使用胆红素氧化酶对二氢槲皮素进行酶促聚合。

Enzymatic polymerization of dihydroquercetin using bilirubin oxidase.

作者信息

Khlupova M E, Vasil'eva I S, Shumakovich G P, Morozova O V, Chertkov V A, Shestakova A K, Kisin A V, Yaropolov A I

机构信息

A. N. Bach Institute of Biochemistry, Russian Academy of Sciences, Moscow, 119071, Russia.

出版信息

Biochemistry (Mosc). 2015 Feb;80(2):233-41. doi: 10.1134/S0006297915020108.

DOI:10.1134/S0006297915020108

PMID:25756538

Abstract

Dihydroquercetin (or taxifolin) is one of the most famous flavonoids and is abundant in Siberian larch (Larix sibirica). The oxidative polymerization of dihydroquercetin (DHQ) using bilirubin oxidase as a biocatalyst was investigated and some physicochemical properties of the products were studied. DHQ oligomers (oligoDHQ) with molecular mass of 2800 and polydispersity of 8.6 were obtained by enzymatic reaction under optimal conditions. The oligomers appeared to be soluble in dimethylsulfoxide, dimethylformamide, and methanol. UV-visible spectra of oligoDHQ in dimethylsulfoxide indicated the presence of highly conjugated bonds. The synthesized oligoDHQ was also characterized by FTIR and (1)H and (13)C NMR spectroscopy. Comparison of NMR spectra of oligoDHQ with DHQ monomer and the parent flavonoids revealed irregular structure of a polymer formed via the enzymatic oxidation of DHQ followed by nonselective radical polymerization. As compared with the monomer, oligoDHQ demonstrated higher thermal stability and high antioxidant activity.

摘要

二氢槲皮素（或紫杉叶素）是最著名的类黄酮之一，在西伯利亚落叶松（Larix sibirica）中含量丰富。研究了以胆红素氧化酶作为生物催化剂对二氢槲皮素（DHQ）进行氧化聚合反应，并对产物的一些物理化学性质进行了研究。在最佳条件下通过酶促反应获得了分子量为2800且多分散性为8.6的DHQ低聚物（oligoDHQ）。这些低聚物似乎可溶于二甲基亚砜、二甲基甲酰胺和甲醇。oligoDHQ在二甲基亚砜中的紫外可见光谱表明存在高度共轭键。合成的oligoDHQ还通过傅里叶变换红外光谱以及氢核磁共振（1H）和碳核磁共振（13C）光谱进行了表征。将oligoDHQ的核磁共振光谱与DHQ单体及母体类黄酮进行比较，结果表明通过DHQ的酶促氧化随后进行非选择性自由基聚合形成的聚合物具有不规则结构。与单体相比，oligoDHQ表现出更高的热稳定性和高抗氧化活性。