthalenesulfonic acid,1,5-naphthalenedisulfonic acid and sodium dodecyl benzene sulfonate(the main ingredient of synthetic detergents) were chosen for the recognition investigation. This thesis was divided into five chapters.Chapter one, as preface of this thesis, basic concepts and theories of supramolecular chemistry and molecular recognition were introduced. Research progresses on the host-guest interaction of cucurbit[n]uril, application of fluorescent probe as well as recognition of sulfonic compounds were overviewed.Chapter two, cucurbit[n]uril has become one kind of macrocyclic molecules with wide application because of its rigid structure, hydrophobic cavity, unique binding-sites and special electrostatic characteristics. Electron-deficient first guest and electron-rich second guest bound autonomously into the host cucurbit[8]uril(CB[8]) and finally formed stable ternary(or more) complex as the result of CT(charge-transfer) interaction between these two guests enhanced by CB[8]’s cavity. Carbazole-tailed imidazolium was synthetized as first guest. After that different naphthalene sulfonic compounds were studied as second guest respectively. And the experimental data of UV-Vis spectra and ESI-MS proved that only1-naphthalenesulfonic acid paired with first guest to form the stable ternary complex. This ternary complex system based on CT interaction in CB[8]"s cavity can also be appropriate for recognition of other second guest with different electron-deficient first guest.Chapter three, a novel supramolecular tripodal fluorescence sensor based on N-core, thiourea as binding-site and1,8-naphthanlimide derivatives as fluorophore was designed and synthesized successfully. Studies on the interaction between the tripodal fluorescence sensor and naphthalene sulfonic compounds were proceeded respectively. Fluorescence spectra of the tripodal sensor in THF on addition of1-naphthalenesulfonic acid showed evident fluorescence enhancement. Oppositely, the fluorescence quenching was caused by adding1.5-naphthalenedisulfonic acid. There is no change of fluorescence spectra after addition of2-naphthalenesulfonic acid. The result showed that the tripodal fluorescence sensor make a distinction between these three types of naphthalenesulfonic acid. What’s more, it is the first time to distinguish mono-substituted naphthalenesulfonic acids, which are constitutional isomers.Chapter four, sodium dodecyl benzene sulfonate (SDBS) is often found in waste oil, which indicates the possibility of distinguishing waste oil by content determination of SDBS. For this purpose, the interaction between the tripodal fluorescence sensor and dodecyl benzene sulfonic anion (SDBA) were investigated. Fluorescence spectra of the fluorescence sensor with addition of SDBA in chloroform showed evident fluorescence enhancement due to PET mechanism. Moreover, this method was found to be with simplicity, high-selectivity and applicability.Chapter five is a summary of the whole thesis.