Comparison of catalytic activities of new La (III) and Ce (III) complexes with different diaza-crown ether ligands for DNA hydrolytic cleavage

A new diaza-crown ether with double hydroxypropyl branches (L = 1,1'-(1,4,10,13-tetraoxa-7,16-diazacyclooctadecane-7,16-diyl)dipropan-2-ol) and its two lanthanide complexes (LaL and CeL) were synthesised and characterised. Their nuclease activities on pUC19 DNA cleavage were investigated using...

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Bibliographic Details
Published in:Progress in reaction kinetics and mechanism 2016-01, Vol.41 (3), p.309-318
Main Authors: Li, Fang-zhen, Xie, Jia-qing, Cai, Shu-lan, Feng, Fa-mei
Format: Article
Language:English
Subjects:
Bonding
Catalysis
Catalysts
Cleavage
Deoxyribonucleic acid
Ethers
Hydrogen bonding
Reaction kinetics
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Summary:A new diaza-crown ether with double hydroxypropyl branches (L = 1,1'-(1,4,10,13-tetraoxa-7,16-diazacyclooctadecane-7,16-diyl)dipropan-2-ol) and its two lanthanide complexes (LaL and CeL) were synthesised and characterised. Their nuclease activities on pUC19 DNA cleavage were investigated using agarose gel electrophoresis, and pseudo-first-order rate constants kobs of 0.067 h–1 for LaL, 0.041 h–1 for CeL, 0.013 h–1 for LaL0, and 0.027 h–1 CeL0 were obtained (L0 = 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane). The results indicated that the CeL complex was more efficient than the LaL complex for DNA cleavage at low concentrations, but the LaL complex was more efficient than the CeL complex at high concentrations. Moreover, kinetic studies demonstrated that introducing hydroxypropyl side arms in the ring of the diaza-crown ether can improve the catalytic ability of the complexes in DNA cleavage, which may be due to the hydroxypropyl side arms enhancing the bonding interaction between the complex and the DNA molecule by hydrogen bonding. A hydrolytic mechanism for DNA cleavage was demonstrated by applying several oxygen scavengers to the DNA catalytic cleavage. A proposed mechanism for the DNA cleavage shows that the hydroxypropyl side groups can recognise and bind the phosphodiester bond of DNA by hydrogen bonding and electrostatic interaction.
ISSN:1468-6783
1471-406X
DOI:10.3184/146867816X14698928943442