Facile and Efficient Acylation of Bioflavonoids Using Whole-Cell Biocatalysts in Organic Solvents
Facile and Efficient Acylation of Bioflavonoids Using Whole-Cell Biocatalysts in Organic Solvents
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使用全细胞生物催化剂在有机溶剂中轻松高效地酰化生物类黄酮
DOI：
10.1021/acssuschemeng.7b02628
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发表时间：
2017-11-01
影响因子：
8.4
通讯作者：
Zhao, Guanglei
中科院分区：
文献类型：
--
作者：
Xing, Xuan;Li, Xiao-Feng;Zhao, Guanglei
生物类黄酮具有许多生物学和药理活性，但由于糖苷形式的亲脂性较差，许多生物类黄酮口服后生物利用度较低。为了提高它们的亲脂性和生物活性，研究了在二元溶剂体系中利用全细胞生物催化剂对四种维生素p类生物黄酮类化合物（曲维芦丁、芦丁、橙皮苷和柚皮苷）进行脂肪酰基修饰的新方法。以troxerutin为典型的重要生物类黄酮，对不同来源的15株菌株的酰化活性进行了评价，结果表明绿脓杆菌（Pseudomonas aeruginosa GIM 1.46）在非水培养基中的酰化活性最高。C-13 NMR、ESI-MS和FT-IR分析证实，P. aeruginosa催化了曲希芦丁的酰化反应，生成了曲希芦丁单丙酸（主要产物）和曲希芦丁二丙酸。在正庚烷和吡啶二元体系中，由于使用二元有机溶剂适当增加了细胞包膜的通透性和细胞活力，细胞表现出比在其他溶剂中更高的催化活性和操作稳定性。结果表明，最佳的正庚烷浓度、丙酸乙烯与曲鲁丁的摩尔比、催化剂用量和反应温度分别为35%、30:1、50 mg/mL和40℃，在此条件下，曲鲁丁的转化率和单酯收率分别达到94%和81.1%。
Bioflavonoids have many biological and pharmacological activities, but many of them display low bioavailability after oral administration owing to poor lipophilicity of glycoside forms. To improve their lipophilicity, as well as their bioactivity, a new efficient approach was developed for fatty acyl-modification of four vitamin P-like bioflavonoids (troxerutin, rutin, hesperidin, and naringin) using whole-cell biocatalysts in binary solvent systems. Using troxerutin as a typical important bioflavonoid, the acylation activities of 15 strains of different sources were evaluated and Pseudomonas aeruginosa GIM 1.46 showed the highest acylation activity in nonaqueous mediums. C-13 NMR, ESI-MS, and FT-IR analysis confirmed that P. aeruginosa catalyzed acylation of troxerutin to produce troxerutin monopropionate (dominant product) and troxerutin dipropionate. In a binary system of n-heptane and pyridine, the cells showed much higher catalytic activity and operational stability than in other solvents, attributing to a proper increase in permeability of cell envelopes and cell viability by using the binary organic solvents. The optimal n-heptane concentration, molar ratio of vinyl propionate to troxerutin, catalyst dosage, and reaction temperature were found as 35%, 30:1, SO mg/mL, and 40 degrees C, respectively, under which the troxerutin conversion and the monoester yield reached 94% and 81.1%, respectively.