Abstract

In this study, synthesis and dynamic properties of amphiphilic core–shell polymers are reported as monitored through their interaction with small amphiphilic ligands. Our findings point to a most complex self-assembling nature of those host and guest molecules.

Highlights

  • In recent years, synthetic pathways have been established to construct graft copolymers from amphiphilic macromonomers[1,2,3,4,5,6,7,8] with high molecular weights of up to 470 kDa and narrow and monomodal weight distributions (PDI < 1.20).[9]

  • We can study paramagnetic fatty acids by continuous wave (CW) electron paramagnetic resonance (EPR) to determine their distribution in different environments based on polarity and their individual binding affinities as well as partition coefficients

  • The overall characteristics of the mutual interactions of amphiphilic ligands and amphiphilic transporters is summarized as the concept of “dynamic hydrophobic attachment” as this term is to the best of our knowledge not used for any particular mechanism elsewhere

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Summary

Introduction

Synthetic pathways have been established to construct graft copolymers from amphiphilic macromonomers[1,2,3,4,5,6,7,8] with high molecular weights of up to 470 kDa and narrow and monomodal weight distributions (PDI < 1.20).[9]. As a nonpolar environment leads to a local shift of the electron spin density towards the oxygen atom in nitroxide radicals, the hyperfine interactions between electron and 14N nucleus and the aiso-value is reduced linearly with decreasing polarity.[36,37] the spectral parameters, i.e., the individual dynamic fractions f and b, as well as τc and aiso, are the key to dissecting multicomponent EPR spectra This forms the foundation of our approach of detecting structural and dynamic changes of the polymer itself, extending the established phenomenon of merely observing ligand binding towards polymers.[14,16,17]. We will in the following show that our deliberate physico-chemical, EPR-based strategic approach can lead to an almost holistic view of how macromolecular structure and dynamic responses can be tuned

Results and discussion
Polymer synthesis and screening by EPR spectroscopy
Temperature dependence of ligand binding
Ligand uptake capabilities
Tunable structure and dynamics of the core-shell polymers
Conclusions
Materials
Copper-catalyzed azide–alkyne cycloaddition of linPPGm and AzUMA
RAFT-polymerization of click-coupled macromonomers
EPR Spectroscopy
DLS measurements
Full Text
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