芹菜素-铜(Ⅱ)配合物研制及其清除自由基活性
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摘要
黄酮类化合物是一类天然的抗氧化剂,有着广泛的药理活性,但大部分黄酮的生物活性与生物利用率都比较低,而大量的研究发现黄酮类金属配合物能提升黄酮稳定性、水溶性及清除自由基能力。实验在乙醇-水混合溶剂中合成了芹菜素-铜(Ⅱ)配合物[Cu(AP)_2(H_2O)]·H_2O(AP=芹菜素阴离子),采用元素分析、红外光谱、紫外可见光谱、热重分析、电导率测定、铜(Ⅱ)滴定等方法确定其组成及结构,推断出芹菜素与铜(Ⅱ)的配位点为4-羰基及5-羟基,配位比为2:1,配合物分子为一变形的四方锥结构。同时着重分别通过NBT光照还原、Fenton反应和抗脂质过氧化方法研究了该配合物对超氧阴离子自由基、羟基自由基及过氧自由基的清除作用。结果表明,相对于芹菜素,配合物具有较强的清除自由基能力。
Flavonoids are a class of natural antioxidants with a wide range of pharmacological activities,but most of the flavonoids have low bioactivity and bioavailability. A large amount of literatures have showed that flavonoid metal complexes can enhance the stability, water solubility and free radical scavenging ability of flavonoids. In this work, the apigenin(AP)-Cu(Ⅱ) complex [Cu(AP)_2(H_2O)]·H_2O was synthesized in an ethanol-water mixed solvent and characterized by elemental analysis, infrared spectroscopy, UVVis absorption spectroscopy, thermogravimetric analysis, and conductance measurement and copper(Ⅱ)titration methods. It was concluded that the coordination sites of apigenin to copper(Ⅱ) were 4-carbonyl and 5-hydroxyl with the ratio of 2:1, and the complex had a distorted square-pyramidal geometry.Importantly, the scavenging abilities of the complex on hydroxyl, superoxide anion and peroxyl free radicals were studied by NBT photoperiod reduction, Fenton reaction and anti lipid peroxidation methods,respectively. The results showed that the complex exhibited stronger free radical scavenging activities than apigenin, which might be attributed the interaction between the central copper(Ⅱ) ion and the ligand.
Flavonoids are a class of natural antioxidants with a wide range of pharmacological activities,but most of the flavonoids have low bioactivity and bioavailability. A large amount of literatures have showed that flavonoid metal complexes can enhance the stability, water solubility and free radical scavenging ability of flavonoids. In this work, the apigenin(AP)-Cu(Ⅱ) complex [Cu(AP)_2(H_2O)]·H_2O was synthesized in an ethanol-water mixed solvent and characterized by elemental analysis, infrared spectroscopy, UVVis absorption spectroscopy, thermogravimetric analysis, and conductance measurement and copper(Ⅱ)titration methods. It was concluded that the coordination sites of apigenin to copper(Ⅱ) were 4-carbonyl and 5-hydroxyl with the ratio of 2:1, and the complex had a distorted square-pyramidal geometry.Importantly, the scavenging abilities of the complex on hydroxyl, superoxide anion and peroxyl free radicals were studied by NBT photoperiod reduction, Fenton reaction and anti lipid peroxidation methods,respectively. The results showed that the complex exhibited stronger free radical scavenging activities than apigenin, which might be attributed the interaction between the central copper(Ⅱ) ion and the ligand.
引文
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[3]汤小玉,魏安琪,李曙光,等.3种天然食品添加剂抑制自由基损伤能力的研究[J].化学与生物工程,2018,35(7):15-20.
[4]杨莉莉,郑明辉,许杨,等.环境持久性自由基的污染特征与生成机制[J].中国科学:化学,2018,48(10):1226-1235.
[5]Chang H,Lei L,Zhou Y,et al.Dietary Flavonoids and the Risk of Colorectal Cancer:An Updated Meta-Analysis of Epidemiological Studies[J].Nutrients,2018,10(7).
[6]冯靖,彭效明,李翠清,等.天然产物中黄酮类化合物的开发研究进展[J].中医药导报,2018,(4):71-74.
[7]刘衍季,何小燕,左华,等.黄酮类金属配合物的生物活性研究进展[J].中国中药杂志,2012,37(13):1901-1904.
[8]Kasprzak M M,Erxleben A,Ochocki J.ChemInform Abstract:Properties and Applications of Flavonoid Metal Complexes[J].Cheminform,2015,46(29):45853-45877.
[9]Panhwar Q K,Memon S,Bhanger M I.Synthesis,characterization,spectroscopic and antioxidation studies of Cu(II)-morin complex[J].Journal of Molecular Structure,2010,967(1-3):47-53.
[10]Zhang L,Liu Y,Wang Y,et al.UV-Vis spectroscopy combined with chemometric study on the interactions of three dietary flavonoids with copper ions[J].Food Chemistry,2018,263:208-215.
[11]Gan Q,Qi Y,Xiong Y,et al.Two New Mononuclear Copper(II)-Dipeptide Complexes of 2-(2’-Pyridyl)Benzoxazole:DNA Interaction,Antioxidation and in Vitro Cytotoxicity Studies[J].Journal of Fluorescence,2017,27(2):701-714.
[12]赵平,任鹏,张月萍.原花青素抗氧化活性测定方法比较[J].现代化工,2012,32(5):119-122.
[13]旷慧,冯建文,范倩,等.红树莓多酚的组分分析及体外抗脂质过氧化活性[J].食品科学,2018,39(3):83-89.
[14]钱俊臻.基于神经网络的黄酮类金属配合物抗肿瘤与抗氧化构效关系模型研究[D].重庆:重庆大学,2014.
[15]Roy S,Mallick S,Chakraborty T,et al.Synthesis,characterisation and antioxidant activity of luteolinvanadium(II)complex[J].Food Chemistry,2015,173:1172-1178.
[16]Geary W J.The use of conductivity measurements in organic solvents for the characterisation of coordination compounds[J].Coordination Chemistry Reviews,1971,7(1):81-122.
[17]Tan J,Wang B,Zhu L.DNA binding and oxidative DNAdamage induced by a quercetin copper(II)complex:potential mechanism of its antitumor properties[J].Journal of Biological Inorganic Chemistry,2009,14(5):727-739.
[18]Juan J Martínez Medina,Naso L G,Ana L Pérez,et al.Apigenin oxidovanadium(IV)cation interactions.Synthesis,spectral,bovine serum albumin binding,antioxidant and anticancer studies[J].Journal of Photochemistry&Photobiology A Chemistry,2017,344:84-100.
[19]Medina J J M,Naso L G,Ana L Pérez,et al.Antioxidant and anticancer effects and bioavailability studies of the flavonoid baicalin and its oxidovanadium(IV)complex[J].Journal of Inorganic Biochemistry,2016,166:150-161.
[20]Naso L G,Lezama L,Valcarcel M,et al.Bovine serum albumin binding,antioxidant and anticancer properties of an oxidovanadium(IV)complex with luteolin[J].Journal of Inorganic Biochemistry,2016,157(5):80-93.