Enzymatic Polymerization of Phenols Catalyzed by Chloroperoxidase in the Presence of Ionic Liquids/Quaternary Ammonium Salts†

doi:10.7503/cjcu20160236

Abstract

Abstract:

A green enzymatic approach for the synthesis of phenol polymersfrom substituted phenols monomer by chloroperoxidase(CPO)-catalyzed H₂O₂-oxidation was proposed in this paper. The yield and thermal stabi-lity of polymers of p-methyl phenol, p-ethyl phenol, p-propyl phenol, p-phenyl phenol and p-hydroxy-cinnamic acid were studied based on the presence of imidazolium-based ionic liquids(ILs) or quaternary ammonium salts(QAS), the effect of structure of the substrates and the reaction microenvironment. The results showed that the introduction of little amount of ILs/QAS can improve the production of polymerization of phenols efficiently, in which ILs/QAS with bigger cation group and shorter hydrophobic chain was much more effective, while the influence of ILs/QAS amount on polymerization of phenols showed a “ball type” pattern. Moreover, it was found that p-substituted phenol and electron-donating group were more beneficial to the increase of yield and thermal stability of phenol polymers compared to o-substituted phenol and electron-withdrawing group. However, the steric hindrance was increased with the increasing size of substituent group, which was not beneficial to the polymerization of phenols. The pH value should be controlled as weak acid or even near-neutral to avoid competitive side reaction, while the adding of H₂O₂ should be in a batch type to suppress the oxidative damage of heme caused by the instantaneous concentrated H₂O₂. The mechanism of polymerization was also analyzed and proposed based on the characteristics of structure of CPO active site.

Key words: Chloroperoxidase, Polyphenol, Ionic liquid/Quaternary ammonium salt, Structure of substrate, Reaction microenvironment

CLC Number:

O632.7

TrendMD:

WANG Shengjie, LIU Lixia, JIANG Yucheng, HU Mancheng, LI Shuni, ZHAI Quanguo. Enzymatic Polymerization of Phenols Catalyzed by Chloroperoxidase in the Presence of Ionic Liquids/Quaternary Ammonium Salts^†[J]. Chem. J. Chinese Universities, 2016, 37(9): 1733.

Figures/Tables 8

Fig.1 Phenols compounds used in the polymerization catalyzed by CPO (A) p-Methyl phenol; (B) p-ethyl phenol; (C) p-propyl phenol; (D) p-phenyl phenol; (E) p-hydrox-cinnamic acid.

Fig.2 FTIR spectra of phenyl polymers (A) Polymer of p-phenyl phenol; (B) polymer of p-methyl phenol.

Fig.3 Mass spectrum of the product of CPO-catalyzed oxidation of p-phenyl phenol

Fig.4 Comparison of different phenols polymerization catalyzed by CPO in aqueous buffer in the presence of 0.08×10-3 mol/L TMABr to that in pure buffer aqueous a. p-Phenyl phenol; b. p-hydroxy-cinnamic acid; c. p-methyl phenol; d. p-ethyl phenol; e. p-propyl phenol.

Fig.5 Effect of ILs/QAS content on the p-phenylphenol polymerization (A) Imidazolium ILs. a. [EMIM][Br], b. [PMIM][Br], c. [BMIM][Br]; (B) QAS. a. TMABr, b. TEABr, c. TPABr, d. TBABr.

Fig.6 Influence of pH on p-phenyl phenol polymerization in aqueous buffer in the presence of 0.08×10-3 mol/L TMABr

Fig.7 Effect of amount of enzyme on poly phenyl phenol

Scheme 1 Polymerization of phenol through oxidation catalyzed by CPO

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