Li Hai-Mei, Xu Ting-Ting, Peng Qing-Xia, Chen Yong-Sheng, Zhou Hua, Lu Yu-Yun, Yan Ri-An
Department of Food Science and Engineering, Jinan University, Guangzhou, Guangdong, China.
College of Pharmacy, Jinan University, Guangzhou, Guangdong, China.
J Food Sci. 2021 May;86(5):1714-1725. doi: 10.1111/1750-3841.15703. Epub 2021 Apr 12.
Rutin (3',4',5,7-tetrahydroxy-flavone-3-rutinoside) was enzymatically acylated with benzoic acid and its esters (methyl benzoate and vinyl benzoate) using Thermomyces lanuginosus lipase (Lipozyme TLIM). The acylation reaction was optimized by varying the reaction medium, reaction temperature, acyl donor, substrate molar ratio, and reaction time. The highest conversion yield (76%) was obtained in tert-amyl alcohol (60 °C, 72 hr) using vinyl benzoate (molar ratio of 1:10) as acyl donor. The acylation occurred at the 2'''-OH and 4'''-OH of the rhamnose unit and the 2''-OH position of the glucose moieties. Three novel rutin acylated derivatives (compounds 1-3) were purified and characterized by HR-MS and 1D and 2D NMR spectroscopy. We found that acylation significantly improved lipophilicity, capacity to inhibit lipid peroxidation, anticancer capacity and substantially maintained the antioxidant activity of rutin. This research provides important insights in the acylation of flavonoids with different glycosyl moieties. PRACTICAL APPLICATION: In this study, three novel rutin derivatives were successfully synthesized and the highest conversion yield (76%) was obtained by reacting the rutin and vinyl benzoate at molar ratio of 1:10 in tert-amyl alcohol for 72 hr at 60 °C. Introducing a benzoic acid substituent into rutin molecule significantly improved their lipophilicity and inhibition of lipid peroxidation in lipophilic system. Furthermore, this study demonstrated that acylation significantly improved anticancer capacity and substantially maintained the antioxidant activity.
芦丁（3',4',5,7 - 四羟基黄酮 - 3 - 芸香糖苷）使用嗜热栖热菌脂肪酶（Lipozyme TLIM）与苯甲酸及其酯类（苯甲酸甲酯和苯甲酸乙烯酯）进行酶促酰化反应。通过改变反应介质、反应温度、酰基供体、底物摩尔比和反应时间对酰化反应进行优化。以苯甲酸乙烯酯（摩尔比1:10）作为酰基供体，在叔戊醇（60℃，72小时）中获得了最高转化率（76%）。酰化反应发生在鼠李糖单元的2'''-OH和4'''-OH以及葡萄糖部分的2''-OH位置。通过高分辨质谱（HR-MS）以及一维和二维核磁共振光谱对三种新型芦丁酰化衍生物（化合物1 - 3）进行了纯化和表征。我们发现酰化显著提高了芦丁的亲脂性、抑制脂质过氧化的能力、抗癌能力，并基本保持了其抗氧化活性。本研究为不同糖基部分的黄酮类化合物酰化提供了重要见解。实际应用：在本研究中，成功合成了三种新型芦丁衍生物，在60℃下于叔戊醇中使芦丁与苯甲酸乙烯酯以1:10的摩尔比反应72小时，获得了最高转化率（76%）。在芦丁分子中引入苯甲酸取代基显著提高了它们在亲脂体系中的亲脂性和对脂质过氧化的抑制作用。此外，本研究表明酰化显著提高了抗癌能力并基本保持了抗氧化活性。
