CN112526034A - Solid phase micro-extraction-high performance liquid chromatography on-line combined detection method of grease antioxidant - Google Patents
Solid phase micro-extraction-high performance liquid chromatography on-line combined detection method of grease antioxidant Download PDFInfo
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- 238000001514 detection method Methods 0.000 title claims abstract description 41
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 37
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 25
- 239000004519 grease Substances 0.000 title claims abstract description 22
- 238000004128 high performance liquid chromatography Methods 0.000 title claims abstract description 22
- 239000007790 solid phase Substances 0.000 title claims abstract description 22
- 239000013310 covalent-organic framework Substances 0.000 claims abstract description 59
- 238000002470 solid-phase micro-extraction Methods 0.000 claims abstract description 40
- 238000004458 analytical method Methods 0.000 claims abstract description 26
- 229920001807 Urea-formaldehyde Polymers 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 60
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 45
- 239000007864 aqueous solution Substances 0.000 claims description 32
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 24
- 239000004005 microsphere Substances 0.000 claims description 23
- 239000000523 sample Substances 0.000 claims description 23
- 238000011068 loading method Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 20
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 claims description 18
- -1 polytetrafluoroethylene Polymers 0.000 claims description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 18
- 239000012071 phase Substances 0.000 claims description 15
- 239000003480 eluent Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
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- 239000003054 catalyst Substances 0.000 claims description 12
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- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 claims description 11
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- 229920002530 polyetherether ketone Polymers 0.000 claims description 11
- 238000010828 elution Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 9
- 235000010388 propyl gallate Nutrition 0.000 claims description 9
- 239000000473 propyl gallate Substances 0.000 claims description 9
- 229940075579 propyl gallate Drugs 0.000 claims description 9
- 239000004250 tert-Butylhydroquinone Substances 0.000 claims description 9
- 235000019281 tert-butylhydroquinone Nutrition 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000004811 liquid chromatography Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 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 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
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- 238000006243 chemical reaction Methods 0.000 claims description 3
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- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
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- 239000000463 material Substances 0.000 claims description 2
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- MRBKEAMVRSLQPH-UHFFFAOYSA-N 3-tert-butyl-4-hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1 MRBKEAMVRSLQPH-UHFFFAOYSA-N 0.000 claims 1
- 125000003172 aldehyde group Chemical group 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 claims 1
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- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 abstract description 2
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- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 7
- 239000004255 Butylated hydroxyanisole Substances 0.000 description 6
- 229940043253 butylated hydroxyanisole Drugs 0.000 description 6
- 239000008157 edible vegetable oil Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
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- 239000000312 peanut oil Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- IMOYOUMVYICGCA-UHFFFAOYSA-N 2-tert-butyl-4-hydroxyanisole Chemical compound COC1=CC=C(O)C=C1C(C)(C)C IMOYOUMVYICGCA-UHFFFAOYSA-N 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/08—Preparation using an enricher
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/027—Liquid chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/08—Preparation using an enricher
- G01N2030/085—Preparation using an enricher using absorbing precolumn
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- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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Abstract
本发明公开了一种油脂抗氧化剂的固相微萃取‑高效液相色谱在线联用检测方法。本发明首先制备共价有机骨架功能化固相微萃取整体柱，再以该整体柱作为固相微萃取介质，结合固相微萃取‑高效液相色谱在线联用系统，建立一种油脂抗氧化剂的固相微萃取‑高效液相色谱在线联用检测方法。本发明利用整体柱的脲醛树脂基质与分析对象之间的亲水相互作用以及共价有机骨架与分析对象之间的π‑π堆积相互作用的协同作用机理，实现油脂抗氧化剂的高效萃取富集，并消除样品基质中杂质对分析检测的干扰。本发明方法简单，工艺巧妙，所需仪器普及度较高，易于推广，可实现复杂实际样品中微量油脂抗氧化剂的高效萃取富集，并满足相关高灵敏检测要求。The invention discloses a solid-phase micro-extraction-high-performance liquid chromatography on-line combined detection method for oil and fat antioxidants. The present invention firstly prepares a covalent organic framework functionalized solid-phase micro-extraction monolithic column, and then uses the monolithic column as a solid-phase micro-extraction medium, and combines the solid-phase micro-extraction-high performance liquid chromatography on-line combined system to establish a grease antioxidant The solid-phase microextraction-high performance liquid chromatography on-line detection method. The invention utilizes the synergistic action mechanism of the hydrophilic interaction between the urea-formaldehyde resin matrix of the monolithic column and the analysis object and the π-π stacking interaction between the covalent organic framework and the analysis object, so as to realize the efficient extraction and enrichment of oil and fat antioxidants. , and eliminate the interference of impurities in the sample matrix on the analytical detection. The method of the invention is simple, the process is ingenious, the required instruments are highly popular, and it is easy to popularize.
Description
Technical Field
The invention belongs to the field of analytical chemistry, and particularly relates to a solid-phase microextraction-high performance liquid chromatography online combined detection method for an oil antioxidant.
Background
If the oil is influenced by factors such as air, illumination, temperature, moisture, impurities, heavy metal ions, microorganisms and the like for a long time in the processing, storage and use processes, oxidative rancidity and deterioration can occur, the rancidity of the oil can not only influence the quality of oil products and products thereof, but also form health hidden troubles such as aging, tumors, cardiovascular diseases and the like for human bodies. In the food industry, it is common to delay or eliminate the oxidative rancidity of fats and oils by adding antioxidants to the fats and oils. Phenolic antioxidants are commonly used antioxidants in fats and oils, and their representative substances mainly include: t-butyl p-hydroxyanisole (BHA), Propyl Gallate (PG), tert-butylhydroquinone (TBHQ), dibutylhydroxytoluene (BHT), and the like. However, it is not negligible that these antioxidants have large toxic and side effects and have adverse effects on human health, such as potential carcinogenicity of BHA, which may inhibit the activity of human respiratory enzymes and cause liver damage. Therefore, it is necessary to detect the antioxidant content in the oil with high sensitivity. Because of the interference of the complex matrix of the actual sample on the analysis and detection, the sample is generally required to be preprocessed before the detection, so as to reduce the interference of impurities, enrich the analysis object and improve the detection sensitivity.
Covalent Organic Frameworks (COFs) are porous organic polymers formed by combining light elements such as C, H, O, N, B and the like through covalent bonds, and show good application potential in sample pretreatment, the action mechanism of the covalent organic frameworks is mainly that the COFs contain rich benzene rings and-C = N functional groups, a strong pi-pi accumulation effect is provided, and meanwhile, the porous structure of the COFs also ensures large adsorption capacity. As phenolic grease antioxidants such as BHA, PG, TBHQ and the like all have pi-pi conjugated systems containing benzene rings in chemical structures, pi-pi stacking interaction can be generated between the substances and COFs, and a new idea is provided for developing selective extraction and enrichment materials of the grease antioxidants. Firstly, preparing a covalent organic framework functionalized solid phase micro-extraction monolithic column; then the monolithic column is used as a solid phase micro-extraction medium, and the synergistic effect of the pi-pi accumulation effect between COFs (chemical organic frameworks) contained in the monolithic column and the phenolic grease antioxidant and the hydrophilic interaction between the urea resin matrix of the monolithic column and the phenolic grease antioxidant is utilized to realize the high-efficiency extraction and enrichment of trace grease antioxidant in the grease sample and eliminate the interference of impurities in the matrix of the actual sample on analysis and detection; and an online combined detection method of the grease antioxidant is established by combining a solid phase microextraction-high performance liquid chromatography online combined system. At present, no report related to on-line enrichment and extraction of the grease antioxidant by using a covalent organic framework functionalized monolithic column exists.
Disclosure of Invention
The invention aims to provide an on-line combined detection method of solid-phase micro-extraction-high performance liquid chromatography of an oil antioxidant. Firstly, preparing a covalent organic framework functionalized solid phase micro-extraction monolithic column; then the monolithic column is used as a solid phase micro-extraction medium; due to the synergistic extraction effect between the integral column and the phenolic grease antioxidant (namely pi-pi accumulation effect of a covalent organic framework and hydrophilic interaction of a urea resin matrix), the efficient extraction enrichment and on-line purification of trace antioxidants in an actual grease sample are realized; and an online combined detection method of the grease antioxidant is established by combining a solid phase microextraction-high performance liquid chromatography online combined system.
In order to achieve the purpose, the invention adopts the following technical scheme:
the construction and operation of the solid phase micro-extraction-high performance liquid chromatography online combined system are as follows:
the invention relates to a solid phase microextraction-high performance liquid chromatography online combined system which is constructed by referring to a related patent (patent number: 2018207623454), and mainly comprises a ten-way valve, a six-way valve, a covalent organic framework functionalized solid phase microextraction monolithic column, a liquid phase chromatography infusion pump-pump A, a 0.5 mL PEEK tube quantitative ring, a liquid phase chromatography infusion pump-pump B, a 0.2 mL PEEK tube quantitative ring, a liquid phase chromatography analysis column and a detector.
The combined system comprises the following specific operation steps:
firstly, a ten-way valve and a six-way valve of an online combined system are both in a LOAD position; the liquid loading is balanced by a pump A to balance the covalent organic framework functionalized solid phase micro-extraction monolithic column, and the flow rate is 0.1 mL/min; the mobile phase passes through the analytical column directly by a pump B to obtain a stable baseline required by chromatographic separation, and the flow rate is 1.0 mL/min; meanwhile, filling a sample solution into a 0.5 mL PEEK tube quantitative ring through a sample injection needle;
secondly, adjusting the six-way valve to an INJECT position, starting on-line solid-phase microextraction, bringing a sample in a 0.5 mL PEEK tube quantitative ring into a covalent organic framework functionalized solid-phase microextraction monolithic column through loading liquid, and adjusting the six-way valve to a LOAD position after a given time;
thirdly, changing the solution conveyed by the pump A from loading liquid to eluent with the flow rate set as 0.1 mL/min, eluting the analysis object enriched on the covalent organic framework functionalized solid phase microextraction monolithic column by using the eluent, and collecting the elution object in a 0.2 mL PEEK tube quantitative ring; when the elution is completed, the ten-way valve is adjusted to the INJECT position, the collected eluent is sent to a liquid chromatographic column by using the mobile phase for separation, and then the detection is carried out by using a detector.
Wherein, the sample solvent and the loading solution comprise: acetonitrile/5 mmol/L pH =6.0 aqueous ammonium formate solution =40/60 by volume fraction ratio; the mobile phase is as follows: acetonitrile/0.05% aqueous formic acid =60/40 by volume fraction; the eluent is as follows: acetonitrile; the analytical column is a C18 liquid chromatographic analytical column; the detector is an ultraviolet detector; the temperature of the column oven is 40 ℃, and the detection wavelength is 201 nm.
The covalent organic framework functionalized solid-phase microextraction monolithic column is prepared by mixing covalent organic framework nano microspheres, urea aqueous solution, formaldehyde aqueous solution and a catalyst, wherein the mass ratio of the covalent organic framework nano microspheres to the urea aqueous solution to the formaldehyde aqueous solution to the catalyst is 2:9:11: 2. The concentration of the urea aqueous solution is 1 g/mL; the mass concentration of formaldehyde in the formaldehyde aqueous solution is 33% -37%; the catalyst is hydrochloric acid aqueous solution, and the concentration of the hydrochloric acid aqueous solution is 0.1 mol/L.
The preparation method of the covalent organic framework functionalized solid phase micro-extraction monolithic column comprises the following steps:
(1) cleaning an empty pipe: washing the empty polytetrafluoroethylene tube with chromatographic pure methanol, and then placing the tube in a drying oven at 60 ℃ for drying for later use; wherein the length of the polytetrafluoroethylene tube is 10 cm, and the inner diameter is 750 mu m;
(2) preparing covalent organic framework nano microspheres; mixing 0.04 mmol of 1,3, 5-tri (4-aminophenyl) benzene and 0.06 mmol of terephthalaldehyde in 5 mL of acetonitrile, carrying out ultrasonic treatment for 1 minute, adding 1 mL of glacial acetic acid of 12 mol/L, carrying out vortex mixing, carrying out violent oscillation for 10 seconds, standing at room temperature for 72 hours, centrifuging, and collecting precipitate; then washing the microspheres with anhydrous tetrahydrofuran and anhydrous ethanol for three times respectively, and drying the microspheres in vacuum at 60 ℃ for 24 hours to obtain the covalent organic framework nano microspheres.
(3) And (3) rapid polycondensation in a tube: uniformly mixing covalent organic framework nano microspheres, formaldehyde aqueous solution, urea aqueous solution and a catalyst in proportion, quickly oscillating for 1 minute, quickly filling the mixture into a clean and dry polytetrafluoroethylene tube, sealing two ends of the polytetrafluoroethylene tube, and soaking the polytetrafluoroethylene tube in a water bath at 65 ℃ to heat the polytetrafluoroethylene tube at constant temperature for 10 minutes;
(4) washing the monolithic column: after the reaction is finished, using water as a mobile phase, washing the monolithic column by using a liquid chromatography pump, and removing residual solvent and unreacted substances in a column bed to obtain the covalent organic framework functionalized solid phase micro-extraction monolithic column; the monolith is equilibrated with a loading liquid for half an hour prior to conducting an on-line solid phase microextraction operation.
The invention has the following remarkable advantages:
1) the traditional enrichment extraction of the phenolic oil antioxidant mainly uses an inverse phase stationary phase, and a large amount of nonpolar substances in the oil cause great interference on the enrichment extraction of an analysis object; the invention takes a covalent organic framework functionalized solid-phase microextraction monolithic column as a solid-phase microextraction medium, and realizes the high-efficiency enrichment and extraction of an analysis object by utilizing the synergistic extraction effect (namely the pi-pi accumulation effect of the covalent organic framework and the hydrophilic interaction of a urea resin matrix) between the monolithic column and a phenolic grease antioxidant; in addition, the hydrophilic action of the monolithic column matrix greatly reduces the adsorption of non-polar impurities and reduces the influence of the actual sample matrix on the enrichment and analysis of an analysis object.
2) The invention carries out analysis and detection based on an online combined system, greatly improves the detection efficiency compared with the conventional detection method, and improves the automation degree of the system.
Drawings
Fig. 1 shows the influence of acetonitrile content in a loading liquid on the enrichment efficiency of an analysis object when a solid phase microextraction-high performance liquid chromatography (hplc) online combined system is constructed by using a covalent organic framework functionalized monolithic column as a solid phase microextraction medium to perform online enrichment detection on Propyl Gallate (PG), tert-butyl hydroquinone (TBHQ) and tert-butyl p-hydroxyanisole (BHA).
FIG. 2 is a chromatogram of an online enrichment detection of trace oil antioxidants added to edible oil by constructing a solid phase microextraction-high performance liquid chromatography online combined system by using a covalent organic framework functionalized monolithic column as a solid phase microextraction medium. a is the analysis chromatogram of a conventional liquid chromatography system; and b is an online coupling system analysis chromatogram.
FIG. 3 is a chromatogram of different edible oil samples on-line enrichment detection by using a covalent organic framework functionalized monolithic column as a solid phase microextraction medium to construct a solid phase microextraction-high performance liquid chromatography on-line combined system. a is an online combined system analysis chromatogram of a certain brand of blend oil; b is an online combined system analysis chromatogram of certain brand sunflower seed oil; c is an online combined system analysis chromatogram of a certain brand of peanut oil.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
The covalent organic framework functionalized solid-phase microextraction monolithic column is prepared by mixing covalent organic framework nano microspheres, urea aqueous solution, formaldehyde aqueous solution and a catalyst, wherein the mass ratio of the covalent organic framework nano microspheres to the urea aqueous solution to the formaldehyde aqueous solution to the catalyst is 2:9:11: 2.
The concentration of the urea aqueous solution is 1 g/mL; the mass concentration of formaldehyde in the formaldehyde aqueous solution is 37%; the catalyst is hydrochloric acid aqueous solution, and the concentration of the hydrochloric acid aqueous solution is 0.1 mol/L.
The preparation method of the covalent organic framework functionalized solid phase micro-extraction monolithic column comprises the following steps:
(1) cleaning an empty pipe: washing the empty polytetrafluoroethylene tube with chromatographic pure methanol, and then placing the tube in a drying oven at 60 ℃ for drying for later use; wherein the length of the polytetrafluoroethylene tube is 10 cm, and the inner diameter is 750 mu m;
(2) preparing covalent organic framework nano microspheres; mixing 0.04 mmol of 1,3, 5-tri (4-aminophenyl) benzene and 0.06 mmol of terephthalaldehyde in 5 mL of acetonitrile, carrying out ultrasonic treatment for 1 minute, adding 1 mL of glacial acetic acid of 12 mol/L, carrying out vortex mixing, carrying out violent oscillation for 10 seconds, standing at room temperature for 72 hours, centrifuging, and collecting precipitate; then washing the microspheres with anhydrous tetrahydrofuran and anhydrous ethanol for three times respectively, and drying the microspheres in vacuum at 60 ℃ for 24 hours to obtain the covalent organic framework nano microspheres.
(3) And (3) rapid polycondensation in a tube: uniformly mixing covalent organic framework nano microspheres, formaldehyde aqueous solution, urea aqueous solution and a catalyst in proportion, quickly oscillating for 1 minute, quickly filling the mixture into a clean and dry polytetrafluoroethylene tube, sealing two ends of the polytetrafluoroethylene tube, and soaking the polytetrafluoroethylene tube in a water bath at 65 ℃ to heat the polytetrafluoroethylene tube at constant temperature for 10 minutes;
(4) washing the monolithic column: after the reaction is finished, using water as a mobile phase, washing the monolithic column by using a liquid chromatography pump, and removing residual solvent and unreacted substances in a column bed to obtain the covalent organic framework functionalized solid phase micro-extraction monolithic column; the monolith is equilibrated with a loading liquid for half an hour prior to conducting an on-line solid phase microextraction operation.
Example 2
The combined system comprises the following specific operation steps:
firstly, a ten-way valve and a six-way valve of an online combined system are both in a LOAD position; the loading liquid passes through a pump A to balance the covalent organic framework functionalized solid phase micro extraction monolithic column (the monolithic column prepared in example 1), and the flow rate is 0.1 mL/min; the mobile phase passes through the analytical column directly by a pump B to obtain a stable baseline required by chromatographic separation, and the flow rate is 1.0 mL/min; meanwhile, filling a sample solution into a 0.5 mL PEEK tube quantitative ring through a sample injection needle;
secondly, adjusting the six-way valve to an INJECT position, starting on-line solid-phase microextraction, bringing a sample in a 0.5 mL PEEK tube quantitative ring into a covalent organic framework functionalized solid-phase microextraction monolithic column through loading liquid, and adjusting the six-way valve to a LOAD position after a given time;
thirdly, changing the solution conveyed by the pump A from loading liquid to eluent with the flow rate set as 0.1 mL/min, eluting the analysis object enriched on the covalent organic framework functionalized solid phase microextraction monolithic column by using the eluent, and collecting the elution object in a 0.2 mL PEEK tube quantitative ring; when the elution is completed, the ten-way valve is adjusted to the INJECT position, the collected eluent is sent to a liquid chromatographic column by using the mobile phase for separation, and then the detection is carried out by using a detector.
According to the technical scheme of the invention, firstly, a covalent organic framework functionalized monolithic column (the monolithic column prepared in example 1) is prepared, and the monolithic column is used as a solid phase microextraction medium, and a solid phase microextraction-high performance liquid chromatography online combined analysis system is constructed by referring to related patents (patent number: 2018207623454). And then, detecting the antioxidant in the grease by means of online enrichment of an online coupling system, and investigating the influence of the acetonitrile content in the loading liquid on the sample enrichment efficiency. The concentration of several antioxidants in the detection sample is 1.0 mg/kg; the loading solution consists of acetonitrile and 5mM ammonium formate aqueous solution with pH =6.0, the sample injection solvent consists of acetonitrile/5 mM ammonium formate aqueous solution with pH =6.0 =40/60 (v/v), the sample injection flow rate is 0.1 mL/min, and the sample injection volume is 500 μ L; the eluent composition is pure acetonitrile, the elution flow rate is 0.1 mL/min, and the elution volume is 200 μ L (the eluent is collected for the first two minutes); the mobile phase for separation was acetonitrile/0.05% aqueous formic acid =60/40 (v/v), the separation flow rate was 1.0 mL/min, the column oven temperature was 40 ℃, and the detection wavelength was 201 nm.
As shown in fig. 1, when the acetonitrile content of the loading solution is increased from 20% (v/v) to 40% (v/v), the enrichment efficiency of the analysis object is continuously improved, which represents the typical hydrophilic interaction between the monolithic urea-formaldehyde resin matrix and the analysis object; as the acetonitrile content of the loading solution is continuously increased from 40% (v/v) to 60% (v/v), the enrichment efficiency of the analysis object is not obviously improved or is reduced, which should be that the pi-pi stacking effect between the analysis object and the covalent organic framework is obviously weakened along with the increase of the acetonitrile content; therefore, we can see that the extraction mode between several antioxidants and the covalent organic framework functionalized monolithic column is the synergistic extraction effect of the hydrophilic effect and the pi-pi stacking effect. Therefore, we chose a loading liquid acetonitrile ratio of 40% (v/v) as the optimum ratio.
Example 3
According to the technical scheme of the embodiment 2, firstly, the covalent organic framework functionalized monolithic column of the embodiment 1 is prepared, and the monolithic column is used as a solid phase microextraction medium, and a solid phase microextraction-high performance liquid chromatography on-line combined analysis system is constructed by referring to a related patent (patent number: 2018207623454). And then, detecting the antioxidant in the grease by virtue of online enrichment of an online coupling system, wherein the operation optimization parameters of the coupling system are as follows: the sample loading fluid was ACN/5 mM pH =6.0 ammonium formate solution =40%/60% (v/v); the eluent is acetonitrile; the sample introduction flow rate is 0.10 mL/min; the elution flow rate is 0.10 mL/min; elution volume 200 μ L (first two minutes of eluate collected); the mobile phase was ACN/0.05% formic acid solution =60%/40% (v/v); the flow rate of the mobile phase is 1.0 mL/min; the temperature of the column oven is 40 ℃; the detection wavelength was set at 201 nm.
FIG. 2 is a chromatogram comparing the on-line system and the conventional liquid chromatography system for detecting several oil antioxidants added at 1.0 mg/kg in edible oil. In fig. 2, the detection peak 1 is Propyl Gallate (PG), the detection peak 2 is tert-butylhydroquinone (TBHQ), and the detection peak 3 is Butylated Hydroxyanisole (BHA). As can be seen from FIG. 2-b, under the conditions of the combined system, the trace amount of the grease antioxidant added into the edible oil is subjected to efficient enrichment extraction and high-sensitivity detection, and the detection limits of several analysis objects are 2.0. mu.g/kg (PG), 0.9. mu.g/kg (TBHQ) and 0.3. mu.g/kg (BHA), respectively. When the same sample is analyzed using a conventional liquid chromatography system, the signal of the detection object is weak and the detection sensitivity is low (FIG. 2-a). FIG. 3 is a chromatogram of on-line enrichment detection of actual samples of different edible oils using the on-line combination system constructed by the present invention. As can be seen, BHA was detected in all 3 edible oil samples, at 140. mu.g/kg (blend oil), 100. mu.g/kg (sunflower oil) and 225. mu.g/kg (peanut oil). This demonstrates the utility and reliability of the method established by the present invention.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (6)
1. A solid phase micro-extraction-high performance liquid chromatography on-line combined detection method of a grease antioxidant is characterized in that: the detection method is characterized in that a covalent organic framework functionalized monolithic column is used as a solid-phase microextraction monolithic column, and an online combined detection method of solid-phase microextraction and high performance liquid chromatography is established; wherein the oil antioxidant specifically refers to propyl gallate, tert-butyl hydroquinone and butyl hydroxy anisol.
2. The method for detecting the oil antioxidant by the solid phase microextraction-high performance liquid chromatography online combination according to claim 1, which is characterized in that: the solid-phase microextraction monolithic column takes covalent organic framework nano microspheres as a functionalized material, the covalent organic framework nano microspheres, urea aqueous solution, formaldehyde aqueous solution and a catalyst are mixed, amino groups and aldehyde groups on the surfaces of the covalent organic framework nano microspheres participate in urea formaldehyde polycondensation reaction to realize immobilization of the covalent organic framework nano microspheres, and the covalent organic framework functionalized solid-phase microextraction monolithic column is prepared; the concentration of the urea aqueous solution is 1 g/mL; the mass concentration of formaldehyde in the formaldehyde aqueous solution is 33% -37%; the catalyst is hydrochloric acid aqueous solution, and the concentration of the hydrochloric acid aqueous solution is 0.1 mol/L.
3. The solid phase micro-extraction-high performance liquid chromatography on-line combined detection method of the grease antioxidant according to claim 2, characterized in that: the mass ratio of the covalent organic framework nano-microspheres to the urea aqueous solution to the formaldehyde aqueous solution to the catalyst is 2:9:11: 2.
4. The solid phase micro-extraction-high performance liquid chromatography on-line combined detection method of the grease antioxidant according to claim 2, characterized in that: the preparation method of the monolithic column comprises the following steps:
(1) cleaning an empty pipe: washing the empty polytetrafluoroethylene tube with chromatographic pure methanol, and then placing the tube in a drying oven at 60 ℃ for drying for later use; wherein the length of the polytetrafluoroethylene tube is 10 cm, and the inner diameter is 750 mu m;
(2) preparing covalent organic framework nano microspheres: mixing 0.04 mmol of 1,3, 5-tri (4-aminophenyl) benzene and 0.06 mmol of terephthalaldehyde in 5 mL of acetonitrile, carrying out ultrasonic treatment for 1 minute, adding 1 mL of glacial acetic acid of 12 mol/L, carrying out vortex mixing, carrying out violent oscillation for 10 seconds, standing at room temperature for 72 hours, centrifuging, and collecting precipitate; then washing the microspheres with anhydrous tetrahydrofuran and anhydrous ethanol for three times respectively, and carrying out vacuum drying for 24 hours at the temperature of 60 ℃ to obtain covalent organic framework nano microspheres;
(3) and (3) rapid polycondensation in a tube: uniformly mixing covalent organic framework nano microspheres, formaldehyde aqueous solution, urea aqueous solution and a catalyst in proportion, quickly oscillating for 1 minute, quickly filling the mixture into a clean and dry polytetrafluoroethylene tube, sealing two ends of the polytetrafluoroethylene tube, and soaking the polytetrafluoroethylene tube in a water bath at 65 ℃ to heat the polytetrafluoroethylene tube at constant temperature for 10 minutes;
(4) washing the monolithic column: after the reaction is finished, using water as a mobile phase, washing the monolithic column by using a liquid chromatography pump, and removing residual solvent and unreacted substances in a column bed to obtain the covalent organic framework functionalized solid phase micro-extraction monolithic column; the monolith is equilibrated with a loading liquid for half an hour prior to conducting an on-line solid phase microextraction operation.
5. The method for detecting the oil antioxidant by the solid phase microextraction-high performance liquid chromatography online combination according to claim 1, which is characterized in that: the online combined detection method comprises the following specific operation steps:
1) firstly, a ten-way valve and a six-way valve of an online combined system are both in a LOAD position; the liquid loading is balanced by a pump A to balance the covalent organic framework functionalized solid phase micro-extraction monolithic column, and the flow rate is 0.1 mL/min; the mobile phase passes through the analytical column directly by a pump B to obtain a stable baseline required by chromatographic separation, and the flow rate is 1.0 mL/min; meanwhile, filling a sample solution into a 0.5 mL PEEK tube quantitative ring through a sample injection needle;
2) when the six-way valve is adjusted to the INJECT position, the online solid-phase microextraction starts, a sample in a 0.5 mL PEEK tube quantitative ring is brought into the covalent organic framework functionalized solid-phase microextraction monolithic column through loading liquid, and after a given time, the six-way valve is adjusted back to the LOAD position;
3) then, the solution delivered by the pump A is changed into eluent from loading liquid, the eluent is utilized to elute the analysis object enriched on the covalent organic framework functionalized solid phase microextraction monolithic column, and the elution object is collected in a 0.2 mL PEEK tube quantitative ring; when the elution is completed, the ten-way valve is adjusted to the INJECT position, the collected eluent is sent to a liquid chromatographic column by using the mobile phase for separation, and then the detection is carried out by using a detector.
6. The on-line detection method for the solid-phase microextraction-high-efficiency liquid chromatography of the grease antioxidant according to claim 5, characterized in that: wherein, the sample solvent and the loading solution comprise: acetonitrile/5 mmol/L pH =6.0 aqueous ammonium formate solution =40/60 by volume fraction ratio; the mobile phase is as follows: acetonitrile/0.05% aqueous formic acid =60/40 by volume fraction; the eluent is as follows: acetonitrile; the analytical column is a C18 liquid chromatographic analytical column.
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