Peroxidase-catalyzed polymerization

The peroxidase-catalyzed polymerization of m-alkyl substituted phenols in aqueous methanol produced soluble phenolic polymers. The mixed ratio of buffer and methanol greatly affected the yields and the molecular weight of the polymer. The enzyme source greatly affected the polymerization pattern of m-substituted monomers. Using SBP catalyst, the polymer yield increased as a function of the bulkiness of the substituent, whereas the opposite tendency was observed when HRP was the catalyst. 

Fluorinated phenols, 3- and 4-fiuorophenols, and 2,6-difluorophenol, were subjected to peroxidase-catalyzed polymerization in an aqueous organic solvent, yielding fluorine-containing polymers. Elimination of fluorine atom partly took place during the polymerization to give polymers with complicated structures. 

Tobimatsu, Y. Takano, T. Kamitakahara, H. Nakatsubo, F. Azide ion as a quinone methide scavenger in the horseradish peroxidase catalyzed polymerization of sinapyl alcohol. J. WoodSci. 2008, 54, 87-89. 

Foumand, D. Cathala, B. Lapierre, C. Initial steps of the peroxidase-catalyzed polymerization of coniferyl alcohol and/or sinapyl aldehyde capillary zone electrophoresis study of pH effect. Phytochemistry 2003, 62, 139-146. 

How the aliphatic monomers are incorporated into the suberin polymer is not known. Presumably, activated co-hydroxy acids and dicarboxylic acids are ester-ified to the hydroxyl groups as found in cutin biosynthesis. The long chain fatty alcohols might be incorporated into suberin via esterification with phenylpro-panoic acids such as ferulic acid, followed by peroxidase-catalyzed polymerization of the phenolic derivative. This suggestion is based on the finding that ferulic acid esters of very long chain fatty alcohols are frequently found in sub-erin-associated waxes. The recently cloned hydroxycinnamoyl-CoA tyramine N-(hydroxycinnamoyl) transferase [77] may produce a tyramide derivative of the phenolic compound that may then be incorporated into the polymer by a peroxidase. The glycerol triester composed of a fatty acid, caffeic acid and a>-hydroxy acid found in the suberin associated wax [40] may also be incorporated into the polymer by a peroxidase. 

Ryu K, Stafford DR, Dordick JS (1989) Peroxidase-catalyzed polymerization of phenols. In Whitaker JR, Sonnet PE, (eds) Biocatalysis in agricultural biotechnology. American Chemical Society, Washington, D.C., p 141... 

Environmental applications of HRP include immunoassays for pesticide detection and the development of methods for waste water treatment and detoxification. Examples of the latter include removal of aromatic amines and phenols from waste water (280-282), and phenols from coal-conversion waters (283). A method for the removal of chlorinated phenols from waste water using immobilised HRP has been reported (284). Additives such as polyethylene glycol can increase the efficiency of peroxidase-catalyzed polymerization and precipitation of substituted phenols and amines in waste or drinking water (285). The enzyme can also be used in biobleaching reactions, for example, in the decolorization of bleach plant effluent (286). 

Liu W, Cholli AL, Kumar J, Tripathy S, Samuelson L (2001) Mechanistic study of the peroxidase-catalyzed polymerization of sulfonated phenol. Macromolecules 34(11) ... 

Ryu. K.. D.R. Stafford, and J.S. Dordick Peroxidase-Catalyzed Polymerization of Phenols Kinetics of p-Cresol Oxidation in Organic Media, in Biocatalysis in Agncultural Biotechnology, J.R. Whitake, ed. ACS Symp. Ser. No. 389. 

Nicell JA, Bewtra JK, Biswas N, Taylor KE. Reactor development for peroxidase catalyzed polymerization and precipitation of phenols from wastewater. Water Res 1993 27(11) 1629—1639. 

Ghioureliotis M, Nicell JA. Assessment of soluble products of peroxidase-catalyzed polymerization of aqueous phenol. Enzyme Microb Technol 1999 25 185-193. 

Ghioureliotis M, Nicell JA. Toxicity of soluble products from the peroxidase-catalyzed polymerization of substituted phenolic compounds. J Chem Technol Biotechnol 2000 75 98-106. 

Yoshida T, Xia Z, Takeda K et al (2005) Peroxidase-catalyzed polymerization and copolymerization of lignin-based macromonomer (lignocresol) having high content of p-cresol and thermal properties of the resulting polymers. Polym Adv Technol 16 783-788... 

Peroxidase-Catalyzed Polymerization of Phenolic Compounds Containing Carbohydrate Residues... 

Peroxidase-Catalyzed Polymerization of p-Cresol. Large scale polymerizations were carried out in a volume of 250 mL in a 500 mL round bottom flask at 25°C with stirring at ca. 250 rpm. p-Cresol (688 mg, 25 mM) was dissolved in 213 mL dioxane and 37 mL aqueous buffer, pH 7 (0.01 M phosphate) added to give a solution consisting of 85% (v/v) dioxane. Horseradish peroxidase (25 mg, free powder) was added and the reaction was initiated by the addition of 0.28 mL of 30% H2O2 (10 mM). The suspension (peroxidase is insoluble in 85% dioxane) immediately turned yellow and the reaction was allowed to proceed 15 min. The concentrations of p-cresol and reaction products were determined by high performance liquid chromatography (HPLC) with a Ci8-reverse phase column (Waters Associates, Milford, MA). The isocratic solvent used was acetonitrile water (56 44) with... 

Numerical and Monte Carlo simulations of the peroxidase-catalyzed polymerization of phenols were demonstrated.14 The monomer reactivity, molecular weight, and index were simulated for precise control of the polymerization of bisphenol A. In aqueous 1,4-dioxane, aggregates from p-phenylphenol were detected by difference UV absorption spectroscopy.15 Such aggregate formation might elucidate the specific solvent effects in the enzymatic polymerization of phenols. 

Peroxidase-catalyzed polymerization of phenols has provided a new methodology for functional polymeric materials. 

To date, approximately 40 publications reporting on peroxidase-catalyzed polymerizations are available. The biocatalyst of choice for these works clearly is HRP. Other catalysts such as soybean peroxidase [30], manganese peroxidase [8], or hematin [15] have been used scarcely. Furthermore, most of these deal with the polymerization of acrylamide and styrene as a model compounds (Table 6.3). 

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