Horseradish peroxidase mediated free radical polymerization of methyl methacrylate

被引:93
作者
Kalra, B [1 ]
Gross, RA [1 ]
机构
[1] Polytech Univ, NSF, Ctr Biocatalysis & Bioproc, Metrotech Ctr 6, Brooklyn, NY 11201 USA
关键词
D O I
10.1021/bm005576v
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
This paper reports the free radical polymerization of methyl methacrylate (MMA) catalyzed by horseradish peroxidase (HRP). A novel method was developed whereby MMA polymerization can be carried out at ambient temperatures in the presence of low concentrations of hydrogen peroxide and 2,4-pentanedione in a mixture of water and a water-miscible solvent. Polymers of MMA formed were highly stereoregular with predominantly syndiotactic sequences (syn-dyad fractions from 0.82 to 0.87). Analyses of the chloroform-soluble fraction of syndio-PMMA products by GPC showed that they have number-average molecular weights, M-n, that range from 7500 to 75 000. By using 25% v/v of the cosolvents dioxane, tetrahydrofuran, acetone, and dimethylformamide, 85, 45, 7 and 2% product yields, respectively, resulted after 24 h. Increasing the proportion of dioxane to water from 1:3 to 1:1 and 3:1 resulted in a decrease in polymer yield from 45 to 38 and 7%, respectively. Increase in the enzyme concentration from 70 to 80 and 90 mg/mL resulted in increased reaction kinetics. By adjustment of the molar ratio of 2,4-pentanedione to hydrogen peroxide between 1.30:1.0 and 1.45:1.0, the product yields and M-n values were increased. On the basis of the catalytic properties of HRP and studies herein, we believe that the keto-enoxy radicals from 2,4-pentanedione are the first radical species generated. Then, initiation may take place through this radical or by the radical transfer to another molecule.
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页码:501 / 505
页数:5
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