Abstract

It has been shown that the thermodynamics of bicontinuous microemulsions can be tailored via the addition of various different amphiphilic polymers. In this manuscript, we now focus on comb-type polymers consisting of hydrophobic backbones and hydrophilic side chains. The distinct philicity of the backbone and side chains leads to a well-defined segregation into the oil and water domains respectively, as confirmed by contrast variation small-angle neutron scattering experiments. This polymer–microemulsion structure leads to well-described conformational entropies of the polymer fragments (backbone and side chains) that exert pressure on the membrane, which influences the thermodynamics of the overall microemulsion. In the context of the different polymer architectures that have been studied by our group with regards to their phase diagrams and small-angle neutron scattering, the microemulsion thermodynamics of comb polymers can be described in terms of a superposition of the backbone and side chain fragments. The denser or longer the side chain, the stronger the grafting and the more visible the brush effect of the side chains becomes. Possible applications of the comb polymers as switchable additives are discussed. Finally, a balanced philicity of polymers also motivates transmembrane migration in biological systems of the polymers themselves or of polymer–DNA complexes.

Highlights

  • The first promising polymers that were added to microemulsions were amphiphilic diblock copolymers [1,2,3], and they remain a topic of active research [4]

  • While in microemulsions the comb polymers unfold quite well and the fragments of different philicity are found in different domains, an important question is of the migration of substances through lipid bilayers and through cell walls

  • We have investigated the structure of comb polymers in bicontinuous microemulsions

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Summary

Introduction

The first promising polymers that were added to microemulsions were amphiphilic diblock copolymers [1,2,3], and they remain a topic of active research [4]. Many different amphiphilic polymer architectures have been examined [5,6,7,8,9] with differing effects on the microemulsion. One area of polymer architecture that has yet to be explored is that of amphiphilic comb polymers. These would appear to be promising as they can be cheaply synthesized using grafting reactions and have already found uses as gene carriers and scaffolds for tissue engineering [10,11,12].

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