The cone-calix[4]arene derivative (1H(3))(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 (1H(3))(2+). At pH 9.5, the rate enhancement of p-nitrophenol liberation from BNPP relative to background hydrolysis is 6.5 x 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.

Salvio, R., Volpi, S., Cacciapaglia, R., Sansone, F., Mandolini, L., Casnati, A. (2016). Phosphoryl Transfer Processes Promoted by a Trifunctional Calix[4]arene Inspired by DNA Topoisomerase i. JOURNAL OF ORGANIC CHEMISTRY, 81(19), 9012-9019 [10.1021/acs.joc.6b01643].

Phosphoryl Transfer Processes Promoted by a Trifunctional Calix[4]arene Inspired by DNA Topoisomerase i

Salvio R.
;
2016-01-01

Abstract

The cone-calix[4]arene derivative (1H(3))(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 (1H(3))(2+). At pH 9.5, the rate enhancement of p-nitrophenol liberation from BNPP relative to background hydrolysis is 6.5 x 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.
2016
Pubblicato
Rilevanza internazionale
Articolo
Esperti anonimi
Settore CHIM/06 - CHIMICA ORGANICA
English
Con Impact Factor ISI
Calixarenes; Carbon-13 Magnetic Resonance Spectroscopy; DNA Topoisomerases, Type I; Humans; Hydrogen-Ion Concentration; Kinetics; Phenols; Phosphorus; Potentiometry; Proton Magnetic Resonance Spectroscopy; Spectrometry, Mass, Electrospray Ionization
Salvio, R., Volpi, S., Cacciapaglia, R., Sansone, F., Mandolini, L., Casnati, A. (2016). Phosphoryl Transfer Processes Promoted by a Trifunctional Calix[4]arene Inspired by DNA Topoisomerase i. JOURNAL OF ORGANIC CHEMISTRY, 81(19), 9012-9019 [10.1021/acs.joc.6b01643].
Salvio, R; Volpi, S; Cacciapaglia, R; Sansone, F; Mandolini, L; Casnati, A
Articolo su rivista
File in questo prodotto:
File Dimensione Formato  
Salvio Joc2016 Topoisomerasi.pdf

solo utenti autorizzati

Tipologia: Versione Editoriale (PDF)
Licenza: Copyright dell'editore
Dimensione 2.24 MB
Formato Adobe PDF
2.24 MB Adobe PDF   Visualizza/Apri   Richiedi una copia

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2108/247685
Citazioni
  • ???jsp.display-item.citation.pmc??? 1
  • Scopus 17
  • ???jsp.display-item.citation.isi??? 15
social impact