A New Method for Enriching baicalin in Scutellaria baicalensis Georgi by Metal Organic Framework Material ZIF-8

doi:10.6023/A19080316

Abstract

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

Cite this article

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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Fig. & Tab. 17

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

Table 1. Codes and levels of RSM experiment

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

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

Figure 4. Effect of adsorbent dosage on adsorption rate

Figure 5. Effect of the initial concentration on adsorption rate

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

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

Table 3. The experimental results of RSM analysis

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

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

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

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

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

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

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

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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金属有机骨架材料ZIF-8富集黄芩中黄芩苷的新方法