异牡荆素是一种天然的碳苷黄酮类活性物质,具有抗癌、抗炎等多种药理活性,但是其有效成分的分离纯化是开发的难点和关键.因此,制备了MOF材料MOF-801,利用MOF材料上带有的—COOH基团,对其进行衍生化反应,使其表面带有C=C终端,然后与共聚单体(甲基丙烯酸月桂酯,LMA)、交联剂(乙二醇二甲基丙烯酸酯)、致孔剂(正己醇)和引发剂(偶氮二异丁腈)混合均匀后制备MOF-801/聚合物整体柱.通过扫描电子显微镜(SEM)、红外光谱(FT-IR)和氮气吸附-脱附等方法进行表征,结果显示,MOF-801和MOF-801/聚合物整体柱均已成功合成.将MOF-801/聚合物整体柱用作固相萃取(SPE)吸附剂,通过与高效液相色谱(HPLC)仪联用对中药中的抗癌活性成分异牡荆素进行在线富集纯化.结果显示,所制备的聚合物整体柱对异牡荆素具有较好的富集能力,并能去除中药中的部分杂质.
Isovitexin is a natural active substance of carboglycoside flavonoids, which has many pharmacological activities such as anti-cancer and anti-inflammation, but its content in medicinal plants is low, and the Chinese herbal medicine extract has some problems such as complex matrix. Therefore, it is necessary to establish a suitable method to enrich and purify isovitexin. In this paper, MOF material MOF-801 was first prepared, and the surface of MOF material was derivatized with —COOH group, so that it had a C=C terminal. Then, it was mixed with comonomer(methyl lauryl acrylate, LMA), cross-linking agent(ethylene glycol dimethacrylate), pore-forming agent(n-hexanol)and initiator(azodiisobutyronitrile)to prepare MOF-801/polymer monolithic column. Then, MOF-801 and MOF-801/ polymer monolithic column were characterized by scanning electron microscope(SEM), FT-IR and nitrogen adsorption-desorption method, which showed that the polymer monolithic column had been successfully synthesized. MOF-801/polymer monolithic column was used as solid-phase extraction(SPE)- DOI:10.3969/j.issn.1000-1565.2025.02.007MOF-801/聚合物整体柱的制备及对异牡荆素的固相萃取柳苹,刘海燕(河北大学 药学院,河北省公共卫生安全重点实验室,药物化学与分子诊断教育部重点实验室,河北 保定 071002)摘 要:异牡荆素是一种天然的碳苷黄酮类活性物质,具有抗癌、抗炎等多种药理活性,但是其有效成分的分离纯化是开发的难点和关键.因此,制备了MOF材料MOF-801,利用MOF材料上带有的—COOH基团,对其进行衍生化反应,使其表面带有C=C终端,然后与共聚单体(甲基丙烯酸月桂酯,LMA)、交联剂(乙二醇二甲基丙烯酸酯)、致孔剂(正己醇)和引发剂(偶氮二异丁腈)混合均匀后制备MOF-801/聚合物整体柱.通过扫描电子显微镜(SEM)、红外光谱(FT-IR)和氮气吸附-脱附等方法进行表征,结果显示,MOF-801和MOF-801/聚合物整体柱均已成功合成.将MOF-801/聚合物整体柱用作固相萃取(SPE)吸附剂,通过与高效液相色谱(HPLC)仪联用对中药中的抗癌活性成分异牡荆素进行在线富集纯化.结果显示,所制备的聚合物整体柱对异牡荆素具有较好的富集能力,并能去除中药中的部分杂质.关键词:聚合物整体柱;固相萃取(SPE);异牡荆素;MOF-801中图分类号:O658 文献标志码:A 文章编号:1000-1565(2025)02-0165-11Preparation of MOF-801/polymer monolithic column and solid phase extraction of isovitexinLIU Ping, LIU Haiyan(Key Laboratory of Medicinal Chemistry and Molecular Diagnosis Ministry of Education, Key Laboratory of Public Health Safety of Hebei Province, College of Pharmacy, Hebei University, Baoding 071002, China)Abstract: Isovitexin is a natural active substance of carboglycoside flavonoids, which has many pharmacological activities such as anti-cancer and anti-inflammation, but its content in medicinal plants is low, and the Chinese herbal medicine extract has some problems such as complex matrix. Therefore, it is necessary to establish a suitable method to enrich and purify isovitexin. In this paper, MOF material MOF-801 was first prepared, and the surface of MOF material was derivatized with —COOH group, so that it had a C=C terminal. Then, it was mixed with comonomer(methyl lauryl acrylate, LMA), cross-linking agent(ethylene glycol dimethacrylate), pore-forming agent(n-hexanol)and initiator(azodiisobutyronitrile)to prepare MOF-801/polymer monolithic column. Then, MOF-801 and MOF-801/ polymer monolithic column were characterized by scanning electron microscope(SEM), FT-IR and nitrogen adsorption-desorption method, which showed that the polymer monolithic column had been successfully synthesized. MOF-801/polymer monolithic column was used as solid-phase extraction(SPE)- 收稿日期:2024-05-29;修回日期:2024-11-06 基金项目:国家自然科学基金资助项目(21974034) 第一作者:柳苹(1998—),女,河北大学在读硕士研究生,主要从事分离材料制备方向研究.E-mail:2761787123@qq.com 通信作者:刘海燕(1971—),女,河北大学教授,博士,主要从事分离材料的制备及对天然产物中抗癌活性成分的富集纯化研究. E-mail:lhy1610@hbu.edu.cn 第2期柳苹等:MOF-801/聚合物整体柱的制备及对异牡荆素的固相萃取河北大学学报(自然科学版) 第45卷adsorbent, and the anticancer active ingredient isovitexin was enriched and purified online by combining with high performance liquid chromatography(HPLC). The results showed that the prepared polymer monolithic column has good ability to enrich isovitexin and remove impurities.
[1] TAO M F, LI R, XU T T, et al. Vitexin and isovitexin delayed ageing and enhanced stress-resistance through the activation of the SKN-1/Nrf2 signaling pathway [J]. Int J Food Sci Nutr, 2023, 74(6): 685-694. DOI: 10.1080/09637486.2023.2243055.
[2] HUANG Y S, LUO W, CHEN S Y, et al. Isovitexin alleviates hepatic fibrosis by regulating miR-21-mediated PI3K/Akt signaling and glutathione metabolic pathway: based on transcriptomics and metabolomics [J]. Phytomedicine, 2023, 121: 155117. DOI: 10.1016/J.PHYMED.2023.155117.
[3] 玄鸿雁,阚璇,朱振胜.异牡荆素调节miR-107/CCND1轴对胰腺癌细胞增殖、凋亡、迁移和侵袭的影响[J].现代肿瘤医学, 2023, 31(15): 2756-2764. DOI: 10.3969/j.issn.1672-4992.2023.15.002.
[4] 赵富周,丁成智,李晓明.异牡荆素对非小细胞性肺癌细胞自我更新和凋亡的影响[J].中国临床药理学杂志, 2022, 38(3): 219-223. DOI: 10.13699/j.cnki.1001-6821.2022.03.007.
[5] LIU M X, LI T, WANG W G, et al. Regulatory effect of isovitexin on MAPK/NF-κB signal in mice with acute ulcerative colitis [J]. J Asian Nat Prod Res, 2023, 25(8):765-782. DOI: 10.1080/10286020.2022.2142121.
[6] FERDAUSI N, ISLAM S, RIMTI F H, et al. Point-specific interactions of isovitexin with the neighboring amino acid residues of the hACE2 receptor as a targeted therapeutic agent in suppressing the SARS-CoV-2 influx mechanism [J]. J Adv Vet Anim Res, 2022, 9(2): 230-240. DOI: 10.5455/JAVAR.2022.I588.
[7] 贺丽苹,余雪婷,周铭林,等.一种从檀香叶中提取高纯牡荆素和异牡荆素的方法: 201811420926.0[P] , 2018-11-22.
[8] 黄瑀莘,韦锦斌,林兴,等.天胡荽黄酮苷类单体异牡荆素的制备方法及应用: 202110476459.9[P] , 2021-04-29
[9] CHE ZAIN M S, LEE S Y, TEO C Y, et al. Adsorption/desorption characteristics and simultaneous enrichment of orientin, isoorientin, vitexin and isovitexin from hydrolyzed oil palm leaf extract using macroporous resins[J]. Processes, 2021, 9(4): 659. DOI: 10.3390/pr9040659.
[10] ACHUTHA S, JOHNSON E, KUMARI NISHA S, et al. Antimicrobial biodegradable polymeric materials for food packaging applications: current status and future directions[J]. Mater Sci Forum, 2022, 1073: 49-56. DOI: 10.4028/p-a5my86.
[11] ARZHAKOVA О V, KOPNOV A Y, CHAPLYGIN D K, et al. Flame-retardant nanocomposite polymeric materials based on high-density polyethylene and aluminum hydroxide nanoparticles[J]. Russ J Gen Chem, 2022, 92(10): 1963-1971. DOI: 10.1134/S1070363222100103.
[12] ZHANG M Q. Self-healing polymeric materials: on a winding road to success[J]. Chin J Polym Sci, 2022, 40(11): 1315-1316. DOI: 10.1007/s10118-022-2870-6.
[13] ZHANG M M, LIU H Y, HAN Y M, et al. On-line enrichment and determination of aristolochic acid in medicinal plants using a MOF-based composite monolith as adsorbent[J]. J Chromatogr B Analyt Technol Biomed Life Sci, 2020, 1159: 122343. DOI: 10.1016/j.jchromb.2020.122343.
[14] TANG T F, LI X H, ZHU J Q, et al. Solid-phase microextraction with MIL-53(Al)-polymer monolithic column coupled to pressurized capillary electrochromatography for determination of chlorogenic acid and ferulic acid in sugarcane samples[J]. Anal Sci, 2023, 39(6): 925-933. DOI: 10.1007/s44211-023-00297-6.
[15] XUAN K, PU Y F, LI F, et al. Metal-organic frameworks MOF-808-X as highly efficient catalysts for direct synthesis of dimethyl carbonate from CO2 and methanol[J]. Chin J Catal, 2019, 40(4): 553-566. DOI: 10.1016/s1872-2067(19)63291-2.
[16] LI X T, ZHANG F, ZHANG M J, et al.Comparative study on the flame retardancy and retarding mechanism of rare earth(La, Ce, and Y)-based organic frameworks on epoxy resin[J]. ACS Omega, 2021, 6(51): 35548-35558. DOI:10.1021/ACSOMEGA.1C05088.
[17] LV Y Q, YU H T, XU P C, et al. Metal organic framework of MOF-5 with hierarchical nanopores as micro-gravimetric sensing material for aniline detection[J]. Sens Actuat B Chem, 2018, 256: 639-647. DOI: 10.1016/j.snb.2017.09.195.
[18] CHEN P, HE X H, PANG M B, et al. Iodine capture using Zr-based metal-organic frameworks(Zr-MOFs): adsorption performance and mechanism [J]. ACS Applied Materials Interfaces, 2020, 12(18): 20429-20439. DOI: 10.1021/acsami.0c02129.
[19] AN G H, ZHENG H M, GUO L S, et al. A metal-organic framework(MOF)built on surface-modified Cu nanoparticles eliminates tumors via multiple cascading synergistic therapeutic effects[J]. J Colloid Interface Sci, 2024, 662: 298-312. DOI: 10.1016/j.jcis.2024.02.055.
[20] ZHANG W J, WEI K, FAN L F, et al. Modification of carnation-like CuInS2 with Cu-MOF nanoparticles for efficient photocatalytic hydrogen production[J]. Int J Hydrog Energy, 2024, 59: 551-560. DOI: 10.1016/j.ijhydene.2024.01.342.
[21] MIRZAEI S, LOTFIKATOOLI L, AHMADPOUR A, et al. Enhancing energy carrier gas storage: novel MOF-decorated carbons with high affinity toward methane and hydrogen[J]. Chem Eng Res Des, 2024, 203: 419-430. DOI: 10.1016/j.cherd.2024.01.049.
[22] YANG Y G, ZHOU Z X, WANG T, et al. MOF-on-MOF heterostructure boosting AIE sensing and triggered structural collapse for histamine detection[J]. Talanta, 2024, 270: 125632. DOI: 10.1016/j.talanta.2024.125632.
[23] RIMI, KUMAR P, UTTAM B, et al. Highly efficient cauliflower-like palladium-loaded porous MOF as a robust material for the degradation of organic dyes[J]. ACS Omega, 2023, 8(42): 38895-38904. DOI: 10.1021/acsomega.3c03014.
[24] KEYPOUR H, KOUHDAREH J, RABIEI K, et al. Pd nanoparticles decorated on a porous Co(BDC-NH2)MOF as an effective heterogeneous catalyst for dye reduction[J]. Nanoscale Adv, 2023, 5(20): 5570-5579. DOI: 10.1039/D3NA00379E.
[25] GUHATHAKURTA S, ERDOGDU N U, HOFFMANN J J, et al. COX17 acetylation via MOF-KANSL complex promotes mitochondrial integrity and function[J]. Nat Metab, 2023, 5(11): 1931-1952. DOI: 10.1038/s42255-023-00904-w.
[26] XUE R J, ZHUGE Y N, LIU G L, et al. Flexible fabrication of a novel SiO2/AF/ZIF-L composite embedded with MOF structure and its thermal insulation properties[J]. Ceram Int, 2023, 49(22): 36619-36627. DOI: 10.1016/j.ceramint.2023.08.345.
[27] GRIFFITHS K, GREENFIELD J L, HALCOVITCH N R, et al. Systematic investigation into the photoswitching and thermal properties of arylazopyrazole-based MOF host-guest complexes[J]. Cryst Growth Des, 2023, 23(10): 7044-7052. DOI: 10.1021/acs.cgd.2c01384.
[28] YUAN N, TAN K Q, LI Q Y, et al. In situ synthesis of MIL-53-type eco-MOF from high-alumina fly ash for efficiently removing fluoride from water[J]. Prog Nat Sci Mater Int, 2023, 33(5): 681-690. DOI: 10.1016/j.pnsc.2023.12.005.
[29] 赵娟霞.ZrO2及Zr基MOFs材料CO2吸附性能研究[D].呼和浩特:内蒙古大学, 2021.
[30] 刘浩.MOF-801的合成设计及气体分离性能研究[D].宁波:中国科学院大学(中国科学院宁波材料技术与工程研究所), 2022. (
