Design,Synthesis,Supramolecular Recognition And Mimic Enzyme Catalysis Of Macrocyclic Polyamine Metal Complexes

Chemical nucleases are a new challenging field that is quickly developing in chemical biology. In this dissertation, new macrocyclic polyamines and their metal complexes have been designed and synthesized, and molecular recognition and mimic enzyme catalysis have been studied. A series of useful and creative results have been obtained.Four new types of macrocyclic polyamines and their metal(transition metal, La3+) complexes, which are monoarm, polyfunctional arm, bridging dinuclear, bridging polyhydroxy dinuclear macrocyclic polyamines, have been designed and prepared. The synthetic methods and effect factors of the title compounds have been systematically studied. A series of convenient and efficient reactions have been developed. The X-ray analysis of the bridging macrocyclic polyamines dinuclear Zn(II) have been studied and discussed.The supramolecular recognition ability of the macrocyclic polyamines metal complexes for base, diacid and nucleosides, and the catalytic hydrolysis for phosphate diester (BNPP) have been investigated by UV-visible spectrophoto-metric tritation. The results show that the host compounds form 1:1 or 1:2 supramolecular complexes with the guestes. The experimental results indicate that the molecular recognition is mainly due to electrostatic force, n-n stacking and hydrogen bond. The hydrolysis for phosphate diester(BNPP) by macrocyclic polyamines metal complexes is very efficiency, the rate enhancement is up to 2.40 X 103~5.94X104 fold. Dinuclear complexes is superior to mononuclear. The resultsalso imply the structure of complexes, the nature of metal ion, the hydrophobic microenvironment all are important factors for the catalytic reactions.The hydrolysis or cleavage of plasmid DNA(PUC18, PBRaai) by macrocyclic polyamine metal complexes has been investigated. They have mimicked successfully the selectivities and the orientation of chemical nucleases, are efficient biomimetic enzymes, and the bridging dinuclear macrocyclic polyamines Zn(II) complexes could cleaved from supercoiled DNA(Form I) to nicked circular DNA(Form II) with 25 u M in SOmin. The results show that these complexes have the same catalysis activity as restriction enzymes.