八元瓜环与黄岑苷的主客体相互作用及对黄岑苷性质的影响

doi:10.7503/cjcu20180337

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (11): 2425.doi: 10.7503/cjcu20180337

八元瓜环与黄岑苷的主客体相互作用及对黄岑苷性质的影响

黄净净¹, 许志玲², 练小卫², 张晓东¹, 陶朱¹, 周清娣³, 张前军¹(), 卫钢⁴()

1. 贵州省大环化学及超分子化学重点实验室, 贵州大学化学与化工学院, 贵阳 550025
2. 精细化工中心, 贵阳 550025
3. 澳大利亚悉尼大学化学学院, 新南威尔士州 2006
4. 澳大利亚联邦科学与工业组织(CSIRO), 新南威尔士州 2070

收稿日期:2018-05-02 出版日期:2018-11-10 发布日期:2018-08-03
作者简介:联系人简介: 张前军, 女, 博士, 教授, 主要从事天然有机化学方面的研究. E-mail: qianjunzhang@126.com; 卫钢, 男, 博士, 教授, 博士生导师, 主要从事超分子化学方面的研究. E-mail: Gang.Wei@csiro.au
基金资助:
教育部春晖计划项目(批准号: Z2015003)资助.

Host-guest Interaction Between Cucurbit[8]uril and Baicalin and Its Effect on the Properties of Baicalin^†

HUANG Jingjing¹, XU Zhiling², LIAN Xiaowei², ZHANG Xiaodong¹, TAO Zhu¹, ZHOU Qingdi³, ZHANG Qianjun^1,^*(), WEI Gang^4,^*()

1. Key Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, Chemistry and Chemical Engineering College, Guiyang 550025, China
2. Research and Development Center of Fine Chemicals, Guizhou University, Guiyang 550025, China
3. College of Chemistry, the University of Sydney, NSW 2006, Australia
4. CSIRO Manufacturing, NSW 2070, Australia

Received:2018-05-02 Online:2018-11-10 Published:2018-08-03
Contact: ZHANG Qianjun,WEI Gang E-mail:qianjunzhang@126.com;Gang.Wei@csiro.au
Supported by:
† Sopported by the Chunhui Project of the Ministry of Education, China(No.Z2015003).

摘要/Abstract

摘要：

利用紫外吸收光谱和核磁共振波谱(NMR)等方法考察了八元瓜环(Q[8])与黄岑苷(BAL)之间的相互作用. 结果表明, Q[8]与BAL形成了摩尔比为1:1的包结配合物, 包结稳定常数K=2.8×10⁴ L/mol. 相溶解度法研究结果表明, 当Q[8]浓度为100 μmol/L时, 可使BAL在水中的溶解度增加4.5倍. 采用2,2-联氮基-双-(3-乙基苯并噻唑-6-磺酸)二铵盐(ABTS)方法考察了Q[8]对BAL抗氧化活性的影响, BAL-Q[8]包合物与游离BAL均对ABTS自由基具有清除能力, IC₅₀值分别为5.48和5.07 μmol/L. 在人工肠液中BAL和BAL-Q[8]包合物较稳定; 而在人工胃液中BAL在6 h后迅速降解, BAL-Q[8]包合物则基本未降解, Q[8]显著提高了BAL在人工胃液中的稳定性. 体外累积释放度研究结果表明, 在人工胃液中Q[8]的介入提高了BAL的累积释放量, 其数值提高了2倍; 在人工肠液中BAL-Q[8]包合物的累积释放速度明显慢于BAL的累计释放速度, 说明Q[8]包合BAL后对BAL有一定的缓释作用.

关键词: 黄岑苷, 八元瓜环, 包结配合物, 稳定性, 抗氧化活性

Abstract:

The interaction between cucurbit[8]uril(Q[8]) and baicalin(BAL) was investigated by ultraviolet-visible absorption spectrometry and nuclear magnetic resonance spectroscopy. The results showed that Q[8] and BAL formed an inclusion complex with molar ratio of 1:1. The inclusion stability constant was 2.8×10⁴ L/mol. The phase solubility experiments revealed that the solubility of BAL in water increased 4.5 fold by interacting with Q[8] at 100 μmol/L. The effect of Q[8] on antioxidant activity of BAL was investigated by 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulphonate acid)(ABTS) method. Both the BAL-Q[8] inclusion complex and BAL had the scavenging ability for ABTS free radicals, and the IC₅₀ values were 5.48 and 5.07 μmol/L, respectively. BAL and BAL-Q[8] were stable in artificial intestinal juice. BAL was degraded rapidly in 6 h, but BAL-Q[8] was not degraded basically in artificial gastric juice, which indicated that Q[8] significantly improved the stability of BAL in artificial gastric juice. In vitro cumulative release results showed that Q[8] increased the cumulative release of BAL in artificial gastric juice by 2 times. The cumulative release rate of BAL-Q[8] was significantly slower than the cumulative release rate of BAL in artificial intestinal juice, which indicated that Q[8] had sustained release effect on BAL.

Key words: Baicalin, Cucurbit[8]uril, Inclusion complex, Stability, Antioxidant activity

中图分类号:

O624
O641.3

TrendMD:

黄净净, 许志玲, 练小卫, 张晓东, 陶朱, 周清娣, 张前军, 卫钢. 八元瓜环与黄岑苷的主客体相互作用及对黄岑苷性质的影响. 高等学校化学学报, 2018, 39(11): 2425.

HUANG Jingjing, XU Zhiling, LIAN Xiaowei, ZHANG Xiaodong, TAO Zhu, ZHOU Qingdi, ZHANG Qianjun, WEI Gang. Host-guest Interaction Between Cucurbit[8]uril and Baicalin and Its Effect on the Properties of Baicalin^†. Chem. J. Chinese Universities, 2018, 39(11): 2425.

图/表 9

Fig.1 Structures of baicalin(BAL, A) and cucurbit[8]uril(Q[8], B)

Fig.2 UV-Vis absorption spectra of BAL with Q[8] in aqueous solution(A) or hydrochloric acid solution(C) and UV-Vis Job’s plot of ΔA against n(Q[8])/[n(Q[8])+n(BAL)] at 275 nm (B,D)c(BAL)=20 μmol/L; (A,C)n(Q[8])/n(BAL): a. 0; b. 0.2; c. 0.4; d. 0.6; e. 0.8; f. 1.0; g. 1.2;h. 1.4; i. 1.6; j. 1.8; k. 2.0. Insets in (A, C) are the plot of absorbances at 275 nm of BAL.

Scheme 1 Interaction model of Q[8] with BAL

Table 1 1H NMR and 1H-1H COSY spectra of BAL and BAL-Q[8]

Position	¹H NMR[400 MHz, V(DCl):V(D₂O)=5:1], δ		¹H-¹H COSY of BAL-Q[8]
Position	BAL	BAL-Q[8]	¹H-¹H COSY of BAL-Q[8]
3	4.19(1H, s)	3.93(1H, s)
8	4.04(1H, s)	4.63(1H, s)
2'	4.77(1H, d)	3.68(1H, m)	2'-H/ 1',3'-H
3'	4.32(1H, t)	3.32(1H, m)	3'-H/ 2', 4'-H
4'	4.49(1H, t)	3.63(1H, m)	4'-H/ 3', 5'-H
5'	4.32(1H, t)	3.08(1H, m)	5'-H/ 4',6'-H
6'	4.77(1H, d)	3.83(1H, m)	6'-H/ 1',5'-H
1″	2.25(1H, d)	2.35(1H, brs)	1″-H/ 2″-H
2″	0.76(1H, t)	0.99(1H, t)	2″-H/ 1″,3″-H
3″	0.62(1H, t)	0.92(1H, t)	3″-H/ 2″, 4″-H
4″	0.49(1H, t)	0.78(1H, t)	4″-H/ 3″ , 5″-H
5″	1.43(1H, d)	1.25(1H, brs)	5″-H/ 4″-H

Fig.3 IR spectra of Q[8](a), BAL(b), physical mixture of BAL-Q[8] (c), BAL-Q[8] inclusion complex(d)

Fig.4 UV spectra of saturated BAL in the presence of different concentrations of Q[8](A) and phase solubility graph of BAL in Q[8] at λ=275 nm(B)c(Q[8])/(μmol·L-1): a. 0; b. 10; c. 30; d. 50; e. 70; f. 90.

Fig.5 Changes of UV absorption intensity of BAL and BAL-Q[8] inclusion complex over time at pH=1.2(A) and 6.8(B)

Fig.6 Scavenging activity of BAL, BAL-Q[8] inclusion complex and L(+)-ascorbic acid at different concentrations

Fig.7 Release curves of BAL and BAL-Q[8] inclusion complex at pH=1.2(A) and 6.8(B)

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八元瓜环与黄岑苷的主客体相互作用及对黄岑苷性质的影响

Host-guest Interaction Between Cucurbit[8]uril and Baicalin and Its Effect on the Properties of Baicalin^†

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八元瓜环与黄岑苷的主客体相互作用及对黄岑苷性质的影响

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Host-guest Interaction Between Cucurbit[8]uril and Baicalin and Its Effect on the Properties of Baicalin^†