Preparation of Defective Ammonia-Fluorine Composite Functionalized UiO-66 and Its Artesunate Adsorption Properties

doi:10.16553/j.cnki.issn1000-985x.2024.0286

Abstract

Abstract: Artesunate， a sesquiterpenoid antimalarial drug derived from artemisinin， has attracted attentions of pharmaceutical scientists due to its specific effect on malaria parasites. However， the extraction process of artesunate is complex， requiring a large amount of organic solvents and high energy consumption. The easily modifiable and porous properties of metal-organic framework materials were used to construct a functionalized UiO-66 for the study of artesunate adsorption property. Amino and thiol groups were selected as hydrophilic and hydrophobic groups， and their influences on the adsorption properties for artesunate at different ratios were studied. Considering that the pore size of UiO-66 is smaller than that of artemether， a defect type functionalized zirconium based MOF was constructed by adding an appropriate amount of water molecules to enhance its pore size. The experimental results show that the adsorption capacity of fluorinated aminated UiO-66 is 10 mg/g higher than that of UiO-66 monomer. The defect fluorinated amination UiO-66 has increased adsorption capacity of 33.0 mg/g， demonstrating superior adsorption property. This experiment significantly improved the adsorption capacity and selectivity through the rational design and modification of materials， providing a potential industrial application solution for the purification and production of drugs such as artesunate.

Key words: MOF; UiO-66; defective ammonia-fluorine; artesunate; adsorption property

CLC Number:

O647.3

WANG Zihao, LIU Jiayu, DONG Zihao, WANG Yuxin, XU Yaxu, ZHU Yu. Preparation of Defective Ammonia-Fluorine Composite Functionalized UiO-66 and Its Artesunate Adsorption Properties[J]. Journal of Synthetic Crystals, 2025, 54(5): 890-897.

Figures/Tables 13

Fig.1 Structural formula of artesunate molecule

Table 1 Experimental reagents

名称	纯度	来源
ZrCl₄	AR	罗恩试剂
N，N-二甲基甲酰胺（DMF）	AR	国药集团化学试剂有限公司
2-氨基对二苯甲酸	AR	萨恩化学技术上海有限公司
2，3，5，6-四氟对苯二甲酸	AR	上海迈瑞尔生化科技有限公司
冰醋酸	AR	国药集团化学试剂有限公司
2，5-二巯基对苯二甲酸	AR	湖南华腾制药有限公司
无水甲醇	AR	国药集团化学试剂有限公司
青蒿琥酯	AR	麦克林生化科技有限公司
无水乙醇	AR	国药集团化学试剂有限公司

Table 2 Experimental instruments

仪器名称	型号	来源
数控超声波清洗器	KQ-600DB	昆山市超声波仪器公司
全波长紫外-可见分光光度计	UV-1200	上海美谱达仪器有限公司
恒温水浴振荡器	THZ-82	上海一恒科学仪器有限公司
分析天平	2011F146-11	塞多利斯科学仪器北京有限公司
高速台式离心机	TG16-WS	湖南湘仪实验仪器开发有限公司
红外光谱分析仪	Nicolet 6700	美国尼高力公司

Fig.2 XRD patterns of defective UiO-66 （n（-NH2）∶n（-F）=1∶20%）， UiO-66 （n（-NH2）∶n（-F）=1∶20%） and UiO-66

Fig.3 Infrared spectra of defective UiO-66 （n（-NH2）∶n（-F）=1∶20%） and UiO-66

Fig.4 SEM （a），（b） and TEM （c），（d） images of UiO-66（n（-NH2）∶n（-F）=1∶20%）， SEM （e），（f） images of defective UiO-66（n（-NH2）∶n（-F）=1∶20%）

Fig.5 XPS analysis of fluorine-based aminated UiO-66

Fig.6 Standard curve of artesunate solution

Fig.7 Adsorption of Aru by defective fluorine-based amination UiO-66

Fig.8 Quasi-primary and quasi-secondary curves of adsorption of artesunate by defective UiO-66（n（-NH2）∶n（-F）= 1∶20%

Fig.9 Isothermal adsorption lines of defective UiO-66（n（-NH2）∶n（-F）=1∶20%）

Table 3 Parameters of isothermal adsorption line for defective UiO-66（n（-NH2）∶n（-F）=1∶20%）

Isothermal equation	Parameter	Defective UiO-66（n（-NH₂）∶n（-F）=1∶20%）
	R²	0.959
Langmuir model	K/（L·mg^-1）	0.005
	q_m /（mg·g^-1）	145.616
	R²	0.943
Freundlich model	K/（L·mg^-1）	2.073
	n	0.654

Fig.10 XRD patterns of defective UiO-66 （n（-NH2）∶n（-F）=1∶20%） and adsorbed defective UiO-66 （n（-NH2）∶n（-F）=1∶20%）

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