Design, Synthesis And Intelligent Design Of Molecularly Imprinted Catalysts

Molecular imprinting and intelligent materials have played important roles in achieving a new generation of smart imprinted polymers.In this thesis,a kind of molecularly imprinted catalyst "switches" capable of selective hydrolysis were synthesized basing on a rational self-assembly between monomers and a TSA template in the presence of intelligent materials.Thermodynamic and kinetic principles were used to analyze and discuss the catalysis behavior of these prepared molecularly imprinted catalysts.The results indicate that the specific catalysis by molecularly imprinted polymer catalysts can be internally a result of the larger speedup for the imprint species. Kinetic analysis indicates that this specific catalysis may be due to the preferential promotion of the imprinted species.Thermodynamic study further implies that the molecular induction,in essence,played a role,which made the imprinted polymer capable of specifically alluring the imprint species to bind.To realize the controllable imprinting recognizing process,combining a 'smart' technique into the preparation of catalyst,the influence of the operation temperature on the catalysis of the prepared catalyst were discussed.The use of N-isopropylacylamide played obviously a role on causing the appearance of temperature-swinging catalyst.At relatively low temperatures, the prepared catalyst provided highly specific catalysis for the imprinted substrate,which is comparable to a traditionally imprinted one.However,at relatively high temperatures, the prepared catalyst did not show significant catalysis.To overcome the drawback of the traditional PNIPA-based imprinted polymer,which generally does not lead to valuable applications because of the low catalyst activity,we have designed a new zipper-like imprinted polymer catalyst.Based on the electrostatic interaction between PAMPS and PAAM,the prepared catalyst at low temperature provided relatively lowly catalysis,but it show significant catalysis at high temperature.The prepared polymer demonstrated obviously a catalysis-switchable behavior,which thus made the modulated catalysis possible.