Phosphoryl Transfer Processes Promoted by a Trifunctional Calix[4]arene Inspired by DNA Topoisomerase I
| Autor: | Alessandro Casnati, Luigi Mandolini, Stefano Volpi, Francesco Sansone, Riccardo Salvio, Roberta Cacciapaglia |
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| Rok vydání: | 2016 |
| Předmět: |
binding
Proton Magnetic Resonance Spectroscopy Type I receptors 01 natural sciences Medicinal chemistry Settore CHIM/06 chemistry.chemical_compound Nucleophile Calixarene Moiety cleavage Guanidine bifunctional artificial phosphodiesterases complexes Chemistry Electrospray Ionization Phosphorus Hydrogen-Ion Concentration DNA Topoisomerases Type I supramolecular catalysis artificial nucleases Spectrometry Mass Electrospray Ionization Stereochemistry Potentiometric titration upper rim guanidinium unit 010402 general chemistry molecular recognition catalysis ion Catalysis Hydrolysis Phenols Humans Carbon-13 Magnetic Resonance Spectroscopy Spectrometry 010405 organic chemistry Organic Chemistry enzyme mimics Mass 0104 chemical sciences reaction mechanisms Kinetics Calixarenes Potentiometry calixarene DNA Topoisomerases Derivative (chemistry) |
| Zdroj: | Journal of organic chemistry 81 (2016): 9012–9019. doi:10.1021/acs.joc.6b01643 info:cnr-pdr/source/autori:Salvio R. (1); Volpi S. (2); Cacciapaglia R. (1); Sansone F. (2); Mandolini L. (1); Casnati A. (2)/titolo:Phosphoryl transfer processes promoted by a trifunctional calix[4]arene inspired by DNA topoisomerase I/doi:10.1021%2Facs.joc.6b01643/rivista:Journal of organic chemistry/anno:2016/pagina_da:9012/pagina_a:9019/intervallo_pagine:9012–9019/volume:81 |
| ISSN: | 1520-6904 |
| Popis: | The cone-calix[4]arene derivative (1H3)2+, decorated at the upper rim with two guanidinium units and a phenolic hydroxyl in an ABAH functionalization pattern, effectively promotes the cleavage of the DNA model compound bis(p-nitrophenyl) phosphate (BNPP) in 80% DMSO solution at pH values in the range 8.5-12.0. The pH dependence of the kinetics was found to be fully consistent with the results of the potentiometric titration of the triprotic acid (1H3)2+. At pH 9.5, the rate enhancement of pnitrophenol liberation from BNPP relative to background hydrolysis is 6.5 × 10^4-fold at 1 mM concentration of the calix[4]arene derivative. Experimental data clearly point to the effective cooperation of the three active units and to the involvement of the phenolate moiety as a nucleophile in the phosphoryl transfer step. Subsequent liberation of a second equivalent of p-nitrophenol from the phosphorylated calixarene intermediate is conceivably promoted by the "built-in" guanidine/guanidinium catalytic dyad. |
| Databáze: | OpenAIRE |
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