Biocatalytic synthesis of polycatechols from toxic aromatic compounds.
A process is described in which toxic aromatic compounds are converted by toluene dioxygenase and in turn toluene cis-dihydrodiol dehydrogenase to catechols which are further polymerized by peroxidase-catalyzed oxidation producing polycatechols. Three approaches for obtaining catechols were employed: (1) addition of halogenated aromatics to P. putida F1, resulting in the accumulation of halogenated catechols; (2) inhibition of catechol 2,3-dioxygenase of P. putida F1 by known aromatic and aliphatic inhibitors; and (3) overexpression of toluene dioxygenase and toluene cis-dihydrodiol dehydrogenase genes in E. coli JM109. The process is suitable for producing novel catechols that upon oxidation may yield polymers with unique properties, presenting a tool for producing tailor-made biopolymers. Formation of 3-chlorocatechol from chlorobenzene, 3,4-dichlorocatechol from 1,2-dichlorobenzene, and catechol from benzene and their subsequent oxidation and polymerization was demonstrated. Oxidation of catechol yielded polymers with molecular weights of up to 4000 Daltons. Their apparently high water solubility eliminates the need for water-miscible solvents. In aqueous solution oxidation of catechols was rapid, yet the presence of 20%, 30%, and 40% ethanol, resulted in a rate decrease of 31%, 95%, and 93%, respectively. The advantage is that significantly less peroxidase is required for performing the reactions if miscible solvents are not employed. Furthermore, water-soluble polymers may be desirable for many applications.
Division of Environmental, Water and Agricultural Engineering, Faculty of Civil and Environmental Engineering, Technion-Israel Institute of Technology, Haifa 32000, Israel.
Gary
G
Ward
Rebecca E
RE
Parales
Carlos G
CG
Dosoretz
D001554:Benzene / Q000378:metabolism; D001704:Biopolymers / Q000378:metabolism*; D001711:Biotransformation; D002384:Catalysis; D002396:Catechols / Q000378:metabolism*; D002722:Chlorobenzenes / Q000378:metabolism; D004926:Escherichia coli / Q000201:enzymology / Q000378:metabolism*; D006861:Hydrogen Peroxide; D010084:Oxidation-Reduction; D010088:Oxidoreductases / Q000378:metabolism; D010105:Oxygenases / Q000378:metabolism; D016958:Pseudomonas putida / Q000201:enzymology / Q000378:metabolism*; D012995:Solubility
D001704:Biopolymers; D002396:Catechols; D002722:Chlorobenzenes; C004726:2-dichlorobenzene; D006861:Hydrogen Peroxide; D010088:Oxidoreductases; D010105:Oxygenases; C023172:toluene dioxygenase; C023171:cis-toluene dihydrodiol dehydrogenase; D001554:Benzene; C031294:chlorobenzene