TY - JOUR
T1 - Molecularly imprinted polymers via living radical polymerization
T2 - Relating increased structural homogeneity to improved template binding parameters
AU - Salian, Vishal D.
AU - White, Charles J.
AU - Byrne, Mark E.
N1 - Funding Information:
This work was supported by a grant from the National Science Foundation (NSF-CBET-0730903, Grant G00003191).
Copyright:
Copyright 2014 Elsevier B.V., All rights reserved.
PY - 2014/5
Y1 - 2014/5
N2 - This work examined imprinted polymer networks prepared via controlled/living radical polymerization (LRP) and conventional radical polymerization (CRP) on chain growth, network formation, and efficiency of producing molecularly imprinted, macromolecular memory sites for the template molecule, diclofenac sodium. LRP extended the reaction-controlled regime of the polymerization reaction and formed more homogeneous polymer chains and networks with smaller mesh sizes. In addition, LRP negated the effect of the template on polymer chain growth resulting in polymers with a more consistent PDI independent of template concentration in the pre-polymerization solution. Improved network homogeneity within imprinted poly(HEMA-co-DEAEM-co-PEG200DMA) networks prepared via LRP resulted in a 38% increase in template binding affinity and 43% increase in the template binding over imprinted networks prepared via CRP and a 97% increase in affinity and 130% increase in capacity over non-imprinted networks prepared by LRP. By varying certain parameters, it was possible to create imprinted networks with even higher template binding affinities (155% over non-imprinted) and capacities (261% over non-imprinted). This work is the first to conclusively demonstrate that the observed improvement in binding parameters in weakly crosslinked, imprinted polymer networks could be explained by the more uniform molecular weight evolution associated with the LRP mechanism and the longer lifetime of an active polymer chain relative to the total polymerization time, which allowed for the formation of a more homogenous imprinted polymer network.
AB - This work examined imprinted polymer networks prepared via controlled/living radical polymerization (LRP) and conventional radical polymerization (CRP) on chain growth, network formation, and efficiency of producing molecularly imprinted, macromolecular memory sites for the template molecule, diclofenac sodium. LRP extended the reaction-controlled regime of the polymerization reaction and formed more homogeneous polymer chains and networks with smaller mesh sizes. In addition, LRP negated the effect of the template on polymer chain growth resulting in polymers with a more consistent PDI independent of template concentration in the pre-polymerization solution. Improved network homogeneity within imprinted poly(HEMA-co-DEAEM-co-PEG200DMA) networks prepared via LRP resulted in a 38% increase in template binding affinity and 43% increase in the template binding over imprinted networks prepared via CRP and a 97% increase in affinity and 130% increase in capacity over non-imprinted networks prepared by LRP. By varying certain parameters, it was possible to create imprinted networks with even higher template binding affinities (155% over non-imprinted) and capacities (261% over non-imprinted). This work is the first to conclusively demonstrate that the observed improvement in binding parameters in weakly crosslinked, imprinted polymer networks could be explained by the more uniform molecular weight evolution associated with the LRP mechanism and the longer lifetime of an active polymer chain relative to the total polymerization time, which allowed for the formation of a more homogenous imprinted polymer network.
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U2 - 10.1016/j.reactfunctpolym.2014.02.003
DO - 10.1016/j.reactfunctpolym.2014.02.003
M3 - Article
AN - SCOPUS:84897508417
SN - 1381-5148
VL - 78
SP - 38
EP - 46
JO - Reactive and Functional Polymers
JF - Reactive and Functional Polymers
IS - 1
ER -