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A polymeric amine–copper(II) complex as catalyst for the hydrolysis of 1,2,2‐trimethylpropyl methylphosphonofluoridate (soman) and bis (1‐methylethyl) phosphorofluoridate (DFP)
Author(s) -
Hammond Philip S.,
Forster Jeffry S.
Publication year - 1991
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.1991.070431017
Subject(s) - soman , hydrolysis , chemistry , catalysis , bromide , reaction rate constant , nuclear chemistry , copper , polymer chemistry , kinetics , organic chemistry , enzyme , physics , quantum mechanics , acetylcholinesterase
The Cu (II) complex of poly‐4‐vinylpyridine, quaternized with 19 mol % ethyl bromide and 36 mol % 4‐chloromethyl‐4′‐methyl‐2,2′‐bipyridine, was examined as a catalyst for the hydrolysis of the toxic organophosphorous compounds bis (1‐methylethyl) phosphorofluoridate ( 1 , Registry no.: 1 , 55‐91‐4; 2 , 96‐64‐0. DFP) and 1,2,2‐trimethylpropyl methylphosphonofluoridate ( 2 , soman). Studies were carried out at 25.0 and 37.0°C for both substrates in MOPS buffer at pH 7.0. In the presence of 7.31 × 10 −3 M catalyst at 25.0°C, soman is hydrolyzed with a first‐order rate constant of 0.019 min −1 (t 1/2 = 37.5 min), whereas DFP hydrolyzes with a rate constant of 0.011 min −1 (t 1/2 = 63.8 min). For soman, this represents a 14‐fold increase over the uncatalyzed rate in the same buffer. Other studies examined the effect of a strongly sorptive polymeric resin on catalysis by this copper‐containing polymer and found a dramatic decrease in the hydrolysis rate of soman in the presence of the polymeric sorbent.