Unusual enhancement of degradation rate induced by polymer chain elongation in quaternized polyethyleneimine derivatives

Rafał Kopiasz , Michał Szczepańczyk , Dominik Jańczewski

Abstract

Our study on antimicrobial ionenes revealed an unusual chemical property of quaternized linear polyethyleneimine (L-PEI) derivatives. The polymer backbone reactivity toward hydroxide strongly increases with the added number of repeating units. Methylated L-PEI and its oligomer containing four mers underwent rapid elimination in such mild alkaline conditions as 0.1 mol/L Na2CO3 solution at 25 °C, whereas two mer oligomer remained stable. The rigid oligomeric analog containing alkylated 1,4-diazabicyclo[2.2.2]octane subunits were even more reactive. The effect can be explained by the increased polarization of CeH bond that follows the chain elongation. Such hypothesis is well supported by a good correlation of reaction rates with 1 H NMR chemical shifts of eliminated hydrogens, what inspired discussion on possibly involved E1cB and E2 mechanisms. The observed correlation can be used to predict stability of polycations, which is an important issue in both biomedical and energy storage fields.
Author Rafał Kopiasz (FC / CPCT)
Rafał Kopiasz,,
- Chair Of Polymer Chemistry And Technology
, Michał Szczepańczyk (FC / CPCT)
Michał Szczepańczyk,,
- Chair Of Polymer Chemistry And Technology
, Dominik Jańczewski (FC / CPCT)
Dominik Jańczewski,,
- Chair Of Polymer Chemistry And Technology
Journal seriesReactive & Functional Polymers, ISSN 1381-5148, (A 35 pkt)
Issue year2019
Vol137
Pages96-103
Publication size in sheets0.5
Keywords in EnglishPolycation, Ionene, Polyethyleneimine stability, PEI, Hofmann elimination
ASJC Classification2505 Materials Chemistry; 2507 Polymers and Plastics; 1500 General Chemical Engineering; 1303 Biochemistry; 2304 Environmental Chemistry; 1600 General Chemistry
DOIDOI:10.1016/j.reactfunctpolym.2019.01.010
Languageen angielski
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1-s2.0-S1381514818309969-main.pdf 915.18 KB
Score (nominal)35
ScoreMinisterial score = 35.0, 12-08-2019, ArticleFromJournal
Publication indicators Scopus SNIP (Source Normalised Impact per Paper): 2017 = 0.993; WoS Impact Factor: 2017 = 2.975 (2) - 2017=2.843 (5)
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