电位滴定法研究单宁酸去质子化特性

doi:10.3969/j.issn.0253-2417.2021.01.001

林产化学与工业 ›› 2021, Vol. 41 ›› Issue (1): 1-6.doi: 10.3969/j.issn.0253-2417.2021.01.001

电位滴定法研究单宁酸去质子化特性

张亮亮¹(), 张禾¹, 徐曼¹, 胡新宇¹, 刘义稳²

1. 中国林业科学研究院林产化学工业研究所; 生物质化学利用国家工程实验室; 国家林业和草原局林产化学工程重点实验室; 江苏省生物质能源与材料重点实验室; 江苏省林业资源高效加工利用协同创新中心, 江苏南京 210042
2. 五峰赤诚生物科技股份有限公司, 国家林业和草原局五倍子高效培育与精深加工工程技术研究中心, 湖北宜昌 443413

收稿日期:2020-10-28 出版日期:2021-02-28 发布日期:2021-03-03
作者简介:张亮亮(1981-), 男, 江苏沭阳人, 副研究员, 博士, 研究方向为植物单宁(多酚)化学; E-mail: zhll20086@163.com
基金资助:
国家重点研发计划资助项目(2018YFD0600404)

Determination of Deprotonation Characteristics of Tannic Acid by Potential Titration Method

Liangliang ZHANG¹(), He ZHANG¹, Man XU¹, Xinyu HU¹, Yiwen LIU²

1. Institute of Chemical Industry of Forest Products, CAF; National Engineering Lab. for Biomass Chemical Utilization; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; Key Lab. of Biomass Energy and Material, Jiangsu Province; Jiangsu Co-Innovation Center for Efficient Processing and Utilization of Forest Resources, Nanjing 210042, China
2. Wufeng Chicheng Biotechnology Co. Ltd., Engineering Techonology Research Center of High-Efficient Cultivation and Deep Processing of Chinese Gall, National Forestry and Grassland Administration, Yichang 443413, China

Received:2020-10-28 Online:2021-02-28 Published:2021-03-03

摘要/Abstract

摘要：

采用pH电位滴定法及分光光度法测定了单宁酸化合物1，2，3，4，6-O-五没食子酰葡萄糖（PGG），及其组成单体化合物没食子酸甲酯（MeG）在溶液中的去质子化特性，运用化学计量学软件Reactlab Equilibrium测定了相应的离解常数，分析了不同pH值条件下各化合物的存在形式及变化规律。研究结果表明：随着pH值的升高，PGG逐渐发生去质子化反应脱去质子，pH>11时，配体失去全部质子。光谱学研究发现PGG分子中共有两个酚羟基依次发生了去质子化，形成氧负离子，并进一步与金属离子发生络合，离解常数分别为pK_a1=10.84±0.03和pK_a2=10.62±0.02；MeG分子中只有一个酚羟基会发生去质子化反应，其离解常数为pK_a=9.68±0.02。

关键词: 单宁酸, 去质子化, 离解常数, 分光光度法, 化学计量学

Abstract:

The deprotonation process of a typical tannic acid, 1, 2, 3, 4, 6-penta-O-galloyl-β-D-glucopyranose(PGG), and its parent compound methyl gallate(MeG) was studied by pH potentiometric titration and spectrophotography. The dissociation constants of PGG and MeG were calculated by chemometric methods using the Reactlab Equilibrium software. Concentration profiles of the fully protonated PGG and its two deprotonated forms at different pH values were also predicted by the chemometric method. The results showed that the deprotonation of phenolic hydroxyl of PGG was found with the increasing of pH value, and fully deprotonated forms of PGG existed at pH>11. These formed negative ions of oxygen can further coordinate with metal ions. Spectroscopic studies showed that there were two deprotonated forms of PGG, and the corresponding pK_a values were 10.84±0.03 and 10.62±0.02. There was only one deprotonated form of MeG during titration, and the corresponding pK_a value was 9.68±0.02.

Key words: tannic acid, deprotonation, dissociation constants, spectrophotography, stochiometry

中图分类号:

TQ35

张亮亮, 张禾, 徐曼, 胡新宇, 刘义稳. 电位滴定法研究单宁酸去质子化特性[J]. 林产化学与工业, 2021, 41(1): 1-6.

Liangliang ZHANG, He ZHANG, Man XU, Xinyu HU, Yiwen LIU. Determination of Deprotonation Characteristics of Tannic Acid by Potential Titration Method[J]. Chemistry and Industry of Forest Products, 2021, 41(1): 1-6.

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参考文献 16

1	石碧, 狄莹. 植物多酚[M]. 北京: 科学出版社, 2000.
	SHI B , DI Y . Plant Polyphenol[M]. Beijing: China Science Publishing & Media Ltd., 2000.
2	孙达旺. 植物单宁化学[M]. 北京: 中国林业出版社, 1992.
	SUN D W . Plant Tannins Chemical[M]. Beijing: China Forestry Publishing House, 1992.
3	ANDJELKOVIC M , VAN-CAMP J , DE-MEULENAER B , et al. Iron-chelation properties of phenolic acids bearing catechol and galloyl groups[J]. Food Chemistry, 2006, 98 (1): 23- 31. doi: 10.1016/j.foodchem.2005.05.044
4	CRUZ B H , DIAZ-CRUZ J M , ARINO C , et al. Heavy metal binding by tannic acid: A voltammetric study[J]. Electroanalysis, 2000, 12 (14): 1130- 1137. doi: 10.1002/1521-4109(200010)12:14<1130::AID-ELAN1130>3.0.CO;2-7
5	HIDER R C , LIU Z D , KHODR H H . Metal chelation of polyphenols[J]. Methods in Enzymology, 2001, 335, 190- 203.
6	Jplus Consulting. Products[EB/OL]. http://jplusconsulting.com/products/reactlab-equilibria.
7	CHEN Y , HAGERMAN A E . Reaction pH and protein affect the oxidation products of β-pentagalloyl glucose[J]. Free Radical Research, 2005, 39 (2): 117- 124. doi: 10.1080/10715760400013789
8	JAFFE H , ORCHIN M . Theory and Application of UV Spectroscopy[M]. London: Wiley and Sons Press, 1962.
9	FAZARY A E , TAHA M , JU Y H . Iron complexation studies of gallic acid[J]. Journal of Chemical & Engineering Data, 2008, 54 (1): 35- 42.
10	HYNES M J , COINCEANAINN M O . The kinetics and mechanisms of the reaction of iron(Ⅲ) with gallic acid, gallic acid methyl ester and catechin[J]. Journal of Inorganic Biochemistry, 2001, 85 (2/3): 131- 142.
11	ZHANG L, LIU Y, HU X, et al. Studies on interactions of pentagalloyl glucose, ellagic acid and gallic acid with bovine serum albumin: A spectroscopic analysis[J/OL]. Food Chemistry, 2020, 324: 1-6[2020-01-20].https://doi.org/10.1016/j.foodchem.2020.126872.
12	ÖHMAN L O , SJOBERG S . Equilibrium and structural studies of silicon(Ⅳ) and aluminium(Ⅲ) in aqueous solution.4:A potentiometric study of polynuclear aluminium(Ⅲ) hydroxo complexes with gallic acid in hydrolyzed aluminium(Ⅲ) solutions[J]. Acta Chem Scand, 1982, 36, 47- 53.
13	ZHANG L , LIU R , GUNG B W , et al. Polyphenol-aluminum complex formation: Implications for aluminum tolerance in plants[J]. Journal of Agricultural and Food Chemistry, 2016, 64 (15): 3025- 3033. doi: 10.1021/acs.jafc.6b00331
14	SLABBERT N. Complexation of condensed tannins with metal ions[M]//HEMINGWAY R W, LAKS P E. Plant Polyphenols: Synthesis, Properties, Significance. NewYork: Plenum Press, 1992: 421-436.
15	刘瑜琛, 张亮亮, 汪咏梅, 等. 分光光度法测定单宁酸-Fe³⁺反应结合常数及其化学计量比[J]. 林业工程学报, 2018, 3 (2): 47- 52.
	LIU Y C , ZHANG L L , WANG Y M , et al. Spectrophotometric determination of formation constants and stoichiometry of tannic acid complexes with Fe³⁺[J]. China Forestry Science and Technology, 2018, 3 (2): 47- 52.
16	FELDMAN K S , SMITH R S . Ellagitannin chemistry: First total synthesis of the 2, 3-and 4, 6-coupled ellagitannin pedunculagin[J]. The Journal of Organic Chemistry, 1996, 61 (8): 2606- 2612. doi: 10.1021/jo952130+

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电位滴定法研究单宁酸去质子化特性

Determination of Deprotonation Characteristics of Tannic Acid by Potential Titration Method

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