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Golba, S.; Loskot, J. The Alphabet of Nanostructured Polypyrrole. Encyclopedia. Available online: (accessed on 23 February 2024).
Golba S, Loskot J. The Alphabet of Nanostructured Polypyrrole. Encyclopedia. Available at: Accessed February 23, 2024.
Golba, Sylwia, Jan Loskot. "The Alphabet of Nanostructured Polypyrrole" Encyclopedia, (accessed February 23, 2024).
Golba, S., & Loskot, J. (2023, November 17). The Alphabet of Nanostructured Polypyrrole. In Encyclopedia.
Golba, Sylwia and Jan Loskot. "The Alphabet of Nanostructured Polypyrrole." Encyclopedia. Web. 17 November, 2023.
The Alphabet of Nanostructured Polypyrrole

Polypyrrole is a significantly useful material derived from an inconspicuous pyrrole ring. The available synthetic procedures allow for the precise sculpturing of both the chemical composition and morphology of the forming polymer. Multiple variations shall be taken into consideration to take advantage of the synergy effect coming from the sophisticated nanostructuring of the material at the stage of choosing the polymer procedure (proper solvent, doping ion, substrate choice), during the polymerization (conditions like temperature, stirring, enhanced impulses, like ultrasounds) or at the post-synthetic functionalization stage.

polypyrrole nano-organization morphology drug delivery neural electrodes

1. Introduction

There is a famous conducting polymers (CPs) triad that includes polythiophene, polyaniline, and polypyrrole (PPy). Among them, it is PPy that is highly attractive due to its wide range of applications. Its utilization spans outer-coating layers [1][2], sensors [3], drug-delivery sponges [4], charge storage in batteries [5], photothermal therapy in cancer [6], and electrodialysis [7]. The form of usage depends on the properties of the polymer and can be tailored to a large extent. It can be deposited as a protective thin layer for oxidizable metals [1] or as a powder [8] in chemical synthesis.
Electroactive conductive polymers can be oxidized (or reduced) by changing the electronic structure of the polymer backbone. The process is accompanied by a charge compensation event as a counterion moves into or out of a layer, forming a kind of ion-enriched sponge [9], an ion gate in the form of a membrane [10], or a hydrogel [11]. Polypyrrole is positively charged in an oxidized state and is neutral and hydrophobic in a reduced state. The ion movement possibility was utilized for the construction of potential controlled drug-delivery systems [4][12]. Many synthetic procedures with multiple ions were studied in this field, with salicylates [13], dexamethasone [14], or chlorpromazine [15] as examples. Drug release kinetics and efficiency served to relate the interconnections between synthetic procedure parameters and system work efficiency. The key parameters affecting the release kinetics of mostly ionic species were studied with the use of various analytical tools like fluorescence spectrometry [16], quartz crystal microbalance (QCMB) [15], or high-performance liquid chromatography (HPLC) [17]. Besides its electroactivity, PPy exhibits also antibacterial properties [8][18]. The tunable photophysical properties of PPy like photothermal conversion ability or Fenton catalysis ability allow for another emerging application, which is cancer therapy for tumor ablation and immune activation [19][20]. Photothermal therapy (PTT) utilizes heat generated locally by light-absorbing agents under near-infrared (NIR) laser radiation [20][21]. The photothermal potential of PPy particles for cancer treatment using NIR absorption was first demonstrated by Yang for material synthesized by aqueous-phase polymerization [22], where tumor growth was inhibited for the NIR laser irradiation (0.5 W/cm2) of the PPy treated samples. The bioinert surface of polypyrrole makes it a prospective contrast agent for photoacoustic imaging [23] studied with the different steric stabilizers of the dispersion polymerization like dextran (Dex) [24]. Smart scaffolds aimed at improving the functionality of the cardiac tissue were proposed by blending PPy into silk fibroin (SF) [25].
The coating ability of PPy makes it a suitable material for the modification of various substrates, imparting multiple functionalizations with prevailing “anti”- or “super”-type characteristics, like antioxidant [26][27], antibacterial [28][29][30], antifungal [31], superhydrophobic [32], anticorrosive [33], antistatic [34], anti-biofilm [35], anticancer [36], antitumor [37] properties. The application of intrinsically conducting polymers as new coatings presents the possibility of the re-passivation of pinholes in organic coatings [38] because of their inherent redox activity. They are also the base for the formation of smart self-healing coatings [2][39]. Protective polymeric film application for industrial substrates was thoroughly discussed by Saviour A. Umoren [40], mainly in terms of anticorrosion coatings and corrosion inhibitors, pointing to the challenges faced by the extended use of polymers for metal protection.

2. Deposition of Electroactive Polypyrrole

Polypyrrole can be synthesized with various approaches using two main methods, namely chemical oxidative polymerization and electrochemical polymerization. For both methods, the template-based approach can be used to the induce nanostructural organization of the polymer [41], while one has to be careful not to destroy the previously formed organization at the template removal stage [42][43]. Also, other less common methods have been proposed, like radiolytic [44], sono-enhanced [45], or cell-assisted enzymatic processes [46].
Material prepared by the oxidation of the monomer with chemical oxidants (usually FeCl3 (either aqueous or anhydrous) [47], K3Fe(CN)6 [48], H2O2 [49], or an enzyme-mediated system [50]) is black powder. Both the yield and conductivity of the final PPy powder depend on parameters like solvent polarity, type of oxidant, pyrrole/oxidant molar ratio, duration, and temperature of the reaction [51]. Covering other materials with PPy coatings from chemically derived powder is problematic. The idea to overcome this obstacle was realized by polymer deposition from the gas phase [52] or by the preparation of composites with poly(N-vinylcarbazole) [53], poly(ethylene oxide) [54], polyvinyl chloride [55], poly(vinyl alcohol) (PVA), poly(vinyl acetate) (PVAc) [56], polyurethane [57], carbon black [58] or proteins like silk [59]. Other forms of materials containing PPy are also available, like substituted polymers, self-doped polymers, polymer/macroion materials, and hybrid materials (where the macroion is inorganic, polymeric, or of an organic blend) [60].
The electrosynthesis of PPy is initiated electrochemically, with the anodic oxidation of monomer leading to subsequent polymer formation. Concurrently, oxidation (doping) of the previously formed polymer occurs, as evidenced by the amount of consumed charge (2.07 to 2.60 F per mole of monomer with 2 F mol devoted to monomer oxidation) [51]. The electropolymerization mechanism has been thoroughly investigated [51][61][62] and involves several stages. The general process starts with monomer oxidation, followed by the coupling reaction, accompanied by the incorporation of the counterion. A charged polymer attracts anions to balance the charge. In the polymer formation process, both anions and electrons move through the film [62]. In the subsequent reduction, electroneutrality is restored by expulsion of the anions or by the incorporation of cations from the electrolyte solution. Upon the application of a positive potential, the neutral film is oxidized, and the anions are inhaled or cations are ejected. The redox activity of a polymer is governed by the electron transfer reaction and mass transport process [62]. The activity brings about serious structural changes manifested by conformation changes, swelling, shrinking, compaction, or relaxation [60]. For standard CP, de-doping is accompanied by the expulsion of anions along with polymer contraction [63]. In the case of anion immobility, movable cations penetrate the polymer to neutralize charge with observed expansion. In the work of Wallace, electrochemical atomic force microscopy (EC-AFM) was used to trace the dynamic actuation of polypyrrole films doped with polystyrene sulfonate [63]. The observation of actuation height displacement gave insight into factors limiting charge balancing processes, either of diffusion or current nature.


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