Anionic-Surfactant-Stabilized Hydrophobic Ionic-Liquid-Based Bicontinuous Microemulsion as a Medium for Enzymatic Oxidative Polymerization of Aniline

[Image: see text] The hydrophobic ionic liquid [C(8)mim][PF(6)] (1-octyl-3-methylimidazolium hexafluorophosphate)-based bicontinuous microemulsion stabilized by the anionic surfactant [C(4)mim][AOT] (1-butyl-3-methylimidazolium bis(2-ethylhexyl) sulfosuccinate) was first tried as a medium for horseradish peroxidase (HRP)-triggered oxidative polymerization of aniline. The effects of the mass ratio of [C(8)mim][PF(6)]-to-water (α), the mass fraction of [C(4)mim][AOT] in the total mixture (γ), and temperature (T) on the enzymatic polymerization were investigated using UV–vis–NIR absorption, electron spin resonance, and small-angle X-ray scattering spectroscopy techniques. The bicontinuous microemulsion is demonstrated to play a template role in the biosynthesis of polyaniline (PANI). The conductivity of the resulting PANI depends on the microemulsion microstructure and the microstructure- and T-dependent catalytic properties of the solubilized HRP. With the increase in α, the conductivity of the synthesized PANI decreases due to the increase in the template curvature (decrease of the microdomain size) and the decrease in the activity and stability of HRP. Compared with α, γ has little effect on the microdomain size of the template; so, the γ-dependent change in the conductivity of PANI is mainly caused by the changes of the microstructure-dependent activity and stability of HRP. Over the range of 20–35 °C, T has little effect on the microdomain size, but it greatly changes the activity and stability of HRP. With the increase in T, the activity of HRP increases steadily, but its stability decreases significantly, which should be one of the reasons why the conductivity of PANI decreases with increasing T. In conclusion, lower values of α, γ, and T are favorable for the biosynthesis of conductive PANI. The present study not only deepens the insight into the role of the template in the process of PANI synthesis, but also opens up a green new way for the biosynthesis of the conducting polymer.