ABSTRACT
Many previous studies have shown that (i) the oxidation of aniline or the aniline dimer p-aminodiphenylamine (PADPA) in a slightly acidic aqueous solution can be catalyzed with heme peroxidases or multicopper laccases and that (ii) subsequent reactions lead to oligomeric or polymeric products, which resemble chemically synthesized polyaniline in its conductive emeraldine salt form (PANI-ES), provided that (iii) an anionic "template" is present in the reaction medium. Good templates are anionic polyelectrolytes, micelles, or vesicles. Under optimal conditions, their presence directs the reactions in a positive way toward the desired formation of PANI-ES-type products. The effect of four different types of anionic templates on the formation of PANI-ES-like products from PADPA was investigated and compared by using Trametes versicolor laccase (TvL) as a catalyst in an aqueous pH 3.5 solution at room temperature. All four templates contain sulfonate groups: the sodium salt of the polyelectrolyte sulfonated polystyrene (SPS), micelles from sodium dodecylbenzenesulfonate (SDBS), vesicles from a 1:1 molar mixture of SDBS and decanoic acid, and vesicles from sodium bis(2-ethylhexyl)sulfosuccinate (AOT). Although with all four templates, stable, inkjet-printable solutions or suspensions consisting of PANI-ES-type products were obtained under optimized conditions, considerably higher amounts of TvL were required with SDBS micelles to achieve comparable monomer conversion to PANI-ES-like products during the same time period when compared to those with SPS or the two types of vesicles. This makes SDBS micelles less attractive as templates for the investigated reaction. In situ UV/vis/near-infrared, electron paramagnetic resonance (EPR), and Raman spectroscopy measurements in combination with an high-performance liquid chromatography analysis of extracted reaction products, which were deprotonated and chemically reduced, showed seemingly small but significant differences in the composition of the mixtures obtained when reaching reaction equilibrium after 24 h. With the two vesicle systems, the content of unwanted substituted phenazine units was lower than in the case of SPS polyelectrolyte and SDBS micelles. The EPR spectra indicate a more localized, narrower distribution of electronic states of the paramagnetic centers of the PANI-ES-type products synthesized in the presence of the two vesicle systems when compared to that of the similar products obtained with the SPS polyelectrolyte and SDBS micelles as templates. Overall, the data obtained from the different complementary methods indicate that with the two vesicle systems structurally more uniform (regular) PANI-ES-type products formed. Among the two investigated vesicle systems, for the investigated reaction (oxidation of PADPA with TvL and O2), AOT appears a somewhat better choice as it leads to a higher content of the PANI-ES polaron form.
ABSTRACT
The polymerization of aniline to polyaniline (PANI) can be achieved chemically, electrochemically or enzymatically. In all cases, the products obtained are mixtures of molecules which are constituted by aniline units. Depending on the synthesis conditions there are variations (i) in the way the aniline molecules are connected, (ii) in the average number of aniline units per molecule, (iii) in the oxidation state, and (iv) in the degree of protonation. For many possible applications, the synthesis of electroconductive PANI with para-N-C-coupled aniline units in their half-oxidized and protonated state is of interest. This is the emeraldine salt form of PANI, abbreviated as PANI-ES. The enzymatic synthesis of PANI-ES is an environmentally friendly alternative to conventional chemical or electrochemical methods. Although many studies have been devoted to the in vitro synthesis of PANI-ES by using heme peroxidases with added hydrogen peroxide (H2O2) as the oxidant, the application of laccases is of particular interest since the oxidant for these multicopper enzymes is molecular oxygen (O2) from air, which is beneficial from environmental and economic points of view. In vivo, laccases participate in the synthesis and degradation of lignin. Various attempts of synthesizing PANI-ES with laccase/O2 in slightly acidic aqueous media from aniline or the linear aniline dimer PADPA (p-aminodiphenylamine) are summarized. Advances in the understanding of the positive effects of soft dynamic templates, as chemical structure guiding additives (anionic polyelectrolytes, micelles, or vesicles), for obtaining PANI-ES-rich products are highlighted. Conceptually, some of these template effects appear to be related to the effect "dirigent proteins" exert in the biosynthesis of lignin. In both cases intermediate radicals are formed enzymatically which then must react in a controlled way in follow-up reactions for obtaining the desired products. These follow-up reactions are controlled to some extent by the templates or specific proteins.
ABSTRACT
Horseradish peroxidase isoenzyme C (HRPC) is often used as catalyst for the preparation of the conductive emeraldine salt form of polyaniline (PANI-ES) from aniline and hydrogen peroxide (H2O2) in the presence of anionic templates in aqueous solution. Here, a direct comparison of three types of soft templates was made, (i) the sodium salt of sulfonated polystyrene (SPS), (ii) micelles from sodium dodecylbenzenesulfonate (SDBS), and (iii) vesicles from either a 1 : 1 molar mixture of SDBS and decanoic acid or from AOT (sodium bis(2-ethylhexyl)sulfosuccinate). Based on UV/vis/NIR, EPR and Raman spectroscopy measurements all three types of templates are similarly suitable, with advantages of the two vesicle systems in terms of aniline conversion degree and radical content in the final PANI-ES product. First experiments with sulfated cellulose nanocrystals (CNCs) indicate that they are promising rigid templates for the preparation of electroconductive PANI-ES-coated cellulose materials or devices.
ABSTRACT
The Trametes versicolor laccase (TvL)-catalysed oligomerisation of the aniline dimer p-aminodiphenylamine (PADPA) was investigated in an aqueous medium of pH = 3.5, containing 80-100 nm-sized anionic vesicles formed from AOT, the sodium salt of bis(2-ethylhexyl)sulfosuccinic acid. If run under optimal conditions, the reaction yields oligomeric products which resemble the emeraldine salt form of polyaniline (PANI-ES) in its polaron state, known to be the only oxidation state of linear PANI which is electrically conductive. The vesicles serve as "templates" for obtaining products with the desired PANI-ES-like features. For this complex, heterogeneous, vesicle-assisted, and enzyme-mediated reaction, in which dissolved dioxygen also takes part as a re-oxidant for TvL, small changes in the composition of the reaction mixture can have significant effects. Initial conditions may not only affect the kinetics of the reaction, but also the outcome, i.e., the product distribution once the reaction reaches its equilibrium state. While a change in the reaction temperature from T ≈ 25 to 5 °C mainly influenced the rate of reaction, increase in enzyme concentration and the presence of millimolar concentrations of chloride ions were found to have significant undesired effects on the outcome of the reaction. Chloride ions, which may originate from the preparation of the pH = 3.5 solution, inhibit TvL, such that higher TvL concentrations are required than without chloride to yield the same product distribution for the same reaction runtime as in the absence of chloride. With TvL concentrations much higher than the elaborated value, the products obtained clearly were different and over-oxidised. Thus, a change in the activity of the enzyme was found to have influence not only on kinetics but also led to a change in the final product distribution, molecular structure and electrical properties, which was a surprising find. The complementary analytical methods which we used in this work were in situ UV/vis/NIR, EPR, and Raman spectroscopy measurements, in combination with a detailed ex situ HPLC analysis and molecular dynamics simulations. With the results obtained, we would like to recall the often neglected or ignored fact that it is important to describe and pay attention to the experimental details, since this matters for being able to perform experiments in a reproducible way.
