咖啡酸的化学改性及产物抗氧化性的研究

doi:10.3969/j.issn.1001-1803.2019.02.007

摘要/Abstract

摘要：

以咖啡酸和氨基酸乙酯盐酸盐为原料,1-（3-二甲基氨基丙基）-3-乙基碳二亚胺盐酸盐（EDC）及1-羟基苯并三唑（HOBt）为催化剂,合成咖啡酰甘氨酸乙酯、咖啡酰丙氨酸乙酯、咖啡酰丝氨酸乙酯、咖啡酰苏氨酸乙酯4种产物。利用核磁共振氢谱（ ¹H NMR）和高效液相色谱-质谱（HPLC-MS）对产物结构进行表征,考察了咖啡酸化学改性产物对DPPH自由基及羟基自由基活性的抑制率及对红细胞膜的刺激性,并与咖啡酸单体进行了比较。结果表明,通过在咖啡酸中引入甘氨酸乙酯、丙氨酸乙酯、丝氨酸乙酯和苏氨酸乙酯后,4种咖啡酸酰胺类产物均呈现较好的抑制DPPH自由基、羟基自由基活性的效果;咖啡酰丝氨酸乙酯清除DPPH自由基能力较强,其IC₅₀值为13.5 μmol/L;咖啡酰丙氨酸乙酯清除羟基自由基能力较强,其IC₅₀值为0.214 mmol/L。红细胞溶血试验结果表明,4种咖啡酸酰胺类衍生物的红细胞溶血率均低于咖啡酸单体。

关键词: 化妆品添加剂, 咖啡酸, 咖啡酰氨基酸酯衍生物, DPPH自由基, 羟基自由基, 红细胞溶血

Abstract:

Caffeoyl glycine ethyl ester, caffeoyl alanine ethyl ester, caffeoyl serine ethyl ester and caffeoyl threonine ethyl ester were synthesized from L-amino acid ethyl ester hydrochloride with caffeic acid in the presence of a catalytic amount of 1-（3-dimethylaminopropyl）-3-ethylcarbodiimide hydrochloride （EDC） and 1-hydroxybenzotriazole （HOBt） . The structure of the products after the reaction was characterized by ¹H NMR and HPLC-MS. The inhibitory rates against DPPH radical and hydroxyl radical and the erythrocyte membrane irritation were investigated for the chemically modified products of caffeic acid which were compared with caffeic acid. The results show that all these four caffeic acid amide derivatives show good inhibition against DPPH radicals and hydroxyl radicals, which have introduced glycine ethyl ester, alanine ethyl ester, serine ethyl ester, and threonine ethyl ester in the molecular structure of caffeic acid. The caffeic acid amide derived from serine ethyl ester has the strongest scavenging activity against DPPH free radicals （IC₅₀=13.5 μmol/L）, while the one derived from alanine ethyl ester is the strongest in scavenging hydroxyl radicals with an IC₅₀value of 0.214 mmol/L. The results of red blood cell hemolysis show that all these four caffeic acid amide derivatives exihibit lower hemolysis ratios than caffeic acid.

Key words: cosmetic additive, caffeic acid, caffeic acid amide derivative from amino acid ethyl ester, DPPH radical, hydroxyl radical, hemolysis of erythrocytes

中图分类号:

TQ658

王东,赵雪,宋京九,祝钧. 咖啡酸的化学改性及产物抗氧化性的研究[J]. 日用化学工业, 2019, 49(2): 98-102.

Dong WANG,Xue ZHAO,Jing-jiu SONG,Jun ZHU. Synthesis and the antioxidation study of the chemically modified derivatives of caffeic acid[J]. China Surfactant Detergent & Cosmetics, 2019, 49(2): 98-102.

图/表 3

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物质	IC₅₀/（μmol·L^-1）
a	18.6
b	29.7
c	13.5
d	14.5
CA	27.6
V_C	80.9

物质	IC₅₀/（mmol·L^-1）
a	0.340
b	0.214
c	0.244
d	0.268
CA	0.286
V_C	1.680

物质	溶血率/%
a	2.38
b	1.07
c	-0.85
d	-0.38
CA	2.39
DMSO	0.89
SDS	74.00