CN112341578A - Molecularly imprinted polymer coated porous silica gel chromatographic packing and preparation method thereof - Google Patents
Molecularly imprinted polymer coated porous silica gel chromatographic packing and preparation method thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000000741 silica gel Substances 0.000 title claims abstract description 74
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 74
- 238000012856 packing Methods 0.000 title claims abstract description 42
- 229920000344 molecularly imprinted polymer Polymers 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004005 microsphere Substances 0.000 claims abstract description 30
- 238000005406 washing Methods 0.000 claims abstract description 29
- PWAOOJDMFUQOKB-WCZZMFLVSA-N ginsenoside Re Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1O[C@H]1[C@H](O[C@@H]2[C@H]3C(C)(C)[C@@H](O)CC[C@]3(C)[C@@H]3[C@@]([C@@]4(CC[C@@H]([C@H]4[C@H](O)C3)[C@](C)(CCC=C(C)C)O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O3)O)C)(C)C2)O[C@H](CO)[C@@H](O)[C@@H]1O PWAOOJDMFUQOKB-WCZZMFLVSA-N 0.000 claims abstract description 28
- AOGZLQUEBLOQCI-UHFFFAOYSA-N ginsenoside-Re Natural products CC1OC(OCC2OC(OC3CC4(C)C(CC(O)C5C(CCC45C)C(C)(CCC=C(C)C)OC6OC(CO)C(O)C(O)C6O)C7(C)CCC(O)C(C)(C)C37)C(O)C(O)C2O)C(O)C(O)C1O AOGZLQUEBLOQCI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 239000003929 acidic solution Substances 0.000 claims abstract description 7
- 238000002444 silanisation Methods 0.000 claims abstract description 7
- 239000006228 supernatant Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000010898 silica gel chromatography Methods 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 description 23
- 229940089161 ginsenoside Drugs 0.000 description 16
- 229930182494 ginsenoside Natural products 0.000 description 16
- 239000000945 filler Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 238000013375 chromatographic separation Methods 0.000 description 8
- 238000004811 liquid chromatography Methods 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 propenyl modified silica gel Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000000144 pharmacologic effect Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000006884 silylation reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- FBFMBWCLBGQEBU-GYMUUCMZSA-N 20-gluco-ginsenoside-Rf Natural products O([C@](CC/C=C(\C)/C)(C)[C@@H]1[C@H]2[C@H](O)C[C@H]3[C@](C)([C@]2(C)CC1)C[C@H](O[C@@H]1[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O2)[C@@H](O)[C@H](O)[C@@H](CO)O1)[C@H]1C(C)(C)[C@@H](O)CC[C@]31C)[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 FBFMBWCLBGQEBU-GYMUUCMZSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- LLPWNQMSUYAGQI-QBQUQATFSA-N Ginsenoside R1 Natural products O([C@](CC/C=C(\C)/C)(C)[C@@H]1[C@H]2[C@@H](O)C[C@H]3[C@](C)([C@]2(C)CC1)C[C@H](O[C@@H]1[C@H](O[C@@H]2[C@@H](O)[C@@H](O)[C@@H](O)CO2)[C@@H](O)[C@H](O)[C@@H](CO)O1)[C@H]1C(C)(C)[C@@H](O)CC[C@]31C)[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O1 LLPWNQMSUYAGQI-QBQUQATFSA-N 0.000 description 1
- UFNDONGOJKNAES-UHFFFAOYSA-N Ginsenoside Rb1 Natural products CC(=CCCC(C)(OC1OC(COC2OC(CO)C(O)C(O)C2O)C(O)C(O)C1O)C3CCC4(C)C3C(O)CC5C6(C)CCC(OC7OC(CO)C(O)C(O)C7OC8OC(CO)C(O)C(O)C8O)C(C)(C)C6CC(O)C45C)C UFNDONGOJKNAES-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 206010063837 Reperfusion injury Diseases 0.000 description 1
- YURJSTAIMNSZAE-UHFFFAOYSA-N UNPD89172 Natural products C1CC(C2(CC(C3C(C)(C)C(O)CCC3(C)C2CC2O)OC3C(C(O)C(O)C(CO)O3)O)C)(C)C2C1C(C)(CCC=C(C)C)OC1OC(CO)C(O)C(O)C1O YURJSTAIMNSZAE-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- DDNRNCSGIYDEMC-UHFFFAOYSA-N ethanol;formic acid Chemical compound CCO.OC=O DDNRNCSGIYDEMC-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- GZYPWOGIYAIIPV-JBDTYSNRSA-N ginsenoside Rb1 Chemical compound C([C@H]1O[C@H]([C@@H]([C@@H](O)[C@@H]1O)O)O[C@@](C)(CCC=C(C)C)[C@@H]1[C@@H]2[C@@]([C@@]3(CC[C@H]4C(C)(C)[C@@H](O[C@H]5[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O5)O[C@H]5[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O5)O)CC[C@]4(C)[C@H]3C[C@H]2O)C)(C)CC1)O[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O GZYPWOGIYAIIPV-JBDTYSNRSA-N 0.000 description 1
- TXEWRVNOAJOINC-UHFFFAOYSA-N ginsenoside Rb2 Natural products CC(=CCCC(OC1OC(COC2OCC(O)C(O)C2O)C(O)C(O)C1O)C3CCC4(C)C3C(O)CC5C6(C)CCC(OC7OC(CO)C(O)C(O)C7OC8OC(CO)C(O)C(O)C8O)C(C)(C)C6CCC45C)C TXEWRVNOAJOINC-UHFFFAOYSA-N 0.000 description 1
- YURJSTAIMNSZAE-HHNZYBFYSA-N ginsenoside Rg1 Chemical compound O([C@@](C)(CCC=C(C)C)[C@@H]1[C@@H]2[C@@]([C@@]3(C[C@@H]([C@H]4C(C)(C)[C@@H](O)CC[C@]4(C)[C@H]3C[C@H]2O)O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)C)(C)CC1)[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O YURJSTAIMNSZAE-HHNZYBFYSA-N 0.000 description 1
- CBEHEBUBNAGGKC-UHFFFAOYSA-N ginsenoside Rg1 Natural products CC(=CCCC(C)(OC1OC(CO)C(O)C(O)C1O)C2CCC3(C)C2C(O)CC4C5(C)CCC(O)C(C)(C)C5CC(OC6OC(CO)C(O)C(O)C6O)C34C)C CBEHEBUBNAGGKC-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 208000031225 myocardial ischemia Diseases 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- LLPWNQMSUYAGQI-UHFFFAOYSA-N notoginsenoside r1 Chemical compound C1CC(C2(CC(C3C(C)(C)C(O)CCC3(C)C2CC2O)OC3C(C(O)C(O)C(CO)O3)OC3C(C(O)C(O)CO3)O)C)(C)C2C1C(C)(CCC=C(C)C)OC1OC(CO)C(O)C(O)C1O LLPWNQMSUYAGQI-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- 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
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
- B01J20/285—Porous sorbents based on 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
- B01J20/3057—Use of a templating or imprinting material ; filling pores of a substrate or matrix followed by the removal of the substrate or matrix
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a molecularly imprinted polymer coated porous silica gel chromatographic packing and a preparation method thereof. The preparation method comprises the following steps: mixing a functional monomer, a reaction solvent 1 and a template molecule, and standing to obtain a prepolymerization system; stirring an allyl silanization reagent, a reaction solvent 2, a catalyst and porous silica gel microspheres activated by an acidic solution at a certain temperature, and washing to obtain allyl modified porous silica gel microspheres; adding an initiator, a cross-linking agent and an allyl modified porous silica gel microsphere into the prepolymer system, heating by a program, reacting for a period of time, and washing the obtained material until the eluted supernatant is detected by an ultraviolet spectrophotometer to obtain template-free molecules; and washing for 2-8 times to obtain the chromatographic packing. The invention takes porous silica gel microspheres as a carrier to obtain the ginsenoside Re molecularly imprinted polymer coated porous silica gel chromatographic packing with high specific surface area, uniform particle size and pore size distribution and good stability.
Description
Technical Field
The invention relates to a molecularly imprinted polymer coated porous silica gel chromatographic packing and a preparation method thereof.
Background
The porous silica gel matrix has high specific surface area (up to hundreds of square meters per gram) and narrow pore size distribution (capable of being intensively distributed at dozens of nanometers), and has wide application in sample pretreatment and chromatographic separation. The molecularly imprinted polymer has specific recognition performance, is beneficial to selectively recognizing compounds with extremely similar molecular structures, but has great difficulty in preparing molecularly imprinted polymer microspheres with narrow pore structure distribution range, uniform particle size and good appearance. The surface imprinting technology can combine the good physical and chemical properties of the porous silica gel microspheres with the good selectivity of the molecularly imprinted polymer to prepare the molecularly imprinted polymer-coated porous silica gel chromatographic packing with good performance. Because the ginsenoside compounds belong to strong polar compounds with extremely similar chemical structures, effective separation and purification of the ginsenoside compounds are difficult to realize by the existing sample pretreatment materials and chromatographic separation materials, and therefore, the development of the novel ginsenoside Re molecularly imprinted polymer coated porous silica gel chromatographic packing for realizing the effective separation of the compounds has important economic benefit and social significance.
Ginsenoside compounds are important effective components of ginseng plants, at present, the number of the ginsenoside compounds is up to 620 or more, the ginsenoside compounds have pharmacological activities of resisting cancer, resisting myocardial ischemia-reperfusion injury, diminishing inflammation, resisting aging and the like, and the ginsenoside compounds with different chemical structures have different pharmacological activities. At present, the high performance liquid chromatography is most commonly used in the separation and analysis of ginsenoside compounds, a chromatographic column is known as the heart of a chromatographic separation system, and chromatographic packing is a key material of the chromatographic column and is the key for realizing high-efficiency separation. Because the ginsenoside compounds belong to strong polar compounds with similar chemical structures, the effective separation of the compounds is difficult to realize by the existing liquid chromatography packing, so that the development of a novel liquid chromatography separation material for realizing the effective separation of the compounds has important economic benefits and social significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a molecularly imprinted polymer coated porous silica gel chromatographic packing and a preparation method thereof. The chromatographic packing prepared by the method has the advantages of high specific surface area, uniform particle size and pore size distribution and good stability.
The invention provides a preparation method of a molecularly imprinted polymer coated porous silica gel chromatographic packing, which comprises the following steps:
(1) mixing the functional monomer, the reaction solvent 1 and the template molecule at a certain temperature, and standing for 6-24 hours to obtain a prepolymerization system;
(2) stirring an allyl silanization reagent, a reaction solvent 2, a catalyst and porous silica gel microspheres activated by an acidic solution at a certain temperature for 5-48 h, and washing to obtain allyl modified porous silica gel microspheres;
(3) adding an initiator, a cross-linking agent and the propenyl modified porous silica gel microspheres obtained in the step (2) into the prepolymerization system in the step (1), heating by a program, reacting for a period of time, and washing the obtained material until the eluted supernatant is detected by an ultraviolet spectrophotometer to obtain template-free molecules; and washing for 2-8 times to obtain the molecular imprinting polymer-coated porous silica gel chromatographic packing.
Further, the specific process of the porous silica gel microspheres activated by the acidic solution in the step (2) is as follows: preparing a nitric acid and hydrochloric acid or a mixed aqueous solution of the nitric acid and the hydrochloric acid, adding porous silica gel microspheres with the particle size of 1-100 micrometers and the pore diameter of 1-100 nanometers, stirring for a period of time at a certain temperature, washing with water to be neutral, washing with absolute ethyl alcohol for 2-5 times, and drying in vacuum for later use.
Further, the reaction solvent 1 in the step (1) is at least one of methanol and acetonitrile; the reaction solvent 2 in the step (2) is at least one of anhydrous toluene, acetonitrile, ethanol or methanol.
Further, the functional monomer in the step (1) is at least one of methacrylic acid, acrylamide, methyl methacrylate, hydroxyethyl methacrylate and 4-vinylpyridine.
Further, the temperature program in the step (3) is 20-60% oCKeeping for 2-24 h, then 50-120oAnd C, keeping for 2-48 h.
Further, in the step (1), the template molecule is ginsenoside Re molecule, and the concentration of the template molecule is 0.001-3 mol/L.
Further, the mass ratio of the functional monomer, the reaction solvent 1 and the template molecule in the step (1) is 1:20 to 1: 1; the ratio of the propenyl silanization reagent, the reaction solvent 2, the catalyst and the porous silica gel microspheres activated by the acidic solution in the step (2) is 0.1 mL to 1 μ L to 0.1 g to 10 mL to 100 μ L to 20 g.
Further, the addition amount of the initiator, the cross-linking agent and the propenyl modified porous silica gel microspheres obtained in the step (2) in the step (3) is between 1 mg to 10 μ L to 1 g and 1000 mg to 1000 μ L to 10 g.
The invention also provides a molecularly imprinted polymer coated porous silica gel chromatographic packing prepared by the preparation method.
Furthermore, the mass fraction of the C element in the chromatographic packing is 1-30%, and the specific surface area of the chromatographic packing is 60 m2/g ~ 650 m2/g。
Has the advantages that: the invention takes porous silica gel microspheres as a carrier to obtain the ginsenoside Re molecularly imprinted polymer coated porous silica gel chromatographic packing with high specific surface area, uniform particle size and pore size distribution and good stability. The obtained ginsenoside Re molecularly imprinted polymer coated porous silica gel chromatographic packing has specific recognition performance on ginsenoside compounds, has strong mechanical stability, controls the thickness of a molecularly imprinted polymer coating by controlling factors such as temperature, reagent types, concentration and the like in the reaction process, and has wide application prospect in the fields of chromatographic packing and solid-phase extraction materials.
Drawings
FIG. 1 is the scanning electron microscope image of the commercial bare silica gel (A) and the obtained ginsenoside Re molecularly imprinted polymer coated porous silica gel chromatographic filler (B) in example 1.
FIG. 2 is an infrared spectrum of a commercial bare silica gel (a) and a obtained ginsenoside Re molecularly imprinted polymer-coated porous silica gel chromatographic filler (b) in example 3.
Fig. 3 is a chromatographic separation chart of a sample mixture of four ginsenoside compounds in example 4, wherein reference numeral 1 is ginsenoside R1, reference numeral 2 is ginsenoside Rb1, reference numeral 3 is ginsenoside Rg1, and reference numeral 4 is ginsenoside Re, and the porous silica gel liquid chromatography packing is coated with ginsenoside Re molecularly imprinted polymer.
FIG. 4 is a flow chart of the synthesis process of ginsenoside Re molecularly imprinted polymer coated porous silicon.
Detailed Description
Example 1
A preparation method of ginsenoside Re molecularly imprinted polymer coated porous silica gel chromatographic packing comprises the following steps:
acid solution activated silica gel: preparing 20 mL of mixed solution of 10 mol/L nitric acid and 10 mol/L hydrochloric acid, adding 2 g of porous silica gel microspheres (particle size 5 μm, pore size 12 nm, purchased from Nami, Suzhou) at 50%oAnd C, stirring for 2 hours under the condition of C, washing to be neutral, washing for 3 times by using absolute ethyl alcohol, and drying in vacuum for later use.
Introduction of double bonds: selecting 25 mL of anhydrous toluene as a reaction solvent, adding1 mL propenyl silylation reagent KH-570 was added, 20. mu.L triethylamine catalyst was added, and the mixture was stirred at 4 deg.CoAnd C, stirring for 10 hours, washing the propenyl modified porous silica gel microspheres by sequentially adopting methylbenzene and methanol, and drying for later use.
Pre-polymerization: using methacrylic acid as a monomer and methanol as a reaction solvent, controlling the concentration of the template molecule ginsenoside Re at 1 mol/L, and standing for 10 hours under a certain temperature condition to obtain a prepolymerization system.
Preparing a ginsenoside Re molecularly imprinted polymer coated porous silica gel chromatographic filler: adding 30 mg of initiator azobisisobutyronitrile, 200 mu L of ethylene glycol dimethacrylate crosslinking agent and 1 g of propenyl modified silica gel into the prepolymerization system, and adopting the temperature programming process of 40 oCKeeping for 6 h, 90 oCThe reaction is kept for 18 h. Washing the obtained material by adopting a formic acid-ethanol mixed solvent with the ratio of 1:20 until the eluted supernatant is detected by an ultraviolet spectrophotometer to have no Re template molecule; washing the obtained material with ethanol for 2 times at 60 oCVacuum drying for 9 h under the condition for later use.
As shown in FIG. 1, FIG. 1 is a scanning electron microscope image of commercial bare silica gel (A) and obtained ginsenoside Re molecularly imprinted polymer-coated porous silica gel chromatographic filler (B) in example 1. As can be seen from FIG. 1, the silica gel before and after modification is still uniform spherical, and no massive particle deposition occurs, which is beneficial to the subsequent chromatographic separation process.
As shown in FIG. 4, the porous silica gel is activated in an acid solution, washed and dried for standby; introducing double bonds on the surface of the porous silica gel by adopting an allyl silanization reagent so as to control the subsequent polymerization reaction; uniformly mixing the propenyl modified porous silica gel microspheres with template molecules, functional monomers, an initiator and a cross-linking agent according to a certain proportion, heating by a program, reacting for a period of time, washing the obtained material by using a certain proportion of mixed organic solvent until no Re template molecule is detected by eluent, washing and drying to obtain the ginsenoside Re molecularly imprinted polymer coated porous silica gel chromatographic packing.
Example 2
A preparation method of ginsenoside Re molecularly imprinted polymer coated porous silica gel chromatographic packing comprises the following steps:
acid solution activated silica gel: preparing 20 mL of mixed solution of nitric acid and hydrochloric acid with the concentration of 8 mol/L, adding 2 g of porous silica gel microspheres (the particle size is 5 mu m, the pore diameter is 20 nm) in the mixed solution at 30 DEGoAnd C, stirring for 2 hours under the condition of C, washing to be neutral, washing for 4 times by using absolute ethyl alcohol, and drying in vacuum for later use.
Introduction of double bonds: selecting 20 mL of anhydrous toluene as a reaction solvent, adding 1 mL of propenyl silanization reagent KH-570, adding 20 mu L of pyridine catalyst, and reacting at a temperature of 4%oAnd C, stirring for 10 hours, washing the propenyl modified porous silica gel microspheres by sequentially adopting methylbenzene and ethanol, and drying for later use.
Pre-polymerization: using hydroxyethyl methacrylate as monomer and ethanol as reaction solvent, controlling the concentration of ginsenoside Re as template molecule at 0.03 mol/L and 4oStanding for 10 h under the condition of C to obtain a prepolymerization system.
Preparing a ginsenoside Re molecularly imprinted polymer coated porous silica gel chromatographic filler: 20 mg of azobisisobutyronitrile as an initiator, 100. mu.L of ethylene glycol dimethacrylate crosslinker and 1 g of propenyl-modified silica gel were added to the prepolymerization system, and the temperature programmed to 30 oCKeeping for 5 h, 80 oCAnd keeping for 24 hours. Washing the obtained material by using a mixed solvent of formic acid and methanol in a ratio of 1:20 until the eluted supernatant is detected by an ultraviolet spectrophotometer to obtain Re-free template molecules; washing the obtained material with ethanol for 2 times at 60 oCDrying under vacuum for 18 h for later use.
Example 3
A preparation method of ginsenoside Re molecularly imprinted polymer coated porous silica gel chromatographic packing comprises the following steps:
acid solution activated silica gel: preparing 20 mL of mixed solution of nitric acid and hydrochloric acid with the concentration of 5 mol/L, adding 2 g of porous silica gel microspheres (the particle size is 5 mu m, the pore diameter is 30 nm) in 80oAnd C, stirring for 1 h, washing to be neutral, washing for 3 times by using absolute ethyl alcohol, and drying in vacuum for later use.
Introduction of double bonds: selecting 30 mL of anhydrous tolueneAs a reaction solvent, 1 mL of acryl silylation reagent KH-570 was added, 30. mu.L of pyridine catalyst was added thereto, and the mixture was heated at 4%oAnd C, stirring for 8 hours, washing the propenyl modified porous silica gel microspheres by sequentially adopting methylbenzene and ethanol, and drying for later use.
Pre-polymerization: using hydroxyethyl methacrylate as monomer and ethanol as reaction solvent, controlling the concentration of ginsenoside Re as template molecule at 2 mol/L and 4oStanding for 12 h under the condition of C to obtain a prepolymerization system.
Preparing a ginsenoside Re molecularly imprinted polymer coated porous silica gel chromatographic filler: adding 50 mg of initiator azobisisobutyronitrile, 80 mu L of ethylene glycol dimethacrylate crosslinking agent and 1 g of propenyl modified silica gel into the prepolymerization system, and adopting a temperature programming process of 55 oCKeeping for 10 h, 95 oCAnd keeping for 48 h. Washing the obtained material by using a mixed solvent of acetic acid and methanol in a ratio of 1:20 until the eluted supernatant is detected by an ultraviolet spectrophotometer to obtain Re-free template molecules; the resulting material was washed with ethanol 2 more times at 55 oCVacuum drying for 12 h under the condition for standby.
As shown in fig. 2, fig. 2 is an infrared spectrum of commercial bare silica gel (a) and obtained ginsenoside Re molecularly imprinted polymer-coated porous silica gel chromatographic filler (b) in example 3. As can be seen from FIG. 2, the ginsenoside Re molecularly imprinted polymer coated porous silica gel chromatographic packing has been successfully prepared.
Example 4
An application of ginsenoside Re molecularly imprinted polymer coated porous silica gel chromatographic packing as a chromatographic packing, wherein the mass fraction of C element in the chromatographic packing is 5%. The specific surface area of the porous silica gel microspheres is 300 m 2/g; the specific surface area of the ginsenoside Re molecularly imprinted polymer coated porous silica gel liquid chromatography filler is 280 m 2/g; the particle size of the porous silica gel microspheres is 5 micrometers, and the pore diameter is 20 nanometers.
The chromatographic packing can be used for chromatographic separation of ginsenoside compounds. The specific usage method can be as follows: filling the obtained chromatographic packing into a stainless steel chromatographic column with the size of 150 mm multiplied by 2.1 mm i.d by a homogenization method, and separating four ginsenoside compounds under the chromatographic conditions: mobile phase, methanol/water 80/20; flow rate: 0.2 mL/min; column temperature: 35 ℃; ultraviolet detection wavelength: 208 nm. The resulting chromatogram is shown in fig. 3, and it can be seen that the four compounds achieved baseline separation.
The molecular imprinting polymer-coated porous silica gel chromatographic packing is applied as a chromatographic packing, and is prepared by a surface imprinting technology. The ginsenoside Re molecularly imprinted polymer coated porous silica gel liquid chromatography packing can be used for chromatographic separation of ginsenoside compounds. Compared with the existing silica gel matrix chromatographic packing, the packing has better chromatographic separation performance on ginsenoside compounds. The ginsenoside Re molecularly imprinted polymer coated porous silica gel liquid chromatography filler can effectively separate four ginsenoside compounds, and the silica gel matrix is difficult to effectively separate the four ginsenoside compounds. Compared with the existing silica gel matrix liquid chromatography packing, the material has good separation selectivity and better application prospect.
The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The above-described embodiments of the invention are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims, and not by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. A preparation method of a molecularly imprinted polymer coated porous silica gel chromatographic packing is characterized by comprising the following steps:
(1) mixing the functional monomer, the reaction solvent 1 and the template molecule at a certain temperature, and standing for 6-24 hours to obtain a prepolymerization system;
(2) stirring an allyl silanization reagent, a reaction solvent 2, a catalyst and porous silica gel microspheres activated by an acidic solution at a certain temperature for 5-48 h, and washing to obtain allyl modified porous silica gel microspheres;
(3) adding an initiator, a cross-linking agent and the propenyl modified porous silica gel microspheres obtained in the step (2) into the prepolymerization system in the step (1), heating by a program, reacting for a period of time, and washing the obtained material until the eluted supernatant is detected by an ultraviolet spectrophotometer to obtain template-free molecules; and washing for 2-8 times to obtain the molecular imprinting polymer-coated porous silica gel chromatographic packing.
2. The preparation method according to claim 1, wherein the specific process of the porous silica gel microspheres activated by the acidic solution in the step (2) is as follows: preparing a nitric acid and hydrochloric acid or a mixed aqueous solution of the nitric acid and the hydrochloric acid, adding porous silica gel microspheres with the particle size of 1-100 micrometers and the pore diameter of 1-100 nanometers, stirring for a period of time at a certain temperature, washing with water to be neutral, washing with absolute ethyl alcohol for 2-5 times, and drying in vacuum for later use.
3. The method according to claim 1, wherein the reaction solvent 1 in the step (1) is at least one of methanol and acetonitrile; the reaction solvent 2 in the step (2) is at least one of anhydrous toluene, acetonitrile, ethanol or methanol.
4. The method according to claim 1, wherein the functional monomer in step (1) is at least one of methacrylic acid, acrylamide, methyl methacrylate, hydroxyethyl methacrylate and 4-vinylpyridine.
5. The method according to claim 1, wherein the temperature-programmed step in the step (3) is 20 to 60% oCKeeping for 2-24 h, then 50-120oAnd C, keeping for 2-48 h.
6. The method according to claim 1, wherein the template molecule in step (1) is a ginsenoside Re molecule, and the concentration of the template molecule is 0.001-3 mol/L.
7. The method according to claim 1, wherein the mass ratio of the functional monomer, the reaction solvent 1 and the template molecule in the step (1) is 1:20 to 1: 1;
the ratio of the propenyl silanization reagent, the reaction solvent 2, the catalyst and the porous silica gel microspheres activated by the acidic solution in the step (2) is 0.1 mL to 1 μ L to 0.1 g to 10 mL to 100 μ L to 20 g.
8. The preparation method of claim 1, wherein the amount of the initiator, the crosslinking agent and the acryl-modified porous silica gel microspheres obtained in the step (2) added in the step (3) is between 1 mg: 10 μ L:1 g and 1000 mg: 1000 μ L: 10 g.
9. A molecularly imprinted polymer-coated porous silica gel chromatography packing material, characterized by being prepared by the preparation method according to any one of claims 1 to 8.
10. The molecularly imprinted polymer-coated porous silica gel chromatographic packing according to claim 9, wherein the chromatographic packing contains 1% to 30% by mass of the C element, and has a specific surface area of 60 m2/g ~ 650 m2/g。
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