Phenolics peroxidase-catalyzed

Wasserman, B.P, Eiberger, L.L., and Guilfoy, M.P., Effect of hydrogen peroxide and phenolic compounds on horseradish peroxidase-catalyzed decolorization of betalain pigments, J. Food Sci., 49, 536, 557, 1984. 

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. 

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. 

In recent years, numerous applications of such peroxidase-catalyzed oxidative coupling of phenols and aromatic amines have been reported (Table 7). These peroxidase-catalyzed biotransformations lead to modified natural products with high biological activities [110-118]. Several examples have also been described for the oxidative coupling of phenols with peroxidases and other oxidative enzymes from a variety of fungal and plant sources as whole cell systems... 

Table 7. Peroxidase-catalyzed coupling of phenols and aromatic amines...

Peroxidases have been used very frequently during the last ten years as biocatalysts in asymmetric synthesis. The transformation of a broad spectrum of substrates by these enzymes leads to valuable compounds for the asymmetric synthesis of natural products and biologically active molecules. Peroxidases catalyze regioselective hydroxylation of phenols and halogenation of olefins. Furthermore, they catalyze the epoxidation of olefins and the sulfoxidation of alkyl aryl sulfides in high enantioselectivities, as well as the asymmetric reduction of racemic hydroperoxides. The less selective oxidative coupHng of various phenols and aromatic amines by peroxidases provides a convenient access to dimeric, oligomeric and polymeric products for industrial applications. 

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). 

Shutava T, Zheng ZG, John V, Lvov Y. Microcapsule modification with peroxidase-catalyzed phenol polymerization. Biomacromolecules 2004 5 914-921. 

Glucose (65) kits Commercial kits are based on the enzymatic process shown in equation 16, followed by a chromogenic oxidation process catalyzed by peroxidase, similar to equation 27, involving 4- aminoantipyrine (81) and a phenol or aniUne derivative, leading to a quinoneimine dye. Among the latter aromatic substrates in use are A -ethyl-Al-(2-hydroxy-3-sulfopropyl)-3, 5- dimethoxyaniline (92) , phenol , p-hydroxybenzoic acid and p-hydroxybenzenesidfonate other chromogenic reactions are peroxidase-catalyzed oxidation of iV,iV,iV, iV -tetramethyl-p-phenylenediamine (89) and D-ditoluidine (93) . d... 

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, McEldoon JP, Pokora AR, Cyrus W, Dordick JS (1993) Numerical and Monte Carlo simulations of phenolic polymerizations catalyzed by peroxidase. Biotechnol Bioeng 42 807-814... 

Yu, J., K. E. Taylor, H. Zou, N. Biswas, and J. K. Bewtra, Phenol conversion and dimeric intermediates in horseradish peroxidase-catalyzed phenol removal from water , Environ. Sci. Technol., 28, 2154-2160 (1994). 

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. 

Wu, Y., Taylor, K., Biswas, N., and Bewtra, J., Kinetic model-aided reactor design for peroxidase-catalyzed removal of phenol in the presence of polyethylene glycol, /. Chem. Technol. Biotechnol., 74(6), 519-526, 1999. 

Considerable efforts have aimed at optimizing the reactor configuration in which the peroxidase-catalyzed removal of phenols can be carried out. Much of this work has focused on maximizing the efficiency of enzyme use since the majority of the operating cost associated with peroxidase treatment is likely to be that of the enzyme itself [24]. Improvements in the useful life of the enzyme, with a corresponding reduction in treatment cost, have been accomplished through the selection of an appropriate reactor configuration... 

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. 

Nakamoto S, Machida N. Phenol removal from aqueous solutions by peroxidase-catalyzed reaction using additives. Water Res 1992 26 49-54. 

Klibanov AM, Tu T-M, Scott KP. Peroxidase-catalyzed removal of phenols from coal-conversion waste waters. Science 1983 221 259-260. 

Wagner M, Nicell JA. Peroxidase-catalyzed removal of phenols from a petroleum refinery wastewater. Water Sci Technol 2001 43(2) 253-260. 

Hammel KE, Tardone PJ. The oxidative 4-dechlorination of polychlorinated phenols is catalyzed by extracellular fungal lignin peroxidases. Biochemistry 1988 27 6563-6568. 

Buchanan ID, Nicell JA. Model development for horseradish peroxidase-catalyzed removal of aqueous phenol. Biotechnol Bioeng 1997 54(3) 251-261. 

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. 

Fig- 6-1 Some examples of peroxidase-catalyzed oxidations of phenols and naphtols in (d), R1 represents a hydrogen or a bromine atom and R2 a hydrogen, methyl, or carboxymethyl groups... 

Dordick JS (1987) Production of phenolic polymers catalyzed by horseradish peroxidase in organic solvents. Proc Mater Biotechnol Symp 225-239... 

Blinkovsky AM, Dordick JS (1993) Peroxidase-catalyzed synthesis of lignin-phenol copolymers. J Polym Sci A Polym Chem 31 1839-1846... 

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