CN117567533A - Zr-based metal organic framework material and application thereof in targeted capturing of honeysuckle active ingredients - Google Patents
Zr-based metal organic framework material and application thereof in targeted capturing of honeysuckle active ingredients Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 61
- 239000004480 active ingredient Substances 0.000 title claims abstract description 36
- 239000013096 zirconium-based metal-organic framework Substances 0.000 title claims abstract description 35
- 241000205585 Aquilegia canadensis Species 0.000 title claims abstract description 30
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003814 drug Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- CWVRJTMFETXNAD-FWCWNIRPSA-N 3-O-Caffeoylquinic acid Natural products O[C@H]1[C@@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-FWCWNIRPSA-N 0.000 claims abstract description 8
- PZIRUHCJZBGLDY-UHFFFAOYSA-N Caffeoylquinic acid Natural products CC(CCC(=O)C(C)C1C(=O)CC2C3CC(O)C4CC(O)CCC4(C)C3CCC12C)C(=O)O PZIRUHCJZBGLDY-UHFFFAOYSA-N 0.000 claims abstract description 8
- CWVRJTMFETXNAD-KLZCAUPSSA-N Neochlorogenin-saeure Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O CWVRJTMFETXNAD-KLZCAUPSSA-N 0.000 claims abstract description 8
- CWVRJTMFETXNAD-JUHZACGLSA-N chlorogenic acid Chemical compound O[C@@H]1[C@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-JUHZACGLSA-N 0.000 claims abstract description 8
- 229940074393 chlorogenic acid Drugs 0.000 claims abstract description 8
- FFQSDFBBSXGVKF-KHSQJDLVSA-N chlorogenic acid Natural products O[C@@H]1C[C@](O)(C[C@@H](CC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O FFQSDFBBSXGVKF-KHSQJDLVSA-N 0.000 claims abstract description 8
- 235000001368 chlorogenic acid Nutrition 0.000 claims abstract description 8
- BMRSEYFENKXDIS-KLZCAUPSSA-N cis-3-O-p-coumaroylquinic acid Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)cc2)[C@@H]1O)C(=O)O BMRSEYFENKXDIS-KLZCAUPSSA-N 0.000 claims abstract description 8
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 claims abstract description 8
- IQPNAANSBPBGFQ-UHFFFAOYSA-N luteolin Chemical compound C=1C(O)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(O)C(O)=C1 IQPNAANSBPBGFQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- LRDGATPGVJTWLJ-UHFFFAOYSA-N luteolin Natural products OC1=CC(O)=CC(C=2OC3=CC(O)=CC(O)=C3C(=O)C=2)=C1 LRDGATPGVJTWLJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000009498 luteolin Nutrition 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 40
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 34
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 23
- 239000000047 product Substances 0.000 claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 17
- 235000019253 formic acid Nutrition 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000000287 crude extract Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000007791 liquid phase Substances 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 241000628997 Flos Species 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000003795 desorption Methods 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 20
- 239000012621 metal-organic framework Substances 0.000 abstract description 17
- 239000003446 ligand Substances 0.000 abstract description 7
- 238000004458 analytical method Methods 0.000 abstract description 4
- 238000000605 extraction Methods 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000012876 carrier material Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000013558 reference substance Substances 0.000 description 15
- 238000000527 sonication Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 238000004729 solvothermal method Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000007970 homogeneous dispersion Substances 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
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- 239000002244 precipitate Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
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- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 229940126680 traditional chinese medicines Drugs 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 239000008176 lyophilized powder Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 230000008685 targeting Effects 0.000 description 3
- 239000001100 (2S)-5,7-dihydroxy-2-(3-hydroxy-4-methoxyphenyl)chroman-4-one Substances 0.000 description 2
- QUQPHWDTPGMPEX-UHFFFAOYSA-N Hesperidine Natural products C1=C(O)C(OC)=CC=C1C1OC2=CC(OC3C(C(O)C(O)C(COC4C(C(O)C(O)C(C)O4)O)O3)O)=CC(O)=C2C(=O)C1 QUQPHWDTPGMPEX-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QUQPHWDTPGMPEX-UTWYECKDSA-N aurantiamarin Natural products COc1ccc(cc1O)[C@H]1CC(=O)c2c(O)cc(O[C@@H]3O[C@H](CO[C@@H]4O[C@@H](C)[C@H](O)[C@@H](O)[C@H]4O)[C@@H](O)[C@H](O)[C@H]3O)cc2O1 QUQPHWDTPGMPEX-UTWYECKDSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- APSNPMVGBGZYAJ-GLOOOPAXSA-N clematine Natural products COc1cc(ccc1O)[C@@H]2CC(=O)c3c(O)cc(O[C@@H]4O[C@H](CO[C@H]5O[C@@H](C)[C@H](O)[C@@H](O)[C@H]5O)[C@@H](O)[C@H](O)[C@H]4O)cc3O2 APSNPMVGBGZYAJ-GLOOOPAXSA-N 0.000 description 2
- VUYDGVRIQRPHFX-UHFFFAOYSA-N hesperidin Natural products COc1cc(ccc1O)C2CC(=O)c3c(O)cc(OC4OC(COC5OC(O)C(O)C(O)C5O)C(O)C(O)C4O)cc3O2 VUYDGVRIQRPHFX-UHFFFAOYSA-N 0.000 description 2
- QUQPHWDTPGMPEX-QJBIFVCTSA-N hesperidin Chemical compound C1=C(O)C(OC)=CC=C1[C@H]1OC2=CC(O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@@H](CO[C@H]4[C@@H]([C@H](O)[C@@H](O)[C@H](C)O4)O)O3)O)=CC(O)=C2C(=O)C1 QUQPHWDTPGMPEX-QJBIFVCTSA-N 0.000 description 2
- 229940025878 hesperidin Drugs 0.000 description 2
- 239000002122 magnetic nanoparticle Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- ARGKVCXINMKCAZ-UHFFFAOYSA-N neohesperidine Natural products C1=C(O)C(OC)=CC=C1C1OC2=CC(OC3C(C(O)C(O)C(CO)O3)OC3C(C(O)C(O)C(C)O3)O)=CC(O)=C2C(=O)C1 ARGKVCXINMKCAZ-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000001042 affinity chromatography Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002539 nanocarrier Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H17/00—Compounds containing heterocyclic radicals directly attached to hetero atoms of saccharide radicals
- C07H17/04—Heterocyclic radicals containing only oxygen as ring hetero atoms
- C07H17/06—Benzopyran radicals
- C07H17/065—Benzo[b]pyrans
- C07H17/07—Benzo[b]pyran-4-ones
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application belongs to the technical field of traditional Chinese medicine extraction materials, and particularly relates to a Zr-based metal organic framework material and application thereof in targeted capturing of honeysuckle active ingredients. Zr is used as a metal node, trimesic acid is used as a ligand, a Zr-based metal organic framework material is prepared, other catalysts are not required to be added in the preparation process, the prepared metal organic framework material has a regular octahedral structure, the specific surface area is high, the porosity is good, and the catalyst can be used as a carrier material to be applied to the enrichment and capture process of active ingredients of traditional Chinese medicine components, and the active ingredients are subjected to targeted enrichment and analysis. The metal organic framework material prepared by the invention enriches one or more active ingredients of the honeysuckle including chlorogenic acid, luteolin and the like, and has high recovery rate.
Description
Technical Field
The application belongs to the technical field of traditional Chinese medicine extraction materials, and particularly relates to a Zr-based metal organic framework material and application thereof in targeted capturing of honeysuckle active ingredients.
Background
The traditional Chinese medicine has very complex components and very low content of most active components, which brings a lot of resistance to screening research of the active components of the traditional Chinese medicine. The traditional screening method of the active ingredients of the traditional Chinese medicine needs continuous separation and purification, which results in long time consumption, large workload and low efficiency in the whole process, and a plurality of active compounds and inactive compounds are separated together, and meanwhile, some trace potential active substances are easily lost and interfered by false positive results.
In order to develop a more convenient, time-saving and efficient strategy, various methods have been established, including bioaffinity chromatography, ultrafiltration, cell membrane affinity chromatography, ligand fishing, etc. Among these techniques, ligand fishing exhibits outstanding advantages due to high efficiency and good stability of immobilizing a target protein. For decades, different types of nanocarriers, such as gold nanoparticles, silica nanospheres, magnetic nanoparticles, and carbon nanotubes, have been used to screen potential ligands from traditional Chinese medicine extracts. However, the relative recovery of activity on conventional nanoparticles or magnetic nanoparticles is not significant.
Metal-organic frameworks (MOFs) are increasingly being used in a variety of applications including catalysis, gas storage and adsorptive separation due to their abundant active sites, uniform pore structures, ultra-large specific surface areas, and flexible and ordered framework structures. Chinese patent CN 115246936a discloses a preparation method of a molecular imprinting material of hesperidin based on MOFs, which has specific selectivity to hesperidin, high extraction efficiency, high purity, stable performance and multiple repeated use, and has multiple active coordination points and larger stokes shift by adopting rare earth yttrium (Y) as a ligand in the metal organic frameworks of MOFs, thereby improving the stability of the metal frameworks in water, enhancing the chemical stability and thermal stability of the metal frameworks, and prolonging the service life of the metal frameworks. However, there is no suitable MOFs for the capture of the active ingredients of honeysuckle.
Disclosure of Invention
Aiming at the problem that MOFs exist in capturing active ingredients of traditional Chinese medicines at the present stage, the application provides a Zr-based metal organic framework material which is simple in preparation method and has a good application effect in targeted capturing of active ingredients of honeysuckle.
The technology of the application is as follows:
application of Zr-based metal organic framework material in targeted capturing of active ingredients of traditional Chinese medicine honeysuckle; the active ingredients are chlorogenic acid and luteolin.
Further, the Zr-based metal organic framework material comprises the following raw materials in parts by weight: zirconium oxychloride, trimesic acid, hydrochloric acid, trifluoroacetic acid; the solvent is a mixed solution of N, N-dimethylformamide DMF and formic acid;
the volume ratio of DMF and formic acid in the solvent is 1:0.75-1;
and/or the mass ratio of the zirconium oxychloride to the trimesic acid is 1.1-1.7:1;
and/or the volume ratio of the hydrochloric acid to the trifluoroacetic acid is 0.5-0.75:1.
Further, the preparation method of the Zr-based metal organic framework material comprises the following steps:
(1) Adding zirconium oxychloride into a solvent, and then adding trimesic acid into the solvent to form a uniform dispersion;
(2) Adding hydrochloric acid and trifluoroacetic acid into the dispersion liquid in the step (1) for reaction; after the reaction is finished, centrifugally collecting a product;
(3) And (3) soaking and activating the product in the step (2) by using a mixed solution of DMF and ethanol or using DMF and ethanol, centrifuging, drying in vacuum, and grinding into uniform powder.
Further, the reaction conditions of step (2) are: reacting for 48-72 h at 110-130 ℃;
and/or, the soaking activation condition of the step (3) is as follows: and the time is 3-4 d, and the solvent is replaced for 6-8 times.
Further, the application specifically comprises the following steps:
s1, preparing a honeysuckle crude extract: extracting flos Lonicerae with water or alcohol to obtain the final product;
s2, active ingredient enrichment and capture: adding Zr-based metal organic framework material into the crude extract in the step S1, stirring, centrifuging, and filtering to obtain the active ingredient.
Preferably, the relation between the addition amounts of the honeysuckle dry flowers and the Zr-based metal organic framework material is as follows: 1mg of honeysuckle flower is added with 5-10 mg of Zr-based metal organic frame material.
Preferably, the specific process of step S2 is: stirring at room temperature for 2-5 h, centrifuging to remove supernatant, adding aqueous solution of formic acid into filter cake, performing ultrasonic treatment, centrifuging to obtain desorption liquid, and filtering with liquid phase filter membrane.
Preferably, the volume concentration of the formic acid aqueous solution is: 0.1-0.3%.
Zr is used as a metal node, and trimesic acid is used as a ligand to directly prepare the metal organic frame material. The preparation process does not need to add other catalysts, and the prepared metal organic framework material has a regular octahedron structure, high specific surface area and good porosity, and can be used as a carrier material for carrying out targeted enrichment and analysis on active ingredients in the enrichment and capture process of the active ingredients of the traditional Chinese medicine components.
The metal organic framework material prepared by the method is used as a carrier to be applied to targeted capturing, enriching and analyzing of active ingredients of traditional Chinese medicines, and honeysuckle is prepared into crude extract, and the obtained metal organic framework material is used for capturing and enriching. The honeysuckle contains one or more active ingredients such as chlorogenic acid, luteolin and the like, and the metal organic framework material prepared by the method enriches target compounds and then adopts a liquid chromatography technology for analysis.
1. The invention firstly adopts a solvothermal method to prepare the metal organic frame material, which retains the excellent characteristics of the metal organic frame material and has good hydrophilicity and stability.
2. The material is based on low-cost ligands and metal nodes, the preparation cost is relatively low, the subsequent preparation process is simple and efficient, the material has higher targeting enrichment efficiency on hydrophilic active ingredients, the recovery rate can reach 91.5%, and the material can be used as a carrier material for enriching the active ingredients of traditional Chinese medicines.
Drawings
FIG. 1 is a flow chart of the synthesis and application of the metal organic framework material of the present invention;
FIG. 2 is a scanning electron microscope image of the metal organic framework material prepared in example 1;
FIG. 3 is a liquid chromatogram of the standard solution (a) and the honeysuckle extract (b) used in example 1;
FIG. 4 is a chromatogram of the supernatant (a) and the desorption solution (b) of example 1 after the metal organic framework material has been reacted with the honeysuckle extract;
fig. 5 is a chromatogram of a desorption solution after repeating the action of the extraction solution multiple times for the metal organic framework material of example 1.
Detailed Description
For a better understanding of the present invention, the preparation and application of a Zr-based metal-organic framework material of the present invention will be described by way of specific examples.
Instrument: vacuum drying oven, DZF-6020 type, shanghai-Heng technology Co., ltd., china; CPA225D one ten thousandth electronic balance (cerdolischen instruments, germany); f7JA36578 clear ultrapure water system (merck milbo laboratory equipment limited); DD-5M medical centrifuge (Hunan trivial technologies Co., ltd.); 90-1 constant temperature magnetic stirrer (Shanghai Xie analytical instruments Co.); high performance liquid chromatograph, agilent 1206 series, U.S.;
reagent: zirconium oxychloride octahydrate (ZrOCl) 2 ·8H 2 O) and trimesic acid (1, 3, 5-BTC) carbofuran technologyCompany limited; heishun tablet (production lot number: 161001, a company of technology development of Fuchi Ji Zhong Ji Zhong Jiu, sichuan province); n, N-Dimethylformamide (DMF), li Anbo Long Hua (Tianjin) pharmaceutical chemistry limited; trifluoroacetic acid (TFA), micin technologies limited; absolute ethanol, acetonitrile, hydrochloric acid, a metallocene chemical reagent plant in Tianjin; distilled water was obtained from the Milli-Q system.
Example 1
A preparation method of a Zr-based metal organic framework material comprises the following steps:
(1) Preparing a mixed solution: zrOCl of 1.08 g is accurately weighed 2 ·8H 2 O was added to a mixture of 75 mL DMF and 75 mL formic acid, after 10 min of sonication, 0.41 g of 1,3,5-BTC was added, and after 10 min of sonication, 1 mL TFA and 0.5 mL of HCl were added to form a homogeneous dispersion.
(2) Preparation of Zr-based metal organic framework material: pouring the dispersion liquid 1 in the step (1) into an autoclave lined with 50 mL polytetrafluoroethylene by adopting a solvothermal method, and placing the autoclave in a drying oven to react at 130 ℃ for 72 h; after the reaction is finished, centrifugally collecting a product, soaking the product in a mixed solution of DMF and absolute ethyl alcohol with the volume ratio of 20 to mL of 1:1 for 3 days, centrifuging and replacing the solution for 6 times, wherein the dosage of each solution is 20 mL, then placing the product in a vacuum drying oven, drying at 150 ℃ for 12 h, cooling to room temperature, and grinding uniformly.
The application of the material in the enrichment of the active ingredients of the honeysuckle comprises the following steps:
s1, preparing a standard solution: and (3) taking a proper amount of chlorogenic acid and luteolin reference substances, precisely weighing, respectively adding methanol to dissolve and fix the volume, and preparing reference substance solutions with the concentration of 0.40 mg/mL and 0.26 mg/mL respectively. Respectively precisely sucking the single reference substance solutions, and diluting the single reference substance solutions according to a certain proportion to obtain mixed reference substance solutions. The above solution is preserved at 4deg.C in dark place for use.
S2, preparing a honeysuckle crude extract: weighing dried flos Lonicerae 200 g, pulverizing, sieving with 5,6 mesh sieve, soaking in 5 times of water for 30 min, ultrasonic extracting at 40deg.C for three times, each time for 30 min, filtering extractive solution, filtering medicinal liquid with 100 mesh sieve, and mixing filtrates. Finally obtaining the water decoction crude extract. After the mixture is cooled to room temperature, 20 mL water decoction is measured for freeze drying 24 h, and freeze-dried water decoction powder is obtained. Dissolving 1mg lyophilized powder in 10 mL methanol solution, and filtering with liquid phase filter membrane.
S3, active ingredient enrichment and capture: weighing dry Zr-based metal organic framework material 5 mg, adding into the crude extract of honeysuckle of 0.1 mg/mL in S2, performing ultrasonic treatment at 40 ℃ for 10 min, magnetically stirring at room temperature for 20 min, centrifuging at 2000 rpm for 5 min to obtain precipitate, adding 1% formic acid aqueous solution into the precipitate, performing ultrasonic treatment at 40 ℃ for 10 min, and repeating the centrifuging step to obtain supernatant, and filtering with a liquid phase filter membrane for later use.
S4, chromatographic detection: the chromatographic conditions were as follows: the mobile phase is acetonitrile (A)/0.4% phosphoric acid aqueous solution (B) (0-15 min 10:90, 15-30 min 10-20% A,90-80% B, v/v), the flow rate is 1.0 mL/min, the sample injection amount is 10 uL, the detection wavelength of an ultraviolet detector is 254 nm, the column temperature is 25 ℃, and C18 column (2.1 mm ×250 mm, 5 μm). The chromatographic separation results are shown in FIG. 3 and FIG. 4.
As can be seen from figures 3 and 4, the Zr-based metal organic framework material has high-efficiency targeting capture efficiency on chlorogenic acid and luteolin in honeysuckle, and the recovery rate can reach 82.6% -91.5%, compared with the traditional method for screening active ingredients of traditional Chinese medicines, the method is very convenient for conventional operation, and the targeting enrichment efficiency is greatly improved. The material prepared by the embodiment takes honeysuckle as an example to realize the targeted enrichment of active ingredients, and the RSD% of the material which is repeatedly used for many times is less than 5%. The Zr-based metal organic framework material can be used for separating active ingredients in traditional Chinese medicine components, and has good application prospect and potential in the field of traditional Chinese medicine analysis.
Example 2
A preparation method of a Zr-based metal organic framework material comprises the following steps:
(1) Preparing a mixed solution: zrOCl of 1.08 g is accurately weighed 2 ·8H 2 O was added to a mixture of 100mL DMF and 75. 75 mL formic acid, after 10 min of sonication, 0.54 g of 1,3,5-BTC was added, and after 10 min of sonication, 1 mL TFA and 0.75 mL of HCl were added to form a homogeneous dispersion.
(2) Preparation of Zr-based metal organic framework material: pouring the dispersion liquid 1 in the step (1) into an autoclave lined with 50 mL polytetrafluoroethylene by adopting a solvothermal method, and placing the autoclave in a drying oven to react at 110 ℃ for 72 h; after the reaction is finished, centrifugally collecting a product, soaking the product in a mixed solution of DMF and absolute ethyl alcohol with the volume ratio of 20 to mL of 1:1 for 3 days, centrifuging and replacing the solution for 6 times, wherein the dosage of each solution is 20 mL, then placing the product in a vacuum drying oven, drying at 150 ℃ for 12 h, cooling to room temperature, and grinding uniformly.
The application of the material in the enrichment of the active ingredients of the honeysuckle comprises the following steps:
s1, preparing a standard solution: and (3) taking a proper amount of chlorogenic acid and luteolin reference substances, precisely weighing, respectively adding methanol to dissolve and fix the volume, and preparing reference substance solutions with the concentration of 0.40 mg/mL and 0.26 mg/mL respectively. Respectively precisely sucking the single reference substance solutions, and diluting the single reference substance solutions according to a certain proportion to obtain mixed reference substance solutions. The above solution is preserved at 4deg.C in dark place for use.
S2, preparing a honeysuckle crude extract: weighing dried flos Lonicerae 200 g, pulverizing, sieving with 5,6 mesh sieve, soaking in 5 times of water for 30 min, ultrasonic extracting at 40deg.C for three times, each time for 30 min, filtering extractive solution, filtering medicinal liquid with 100 mesh sieve, and mixing filtrates. Finally obtaining the water decoction crude extract. After the mixture is cooled to room temperature, 20 mL water decoction is measured for freeze drying 24 h, and freeze-dried water decoction powder is obtained. Dissolving 1mg lyophilized powder in 10 mL methanol solution, and filtering with liquid phase filter membrane.
S3, active ingredient enrichment and capture: weighing dry Zr-based metal organic framework material 10 mg, adding into the crude extract of honeysuckle of 0.1 mg/mL in S2, performing ultrasonic treatment at 40 ℃ for 10 min, magnetically stirring at room temperature for 20 min, centrifuging at 2000 rpm for 5 min to obtain precipitate, adding 1% formic acid aqueous solution into the precipitate, performing ultrasonic treatment at 40 ℃ for 10 min, and repeating the centrifuging step to obtain supernatant, and filtering with a liquid phase filter membrane for later use.
S4, chromatographic detection: as in example 1.
Example 3
A preparation method of a Zr-based metal organic framework material comprises the following steps:
(1) Preparing a mixed solution: zrOCl of 1.08 g is accurately weighed 2 ·8H 2 O was added to a mixture of 75 mL DMF and 75 mL formic acid, after 10 min of sonication, 0.36 g of 1,3,5-BTC was added, and after 10 min of sonication, 1 mL TFA and 0.5 mL of HCl were added to form a homogeneous dispersion.
(2) Preparation of Zr-based metal organic framework material: pouring the dispersion liquid 1 in the step (1) into an autoclave lined with 50 mL polytetrafluoroethylene by adopting a solvothermal method, and placing the autoclave in a drying oven to react at 110 ℃ for 72 h; after the reaction, the product was collected by centrifugation, the product was immersed in 20 mL of DMF solution for 3 days, during which the solution was centrifuged and replaced 6 times, each time the solution was 20 mL, and then the product was immersed in 20 mL absolute ethanol for 3 days, during which the solution was centrifuged and replaced 6 times, each time the solution was 20 mL, and then the product was dried at 150 ℃ in a vacuum oven for 12 h, cooled to room temperature and then ground uniformly.
The application of the material in the enrichment of the active ingredients of the honeysuckle comprises the following steps:
s1, preparing a standard solution: and (3) taking a proper amount of chlorogenic acid and luteolin reference substances, precisely weighing, respectively adding methanol to dissolve and fix the volume, and preparing reference substance solutions with the concentration of 0.40 mg/mL and 0.26 mg/mL respectively. Respectively precisely sucking the single reference substance solutions, and diluting the single reference substance solutions according to a certain proportion to obtain mixed reference substance solutions. The above solution is preserved at 4deg.C in dark place for use.
S2, preparing a honeysuckle crude extract: weighing dried flos Lonicerae 200 g, pulverizing, sieving with 5,6 mesh sieve, soaking in 5 times of water for 30 min, ultrasonic extracting at 40deg.C for three times, each time for 30 min, filtering extractive solution, filtering medicinal liquid with 100 mesh sieve, and mixing filtrates. Finally obtaining the water decoction crude extract. After the mixture is cooled to room temperature, 20 mL water decoction is measured for freeze drying 24 h, and freeze-dried water decoction powder is obtained. Dissolving 1mg lyophilized powder in 10 mL methanol solution, and filtering with liquid phase filter membrane.
S3, active ingredient enrichment and capture: weighing 8mg of dry Zr-based metal organic framework material, adding into 0.1 mg/mL of honeysuckle crude extract in S2, performing ultrasonic treatment at 40 ℃ for 10 min, performing magnetic stirring at room temperature for 20 min, centrifuging at 2000 rpm for 5 min to obtain precipitate, adding 1% formic acid aqueous solution into the precipitate, performing ultrasonic treatment at 40 ℃ for 10 min, and repeating the centrifugation step to obtain supernatant, and filtering with a liquid phase filter membrane for later use.
S4, chromatographic detection: as in example 1.
Comparative example 1 (without hydrochloric acid and TFA)
A preparation method of a Zr-based metal organic framework material comprises the following steps:
(1) Preparing a mixed solution: zrOCl of 1.08 g is accurately weighed 2 ·8H 2 O was added to a mixture of 75 mL DMF and 75 mL formic acid, and after 10 min of sonication, 0.36 g of 1,3,5-BTC was added and after 10 min of sonication a homogeneous dispersion was formed.
(2) Preparation of Zr-based metal organic framework material: pouring the dispersion liquid 1 in the step (1) into an autoclave lined with 50 mL polytetrafluoroethylene by adopting a solvothermal method, and placing the autoclave in a drying oven to react at 110 ℃ for 72 h; after the reaction is finished, centrifugally collecting a product, soaking the product in a mixed solution of DMF and absolute ethyl alcohol with the volume ratio of 20 to mL of 1:1 for 3 days, centrifuging and replacing the solution for 6 times, wherein the dosage of each solution is 20 mL, then placing the product in a vacuum drying oven, drying at 150 ℃ for 12 h, cooling to room temperature, and grinding uniformly.
The procedure is as in example 1.
The yield of the resultant Zr-based metal-organic framework material without TFA and HCl was reduced by about 9% compared to example 1, and the morphology edges of the octahedron were blurred and the dimensional uniformity was poor.
Comparative example 2 case where only hydrochloric acid was added
A preparation method of a Zr-based metal organic framework material comprises the following steps:
(1) Preparing a mixed solution: zrOCl of 1.08 g is accurately weighed 2 ·8H 2 O was added to a mixture of 75 mL DMF and 75 mL formic acid, after 10 min of sonication, 0.41 g of 1,3,5-BTC was added, and after 10 min of sonication, 1.5 mL of HCl was added to form a homogeneous dispersion.
(2) Preparation of Zr-based metal organic framework material: pouring the dispersion liquid 1 in the step (1) into an autoclave lined with 50 mL polytetrafluoroethylene by adopting a solvothermal method, and placing the autoclave in a drying oven to react at 130 ℃ for 72 h; after the reaction is finished, centrifugally collecting a product, soaking the product in a mixed solution of DMF and absolute ethyl alcohol with the volume ratio of 20 to mL of 1:1 for 3 days, centrifuging and replacing the solution for 6 times, wherein the dosage of each solution is 20 mL, then placing the product in a vacuum drying oven, drying at 150 ℃ for 12 h, cooling to room temperature, and grinding uniformly.
The procedure is as in example 1.
Comparative example 3 addition of trifluoroacetic acid alone
A preparation method of a Zr-based metal organic framework material comprises the following steps:
(1) Preparing a mixed solution: zrOCl of 1.08 g is accurately weighed 2 ·8H 2 O was added to a mixture of 75 mL DMF and 75 mL formic acid, and after 10 min of sonication, 0.41 g of 1,3,5-BTC was added, and after 10 min of sonication, 1.5 mL TFA was added to form a homogeneous dispersion.
(2) Preparation of Zr-based metal organic framework material: pouring the dispersion liquid 1 in the step (1) into an autoclave lined with 50 mL polytetrafluoroethylene by adopting a solvothermal method, and placing the autoclave in a drying oven to react at 130 ℃ for 72 h; after the reaction is finished, centrifugally collecting a product, soaking the product in a mixed solution of DMF and absolute ethyl alcohol with the volume ratio of 20 to mL of 1:1 for 3 days, centrifuging and replacing the solution for 6 times, wherein the dosage of each solution is 20 mL, then placing the product in a vacuum drying oven, drying at 150 ℃ for 12 h, cooling to room temperature, and grinding uniformly.
The procedure is as in example 1.
Effect of the invention
The active ingredients extracted in examples 1 to 3 and comparative examples 1 to 3 were compared, and the results are shown in Table 1.
TABLE 1 comparison of the effects of the active ingredients extracted from examples 1-3 and comparative examples 1-3
Claims (7)
1. Application of Zr-based metal organic framework material in targeted capturing of active ingredients of traditional Chinese medicine honeysuckle; the active ingredient is chlorogenic acid and luteolin;
the Zr-based metal organic framework material comprises the following raw materials in parts by weight: zirconium oxychloride, trimesic acid, hydrochloric acid, trifluoroacetic acid;
the solvent is a mixed solution of N, N-dimethylformamide DMF and formic acid;
the volume ratio of DMF and formic acid in the solvent is 1:0.75-1;
the mass ratio of the zirconium oxychloride to the trimesic acid is 1.1-1.7:1;
the volume ratio of the hydrochloric acid to the trifluoroacetic acid is 0.5-0.75:1.
2. The use according to claim 1, wherein the method for preparing the Zr-based metal organic framework material comprises the steps of:
(1) Adding zirconium oxychloride into a solvent, and then adding trimesic acid into the solvent to form a uniform dispersion;
(2) Adding hydrochloric acid and trifluoroacetic acid into the dispersion liquid in the step (1) for reaction; after the reaction is finished, centrifugally collecting a product;
(3) And (3) soaking and activating the product in the step (2) by using a mixed solution of DMF and ethanol or using DMF and ethanol, centrifuging, drying in vacuum, and grinding into uniform powder.
3. The use according to claim 2, wherein the reaction conditions of step (2) are: reacting for 48-72 h at 110-130 ℃;
and/or, the soaking activation condition of the step (3) is as follows: and the time is 3-4 d, and the solvent is replaced for 6-8 times.
4. A use according to any one of claims 1-3, characterized in that it comprises in particular the following steps:
s1, preparing a honeysuckle crude extract: extracting flos Lonicerae with water or alcohol to obtain the final product;
s2, active ingredient enrichment and capture: adding Zr-based metal organic framework material into the crude extract in the step S1, stirring, centrifuging, and filtering to obtain the active ingredient.
5. The use according to claim 4, wherein the dry honeysuckle and the Zr-based metal organic framework material are added in the following amount: 1mg of honeysuckle flower is added with 5-10 mg of Zr-based metal organic frame material.
6. The application according to claim 4, wherein the specific process of step S2 is: stirring at room temperature for 2-5 h, centrifuging to remove supernatant, adding aqueous solution of formic acid into filter cake, performing ultrasonic treatment, centrifuging to obtain desorption liquid, and filtering with liquid phase filter membrane.
7. The use according to claim 6, wherein the aqueous formic acid solution has a volume concentration of: 0.1-0.3%.
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| CN113121352A (en) * | 2021-04-25 | 2021-07-16 | 李辉 | Method for separating and purifying chlorogenic acid by using novel composite imprinted polymer |
| CN113945613A (en) * | 2021-08-30 | 2022-01-18 | 山东理工大学 | Preparation method and application of novel electrochemical sensor for detecting chlorogenic acid |
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| CN108864021A (en) * | 2017-10-13 | 2018-11-23 | 昌邑市银江生物科技有限公司 | A method of high-purity luteolin is prepared using zinc salt |
| CN108373413A (en) * | 2018-05-14 | 2018-08-07 | 肖锦 | A method of the chlorogenic acid extracting from Cortex Eucommiae |
| CN108484401A (en) * | 2018-05-14 | 2018-09-04 | 肖锦 | A kind of technique of the chlorogenic acid extracting from new fresh honeysuckle |
| CN113121352A (en) * | 2021-04-25 | 2021-07-16 | 李辉 | Method for separating and purifying chlorogenic acid by using novel composite imprinted polymer |
| CN113945613A (en) * | 2021-08-30 | 2022-01-18 | 山东理工大学 | Preparation method and application of novel electrochemical sensor for detecting chlorogenic acid |
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