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. 2022 Dec 22;15(1):45.
doi: 10.3390/polym15010045.

Periodic Self-Assembly of Poly(ethyleneimine)-poly(4-styrenesulfonate) Complex Coacervate Membranes

Ekaterina V Kukhtenko  1 , Filipp V Lavrentev  1 , Vladimir V Shilovskikh  1 , Polina I Zyrianova  1 , Semyon I Koltsov  1 , Artemii S Ivanov  1 , Alexander S Novikov  1 , Anton A Muravev  1 , Konstantin G Nikolaev  1 , Daria V Andreeva  2 , Ekaterina V Skorb  1
Affiliations

Periodic Self-Assembly of Poly(ethyleneimine)-poly(4-styrenesulfonate) Complex Coacervate Membranes

Ekaterina V Kukhtenko et al. Polymers (Basel). .

Abstract

Coacervation is a self-assembly strategy based on the complexation of polyelectrolytes, which is utilized in biomedicine and agriculture, as well as automotive and textile industries. In this paper, we developed a new approach to the on-demand periodic formation of polyelectrolyte complexes through a Liesegang-type hierarchical organization. Adjustment of reaction conditions allows us to assemble materials with a tunable spatiotemporal geometry and establish materials' production cycles with a regulated periodicity. The proposed methodology allows the membrane to self-assemble when striving to reach balance and self-heal after exposure to external stimuli, such as potential difference and high pH. Using chronopotentiometry, K+ ion permeability behavior of the PEI-PSS coacervate membranes was demonstrated. The periodically self-assembled polyelectrolyte nanomembranes could further be integrated into novel energy storage devices and intelligent biocompatible membranes for bionics, soft nanorobotics, biosensing, and biocomputing.

Keywords: Liesegang rings; complex coacervation; ion permeability; periodic structure; polyelectrolytes; reaction-diffusion; self-healing.

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Conflict of interest statement

The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

Figures

Figure 1
Figure 1
PEC formation at the nano- (nm), micro- (µm) and macro- (mm) scale.
Figure 2
Figure 2
Experimental setups for the formation of diffusion-controlled spatially distributed PEC from PEI (c = 2.5 g/L, Mw ≈ 25 kDa) and PSS (c = 2.5 g/L, Mw ≈ 70 kDa) in 0.1 M NH4F: (a) tangential periodic bands (method I) (b) radial concentric rings (method II) (c) semicircles (method III).
Figure 3
Figure 3
Diffusion-controlled formation of spatially distributed PEC according to method II from (a–c) variable molecular weight 2.5 g/L PEI (Mw ~ (a,b) 750 kDa, (c) 25 kDa) and 2.5 g/L PSS (Mw ~ (a) 1000 kDa, (b,c) 70 kDa) in 0.1 M NH4F and (d–f) variable-concentration 25-kDa PEI and 70-kDa PSS (C = (d) 1.25, (e) 2.50, and (f) 5.00 g/L).
Figure 4
Figure 4
(a) Scheme of pristine, damaged, and healed membrane; (b) Interdiffusion mechanism of PECs and (c) dynamics of its conversion from damaged to self-healed membrane; (d) scheme and (e) photograph of PEC association-dissociation setup under applied voltage of 5 V and dynamics of self-healing after current cut-off: (f) PEC membrane after 24 h of RD self-assembly, w0 = 2.42 mm (g) damaged PEC membrane after 1 h of applied voltage, w1 = 1.1 mm; and (h) self-healed PEC membrane, 24 h after maintenance with applied potential gave the thickness of 1.83 mm.
Figure 5
Figure 5
(a) Photograph of the electrochemical setup demonstrating K+ ion permeability of the PEC membrane (WE = working electrode, RE = reference electrode) and (b) chronopotentiograms recorded from K+-selective electrode and corresponding to different concentrations of PEC.
See this image and copyright information in PMC

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