A comparative study of water dispersible polyaniline nanocomposites prepared by laccase‐catalyzed and chemical methods

Abstract

A comparative study of chemical and enzymatic methods of aniline polymerization was carried out. Fungal laccase from Trametes hirsuta was used in the synthesis of polyaniline nanoparticles made with poly(2acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS). Template polymerization of aniline was carried out in aqueous buffer. It was shown that the laccase had high long-term and operating stabilities under acidic condition favorable for synthesis of conducting polyaniline. UV-vis, FTIR spectroscopy, and cyclic voltammetry analysis are used for the characterization of the polyelectrolyte complexes of polyaniline and PAMPS. The incorporation of the polymeric acid in polyaniline has been demonstrated by atomic force microscopy. The size and morphology of the nanoparticles of the polyaniline-PAMPS complexes depended on the method of the synthesis. A comparison of some physical and chemical properties of water dispersible conducting polyaniline-PAMPS was performed under production by enzymatic and chemical methods. It was found a difference in structures and some physicochemical properties of polyaniline colloids prepared by chemical and laccase-catalyzed methods.

Anionic Polysaccharides as Templates for the Synthesis of Conducting Polyaniline and as Structural Matrix for Conducting Biocomposites

“…When polymerization was performed using κ‐GCN, NFC, or GGM PolyU as template, a broad absorption band between 700–800 nm and a shoulder at 400–420 nm slowly appeared. These absorption bands can be assigned to the polaron of conducting PANI 21. As expected, unmodified GGM, containing very few charged groups, was a poor template.…”

“…Besides this, the template also provides counter ions for doping of the synthesized PANI and helps to maintain the water solubility of the product 13–15. Different anionic templates have successfully been applied 14, 16–21. Suitable templates are typically strong polyelectrolytes with p K a values that are lower than the p K a of aniline (≈4.6) 14.…”

Advanced Synthesis of Conductive Polyaniline Using Laccase as Biocatalyst

“…Even if studies on enzymatic polymerization of aniline scarcely illustrate the electro-conductivities of the resulting polymers [ 2 , 37 ], this value is three orders of magnitude higher than that reported for PANI obtained after 18 days of reaction with Trametes versicolor laccase and AOT (after re-doping with camphor-10-sulfonic acid) [ 12 ]. We also use milder reaction conditions (much less enzyme, room temperature, shorter reaction times) than other polymerization reactions catalyzed by laccase [ 12 , 38 , 39 ]. On the other hand, conductivities of PANI obtained by conventional means range from 10 −10 to 27 S/cm [ 40 , 41 ], although conductivity values above 10 −3 S/cm are only attained in strongly acidic media.…”

Synthesizing Polyaniline With Laccase/O2 as Catalyst

“…Applications of laccase-catalyzed in vitro reactions include the laccase/O 2 -mediated syntheses of polymeric (or oligomeric) products from methyl methacrylate or styrene (with acetylacetone as mediator, see Tsujimoto et al, 2001), acrylamide (Ikeda et al, 1998), phenols (Mita et al, 2003; Marjasvaara et al, 2006; Sun et al, 2013; Su et al, 2018a, 2019a), pyrrole (Song and Palmore, 2005; Junker et al, 2015), dopamine (Tan et al, 2010; Li et al, 2018), 3,4-ethylenedioxythiophene (Shumakovich et al, 2012b; Vasil'eva et al, 2018), or various arylamines (Ćirić-Marjanović et al, 2017; Zhang T. et al, 2018; Su et al, 2019a,b). With respect to the latter type of monomers, the focus often was—and still is—on the synthesis of oligo- or polyaniline (PANI) from aniline (Karamyshev et al, 2003; Vasil'eva et al, 2007, 2009; Streltsov et al, 2008, 2009; Shumakovich et al, 2010, 2012a, 2014; Leppänen et al, 2013; Zhang et al, 2014, 2016; Zhang Y. et al, 2018; Junker et al, 2014a; de Salas et al, 2016; Su et al, 2018b) or from p -aminodiphenylamine (PADPA), the linear para N-C-coupled aniline dimer Shumakovich et al, 2011; Junker et al, 2014b; Janoševic Ležaić et al, 2016; Luginbühl et al, 2016; Kashima et al, 2018;Kashima et al, 2019).…”

“…This allows monitoring the formation of desired functional groups during polymerization and after reaching reaction equilibrium, for example by simple UV/vis/NIR measurements (Junker et al, 2014a). Interestingly, independent from the type of laccase and type of chosen template used, the UV/vis/NIR spectrum of the reaction mixture always appears to have an absorption maximum (λ max ) between λ = 700 and 800 nm, and not at λ ≈ 800–1,100 nm, as expected for the π → polaron transition of PANI-ES (see above): λ max ≈ 750 nm (with Trametes hirsuta laccase and SPS as template at pH = 3.5 and T = 20°C; Karamyshev et al, 2003); λ max = 740–800 nm (with Trametes hirsuta laccase and SDBS micelles at pH = 3.8 and T = 20°C, Streltsov et al, 2008); λ max ≈ 700 nm (with Trametes hirsuta laccase and poly(2-acrylamido-2-methyl-1-propanesulfonic acid) at pH = 3.5 and T = 20°C, Shumakovich et al, 2010); λ max ≈ 750 nm (with Trametes versicolor laccase and κ-carrageenan at pH = 3.7 and room temperature, Leppänen et al, 2013); λ max ≈ 750 nm (with Denlite®, a laccase preparation from Aspergillus , and SDBS micelles at pH = 4.5 and T = 10°C, Zhang et al, 2014); λ max ≈ 750 nm (with Denlite® and lignosulfonate at pH = 3.5 and T = 5°C, Zhang et al, 2016); and λ max ≈ 730 nm (with Trametes versicolor laccase and AOT vesicles at pH = 3.5 and T = 25 or 8°C, Junker et al, 2014a). These observed absorption maxima contrast with what has been observed for the HRPC/H 2 O 2 -catalyzed polymerization of aniline, even if the same template was used, e.g., AOT vesicles (λ max ≈ 1,000 nm at pH = 4.3 and T ≈ 25°C, Junker et al, 2012; Pašti et al, 2017).…”