金属有机骨架材料ZIF-8富集黄芩中黄芩苷的新方法

doi:10.6023/A19080316

摘要/Abstract

本工作旨在探索MOFs材料高效富集黄芩中黄芩苷的新方法，拓展MOFs在吸附领域的用途.溶剂热法合成了沸石咪唑酯骨架-8（ZIF-8），并进行了结构表征，以确保其准确合成.研究了ZIF-8对黄芩苷的吸附规律和作用机理：ZIF-8对黄芩苷的吸附符合准二级动力学方程，平衡吸附数据符合Langmuir吸附等温模型.采用响应面法（RSM）得到优化后的最佳吸附参数，在此条件下，ZIF-8对黄芩中黄芩苷的吸附率高达98.22%，且对黄芩中其它成分吸附效果不显著，以pH 6.8的PBS溶液作解吸液，ZIF-8对黄芩苷的解吸率为62.46%，而黄芩苷的纯度由吸附前的21.55%提高到解吸后的64.27%，且ZIF-8在吸附前后稳定性良好，回收率达到83.50%.因此，ZIF-8在吸附纯化黄芩苷方面具有潜在的应用价值.

关键词: 金属有机框架, 吸附, X射线光电子能谱(XPS)

This work aims to explore a new method for the efficient enrichment of baicalin in Scutellaria baicalensis Georgi by using metal organic frameworks (MOFs) materials, and to open up new applications for MOFs in the adsorption direction. The zeolitic imidazolate framework-8 (ZIF-8) was synthesized by solvothermal method and characterized by structure to ensure its accurate synthesis. Baicalin was extracted from Scutellaria baicalinsis Georgi by ethanol extraction and acid precipitation method. The ZIF-8 was used to carry out the static adsorption experiment on the crude extract of Radix Scutellariae. After the adsorption equilibrium was reached, the mixture was centrifuged, and the residual concentration of baicalin was detected by high performance liquid chromatography method (HPLC). The recovered saturated adsorbed ZIF-8 material was washed with water and dried, and the phosphate buffered saline (PBS) solution of pH 6.8 was used as a desorption solution, and the desorption was performed by shaking. The content of baicalin in the desorbed solution was determined by HPLC to calculate the desorption rate and achieve the purpose of adsorbent recovery. In the adsorbing process, the effects of adsorbent dosage, pH and adsorbate concentration of the crude extract of Radix Scutellariae were also optimized, and the response surface test (RSM) was performed using Design Expert software to obtain optimal adsorption conditions. Under these conditions, the adsorption rate of ZIF-8 to baicalin in Radix Scutellariae was as high as 98.22%, and the adsorption effect was not significant on other components in Radix Scutellariae. The desorption rate of ZIF-8 adsorbed baicalin in pH 6.8 solution was 62.46%, and the purity of baicalin increased from 21.55% before adsorption to 64.27% after desorption, and ZIF-8 had good stability before and after adsorption, and the recovery rate reached 83.50%. Therefore, ZIF-8 has potential application value in the adsorption and purification of baicalin. The adsorption law and mechanism of ZIF-8 on baicalin were studied:The adsorption of baicalin on ZIF-8 accorded with the quasi-second-order kinetic equation, and the equilibrium adsorption data accorded with the Langmuir adsorption isotherm model.

Key words: metal-organic framework, adsorption, X-ray photoelectron spectroscopy

引用此文

郭文娟, 于洁, 代昭, 侯伟钊. 金属有机骨架材料ZIF-8富集黄芩中黄芩苷的新方法[J]. 化学学报, 2019, 77(11): 1203-1210.

Guo Wenjuan, Yu Jie, Dai Zhao, Hou Weizhao. A New Method for Enriching baicalin in Scutellaria baicalensis Georgi by Metal Organic Framework Material ZIF-8[J]. Acta Chimica Sinica, 2019, 77(11): 1203-1210.

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图/表 17

图 1. 黄芩苷结构式

Figure 1. Structural formula of baicalin

因素	编码	水平
因素	编码	－1	0	1
吸附剂用量/mg	A	16	24	32
初始浓度/(mg?L^－1)	B	200	300	400
pH	C	3	4	5

表 1. 响应面设计因素编码及水平

Table 1. Codes and levels of RSM experiment

图 2. (a) 合成ZIF-8的XRD图; (b)合成ZIF-8的TG图; (c)合成ZIF-8的SEM图; (d)合成ZIF-8的N2吸附-脱附曲线

Figure 2. (a) X-ray diffraction patterns of the synthesized ZIF-8; (b) TG curve of the synthesized ZIF-8; (c) SEM image of the synthesized ZIF-8; (d) N2 adsorption-desorption curves of the synthesized ZIF-8

图 3. ZIF-8吸附黄芩粗提物前后及解吸后HPLC对比

Figure 3. HPLC chromatograms of the Scutellaria baicalensis Georgi crude extract before and after adsorption with ZIF-8, and the desorption solution of ZIF-8 after adsorption

图 4. 吸附剂用量对吸附率的影响

Figure 4. Effect of adsorbent dosage on adsorption rate

图 5. 初始浓度对吸附率的影响

Figure 5. Effect of the initial concentration on adsorption rate

图 6. 初始pH对吸附率的影响

Figure 6. Effect of initial pH on adsorption rate

实验号	因素			吸附率/%
实验号	A	B	C	吸附率/%
1	0	0	0	56.74
2	1	1	0	98.22
3	0	－1	1	84.95
4	0	－1	－1	81.38
5	1	－1	0	92.36
6	0	1	－1	94.26
7	－1	0	－1	71.64
8	0	0	0	56.74
9	1	0	1	95.68
10	1	0	－1	95.89
11	－1	0	1	63.90
12	－1	－1	0	56.52
13	0	0	0	57.02
14	0	0	0	56.68
15	0	1	1	92.19
16	0	0	0	56.53
17	－1	1	0	72.68

表 2. 响应面分析实验结果

Table 2. The experimental results of RSM analysis

类型	平方和	自由度	均方	F值	P值	显著性
模型	4638.92	9	515.44	235.65	＜0.0001	显著
A	1722.80	1	1722.80	787.66	＜0.0001
B	221.96	1	221.96	101.48	＜0.0001
C	5.18	1	5.18	2.37	0.1676
AB	26.51	1	26.51	12.12	0.0103
AC	14.15	1	14.15	6.47	0.0384
BC	7.97	1	7.97	3.64	0.0980
A²	296.50	1	296.50	135.56	＜0.0001
B²	923.46	1	923.46	422.20	＜0.0001
C²	1166.17	1	1166.17	533.17	＜0.0001
残差	15.31	7	2.19
失拟残差	15.18	3	5.06	159.93	0.0001	不显著
纯误差	0.13	4	0.03
总和	4654.23	16

表 3. 响应面分析实验结果

Table 3. The experimental results of RSM analysis

图 7. 吸附剂用量与初始浓度对吸附率的交互作用

Figure 7. Interaction between adsorbent dosage and the initial concentration on the adsorption rate

图 8. 吸附剂用量与pH对吸附率的交互作用

Figure 8. Interaction between adsorbent dosage and pH on the adsorption rate

图 9. 初始浓度与pH对吸附率的交互作用

Figure 9. Interaction between the initial concentration and pH on the adsorption rate

图 10. ZIF-8对黄芩苷的吸附动力学曲线

Figure 10. Adsorption kinetics curve on baicalin by ZIF-8

q_e/(mg?g^－1)	准一级动力学参数			准二级动力学参数
q_e/(mg?g^－1)	k₁/min^－1	q_e/(mg?g^－1)	R²	K₂/(g?mg^－1?h^－1)	q_e/(mg?g^－1)	R²
21.54	0.79	20.63	0.9629	0.06	22.12	0.9965

表 4. ZIF-8吸附黄芩苷的动力学参数

Table 4. Kinetic parameters for adsorption of baicalin on ZIF-8

图 11. ZIF-8对黄芩苷的吸附动力学曲线

Figure 11. Adsorption kinetics curve on baicalin by ZIF-8

Langmuir			Freundich
q_m/(mg?g^－1)	K_L/(L?mg^－1)	R²	K_F	n	R²
469.02	0.05	0.9732	49.32	2.05	0.9688

表 5. ZIF-8吸附黄芩苷的等温线拟合参数

Table 5. Fitting parameters of adsorption isotherm for baicalin on ZIF-8

图 12. (a) 合成和回收的ZIF-8 XRD图谱.黄芩苷吸附前后ZIF-8的XPS光谱: (b)宽扫描光谱; (c)具有高分辨率的N 1s光谱; (d)具有高分辨率的Zn 2p光谱

Figure 12. (a) XRD patterns of the synthesized and reused ZIF-8. XPS spectra of ZIF-8 before and after baicalin adsorption: (b) Wide scan spectra; (c) N 1s spectra with high resolution; (d) Zn 2p spectra with high resolution

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