Coupling mechanism at the early stage of enzymatic polymerization of phenol and substituted phenol such as p-sulfonated phenol and p-cresol was investigated by in-situ H-1 NMR spectroscopy, The progress of the reaction was monitored in-situ with incremental addition Of H2O2. At the beginning, the reaction mixture contains mainly monomers along with low molecular weight oligomeric species such as dimers, trimers, etc. Except in the case of p-cresol, the consumption of monomers and dimers appeared to be a competing process at the later stage of polymerization. NMR data analysis allows structural identification of various dimers that are formed at the early stage of the reaction. In case of phenol, mixture of C-C and C-O-C coupled products are dominant from the beginning of the polymerization. In contrast, the enzymatic polymerization of p-sulfonated phenol shows the predominance of C-O-C coupling while C-C coupling is favored in the case of p-cresol.
Electronic and photo-active polymers as a class of advanced materials have attracted a lot of interest during last two decades. Typically these materials are synthesized chemically or electrochemically under harsh conditions such as extremely low pH, toxic catalysts and byproducts. New enzymatic approaches have been developed for the synthesis of electro and photo active polymers such as polyanilines, polyazophenols, and polypyrene derivatives. These enzymatically synthesized materials show interesting optical and electronic properties.
A new biological strategy has been developed to synthesize water-soluble conducting polyaniline. In this approach, anilines are polymerized by the enzyme horseradish peroxidase (HRP) catalysis in aqueous buffer solution at pH 4.3 in the presence of a template. Strong acid polyelectrolytes such as polystyrene sulfonate (SPS) and the aqueous micelles formed by strong acid surfactants such as dodecylbenzenesulfonic acid (SDBS) are favorable templates to form nano-scale reactors for the growth of conducting polyaniline. The properties of this enzymatically synthesized polyaniline are consistent with the polyaniline that is traditionally prepared via either chemical or electrochemical procedures. This biological approach offers unsurpassed ease of synthesis, processability, stability (electrical and chemical), and environmental compatibility.
Electrospinning employs strong electric fields to create nanometer scale fibers. The fibers are collected as a non-woven fiber membrane with a very large surface area to volume ratio. Sulfonated polystyrene, enzymatically synthesized polyaniline and blends thereof, and dyesensitized composite polymeric systems were electrospun and studied to optimize fiber formation. It is expected that these types of electrospun materials will find potential use as new lightweight electronic and photonic materials in numerous device applications.