Self-Assembled Quaternary Ammonium-Containing Comb-Like Polyelectrolytes for the Hydrolysis of Organophosphorous Esters: Effect of Head Groups and Counter-Ions

Tatiana N Pashirova; Petr A Fetin; Alexey A Lezov; Matvey V Kadnikov; Farida G Valeeva; Evgenia A Burilova; Alexander Yu Bilibin; Ivan M Zorin

doi:10.1002/cplu.202000417

Self-Assembled Quaternary Ammonium-Containing Comb-Like Polyelectrolytes for the Hydrolysis of Organophosphorous Esters: Effect of Head Groups and Counter-Ions

Chempluschem. 2020 Aug;85(8):1939-1948. doi: 10.1002/cplu.202000417.

Authors

Tatiana N Pashirova¹, Petr A Fetin², Alexey A Lezov³, Matvey V Kadnikov², Farida G Valeeva¹, Evgenia A Burilova¹, Alexander Yu Bilibin², Ivan M Zorin²

Affiliations

¹ Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzov St., 8, Kazan, 420088, Russian Federation.
² Institute of Chemistry, St. Petersburg State University, 7/9 Universitetskaya nab, St., Petersburg, 199034, Russian Federation.
³ Department of Molecular Biophysics and Polymer Physics, Physical Faculty, St. Petersburg State University, 7/9 Universitetskaya nab, St., Petersburg, 199034, Russian Federation.

PMID: 32865345
DOI: 10.1002/cplu.202000417

Abstract

The aim of this work was to increase the efficiency of catalytic systems for the hydrolytic cleavage of 4-nitrophenyl esters of phosphonic acids. Quaternary ammonium-containing comb-like polyelectrolytes («polymerized micelles») with ester cleavable fragments and a low aggregation threshold were used as catalysts. The synthesis of poly(11-acryloyloxyundecylammonium) surfactants with different counterions (Br^- , NO₃^- , CH₃ C₆ H₄ SO₃^- ) and head groups was realized by micellar free-radical polymerization. Molecular weight, critical association concentration, particle sizes and solubilization properties toward Orange OT were determined. Self-assemblies organized by poly(11-acryloyloxyundecyltrimethyl ammonium) bromide successfully catalyze the hydrolysis of 4-nitrophenyl butylchloromethylphosphonate up to two orders of magnitude compared to aqueous alkaline hydrolysis. The development of these catalysts is promising for industrial applications and organophosphorus compound detoxification.

Keywords: hydrolysis; phosphorous acid esters; polyelectrolytes; self-assembly; surfactants.

Publication types

Research Support, Non-U.S. Gov't