CN115015407B - Method for determining parahydroxybenzoate isomer in essence - Google Patents
Method for determining parahydroxybenzoate isomer in essence Download PDFInfo
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- CN115015407B CN115015407B CN202210557546.1A CN202210557546A CN115015407B CN 115015407 B CN115015407 B CN 115015407B CN 202210557546 A CN202210557546 A CN 202210557546A CN 115015407 B CN115015407 B CN 115015407B
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- 238000000034 method Methods 0.000 title claims abstract description 39
- FJKROLUGYXJWQN-UHFFFAOYSA-M 4-hydroxybenzoate Chemical class OC1=CC=C(C([O-])=O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-M 0.000 title claims abstract description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000004005 microsphere Substances 0.000 claims abstract description 50
- 239000012488 sample solution Substances 0.000 claims abstract description 20
- 238000004885 tandem mass spectrometry Methods 0.000 claims abstract description 19
- 239000012530 fluid Substances 0.000 claims abstract description 14
- 238000004458 analytical method Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000004808 supercritical fluid chromatography Methods 0.000 claims abstract description 6
- 238000000605 extraction Methods 0.000 claims description 56
- 239000000523 sample Substances 0.000 claims description 35
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical class OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 23
- 238000010828 elution Methods 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 239000003205 fragrance Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000001819 mass spectrum Methods 0.000 claims description 5
- 235000010232 propyl p-hydroxybenzoate Nutrition 0.000 claims description 5
- 239000004405 propyl p-hydroxybenzoate Substances 0.000 claims description 5
- QELSKZZBTMNZEB-UHFFFAOYSA-N propylparaben Chemical group CCCOC(=O)C1=CC=C(O)C=C1 QELSKZZBTMNZEB-UHFFFAOYSA-N 0.000 claims description 5
- QFOHBWFCKVYLES-UHFFFAOYSA-N Butylparaben Chemical compound CCCCOC(=O)C1=CC=C(O)C=C1 QFOHBWFCKVYLES-UHFFFAOYSA-N 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- XPJVKCRENWUEJH-UHFFFAOYSA-N Isobutylparaben Chemical compound CC(C)COC(=O)C1=CC=C(O)C=C1 XPJVKCRENWUEJH-UHFFFAOYSA-N 0.000 claims description 2
- CMHMMKSPYOOVGI-UHFFFAOYSA-N Isopropylparaben Chemical compound CC(C)OC(=O)C1=CC=C(O)C=C1 CMHMMKSPYOOVGI-UHFFFAOYSA-N 0.000 claims description 2
- 238000004807 desolvation Methods 0.000 claims 2
- 239000000796 flavoring agent Substances 0.000 claims 2
- 235000019634 flavors Nutrition 0.000 claims 2
- 150000001450 anions Chemical group 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 14
- 238000001514 detection method Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000013375 chromatographic separation Methods 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 238000007689 inspection Methods 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 27
- 238000011084 recovery Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 230000010355 oscillation Effects 0.000 description 10
- 238000000746 purification Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 7
- 238000005192 partition Methods 0.000 description 7
- 239000003755 preservative agent Substances 0.000 description 7
- NUHSROFQTUXZQQ-UHFFFAOYSA-N isopentenyl diphosphate Chemical compound CC(=C)CCO[P@](O)(=O)OP(O)(O)=O NUHSROFQTUXZQQ-UHFFFAOYSA-N 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 235000013373 food additive Nutrition 0.000 description 4
- 239000002778 food additive Substances 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 239000012224 working solution Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003556 assay Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 235000011194 food seasoning agent Nutrition 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- ZLVSYODPTJZFMK-UHFFFAOYSA-M sodium 4-hydroxybenzoate Chemical compound [Na+].OC1=CC=C(C([O-])=O)C=C1 ZLVSYODPTJZFMK-UHFFFAOYSA-M 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- G01N30/14—Preparation by elimination of some components
-
- 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
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
-
- 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
- G01N30/60—Construction of the column
- G01N30/6052—Construction of the column body
-
- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
- G01N30/7233—Mass spectrometers interfaced to liquid or supercritical fluid chromatograph
- G01N30/724—Nebulising, aerosol formation or ionisation
- G01N30/7266—Nebulising, aerosol formation or ionisation by electric field, e.g. electrospray
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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
- G01N2030/042—Standards
- G01N2030/047—Standards external
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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
- G01N30/14—Preparation by elimination of some components
- G01N2030/143—Preparation by elimination of some components selective absorption
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention belongs to the technical field of physical and chemical inspection, and particularly relates to a method for measuring an isomer of parahydroxybenzoate in essence. The method comprises the following steps: (1) Mixing and extracting essence, methanol and magnetic microspheres, magnetically adsorbing the magnetic microspheres, and separating to obtain a sample solution to be detected; (2) Carrying out determination analysis on a sample solution to be detected by using supercritical fluid chromatography-tandem mass spectrometry; the chromatographic column of the supercritical fluid chromatography in the supercritical fluid chromatography-tandem mass spectrometry is Chiralpak IG-3. The magnetic microspheres can play a good role in adsorbing and purifying pigments, additives and other polar and nonpolar non-target objects in the essence, and the para-hydroxybenzoate isomer in the essence is analyzed by supercritical fluid chromatography-tandem mass spectrometry, and the chromatographic separation time is greatly shortened and the separation effect is good by optimizing the detection conditions of an instrument.
Description
Technical Field
The invention belongs to the technical field of physical and chemical inspection, and particularly relates to a method for measuring an isomer of parahydroxybenzoate in essence.
Background
Parahydroxybenzoate (Paraben) is also known as Paraben, and is a low-toxicity and high-efficiency preservative because of its low toxicity, non-volatility, strong bactericidal ability and good stability. The mechanism of action of the parabens isomers is to change the permeability of cell membranes and cell walls, so that enzymes and metabolites in microorganisms can escape. The range of the research matrix for measuring the parahydroxybenzoate is wide, and the detection method is not uniform, and the adopted detection method is also not uniform, and a High Performance Liquid Chromatography (HPLC) method, a Gas Chromatography (GC) method and a gas chromatography-mass spectrometry (GC/MS) method are adopted. However, there are few methods currently involving the separation of the paraben isomers.
The method for measuring the content of 6 low-carbon chain alkyl parabens (A, B, isopropyl, C, isobutyl and butyl) with relatively high toxicity in food is established by using a gas chromatography (FID detector) of the 6 parabens in food by using gas chromatography of high navy et al. Ju Fulong and the like for simultaneously detecting 7 preservatives in the seasoning by using a gas chromatography-mass spectrometry method, and simultaneously detecting 7 preservatives such as propyl p-hydroxybenzoate and sodium salt thereof in the seasoning by using a gas chromatography-mass spectrometry method. However, sodium paraben is a sodium salt form of paraben, and the melting point of sodium salt is very high, which is difficult to gasify. When GC or GC-MS is used, acidification and extraction treatment are needed in the sample treatment process, the operation is complex, and experimental influence factors are many. Liu Ying, 16 food additives such as propyl p-hydroxybenzoate in confection are simultaneously determined by high performance liquid chromatography. Zhao Kongxiang "determination of 10 limiting substances in cosmetics by high Performance liquid chromatography" the use of high Performance liquid chromatography to determine 10 limiting substances in cosmetics, such as propyl p-hydroxybenzoate, was used.
Although the prior art realizes effective detection of the parabens in foods, no related research on determination of the paraben isomers in essence exists at present.
Disclosure of Invention
The invention aims to provide a method for measuring the parahydroxybenzoate isomer in essence, which can lead the isomers (PP, IPP, BP and IBP) to obtain complete baseline separation and has good quantitative effect.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a method for determining the paraben isomer in a fragrance comprising the steps of:
(1) Mixing and extracting essence, methanol and magnetic microspheres, magnetically adsorbing the magnetic microspheres, and separating to obtain a sample solution to be detected;
(2) Carrying out determination analysis on a sample solution to be detected by using supercritical fluid chromatography-tandem mass spectrometry; the chromatographic column of the supercritical fluid chromatography in the supercritical fluid chromatography-tandem mass spectrometry is Chiralpak IG-3;
the magnetic microspheres are C18 magnetic microspheres and aminated magnetic microspheres.
The method adopts the magnetic microspheres to extract the essence sample, integrates the extraction and purification of the sample, and is simpler and faster to operate. The magnetic microspheres can play a good role in adsorbing and purifying pigments, additives and other polar and nonpolar non-target objects in the essence, and avoid the loss of components to be detected caused by the concentration and purification processes of the sample.
The invention adopts supercritical fluid chromatography-tandem mass spectrometry (SFC-MS/MS) analysis to determine the paraben isomer in the essence by supercritical CO 2 And ethanol is used as a mobile phase, and has the advantages of high separation speed and strong specificity, and chromatographic separation time is greatly shortened by optimizing instrument detection conditions, and the separation degree is good (baseline separation) only for 5.5 min.
Further, the determination conditions of the supercritical fluid chromatography in the supercritical fluid chromatography-tandem mass spectrometry are as follows: mobile phase A is supercritical CO 2 Mobile phase B is ethanol; the total flow rate of the two phases after mixing is 1.8-2.0mL/min; the column temperature is 35-40 ℃; the sample injection amount is 2-5 mu L; the elution mode is gradient elution.
Further, the volume ratio of the mobile phase A in the gradient elution is reduced from 99% to 90%, and then is recovered to 99%. Further, the volume ratio of the mobile phase A is 99 percent, the volume ratio of the mobile phase A is 1 to 3 minutes, the volume ratio of the mobile phase A is reduced to 95 percent, the volume ratio of the mobile phase A is reduced to 90 percent, the volume ratio of the mobile phase A is 4.0 to 4.5 minutes, the volume ratio of the mobile phase A is kept 90 percent, the volume ratio of the mobile phase A is 4.5 to 4.6 minutes, the volume ratio of the mobile phase A is increased to 99 percent, the volume ratio of the mobile phase A is 4.6 to 5.5 minutes, and the volume ratio of the mobile phase A is kept 99 percent; the volume fraction of mobile phase a varies uniformly.
Further, the specification of the column was 3.0mm×100mm, and the particle size was 3.0 μm.
The effective separation of the components to be tested is facilitated by selecting chromatographic test conditions and gradient elution modes, and the accuracy of test results is improved.
Further, the determination conditions of the mass spectrum in the supercritical fluid chromatography-tandem mass spectrum are as follows: the scanning mode is negative ion scanning; an electrospray ion source; the temperature of the ion source is 140-150 ℃; the capillary voltage is 2.4-2.6kV; the air flow of the taper hole is 60-70L/h; the flow rate of the desolventizing agent is 600-650L/h; the temperature of the desolventizing gas is 300-330 ℃; and adopting MRM mode acquisition.
Further, the amount of methanol used is 9 to 11mL per 0.18 to 0.22g of sample; the amounts of the C18 magnetic microspheres and the aminated magnetic microspheres were 2mg per 0.02g sample.
The dosage of the methanol and the magnetic microspheres is adjusted within a proper range, so that the components to be detected of the essence sample can be effectively extracted, the use of organic solvents is reduced, the cost is reduced, and the pollution to the environment is reduced.
Further, the mixed extraction is performed in an extraction container, and the magnetic adsorption is to place the extraction container on a magnet for standing separation.
Further, the time of the stationary separation is 6min.
The extraction device is placed on the magnet for standing separation, so that the magnetic microspheres can be quickly settled, no magnetic microspheres in the sample solution to be detected are ensured, and the accuracy of the subsequent test results is improved.
Further, the particle size of the C18 magnetic microsphere and the amino magnetic microsphere is 0.5-1 mu m.
The particle size of the magnetic microspheres is selected to be in the range of 0.5-1 mu m, so that the magnetic microspheres can be ensured to have larger surface area, the effective adsorption of non-target objects can be realized, the rapid precipitation under the action of a magnet can be ensured, the separation can be realized, and the extraction time of a sample solution to be detected can be shortened.
Further, the extraction is an oscillation extraction.
Further, the oscillation speed is 200-250r/min during oscillation extraction, and the time of the oscillation extraction is 8-10min.
The proper vibration frequency and the time for oscillation extraction can improve the extraction effect of the magnetic microsphere on the components to be detected and save the time cost.
Further, the magnetic microspheres are reused after being washed with methanol after each extraction.
The magnetic microspheres are repeatedly used after being cleaned by methanol, so that the cost of sample detection can be reduced.
Drawings
FIG. 1 is a flow chart of an assay method of the present invention;
FIG. 2 is a front view of an extraction tube used in the present invention; in the figure: 1 is an extraction pipe plug, 2 is a capillary, 3 is an extraction pipe orifice, 4 is a left purification cavity, 5 is a glass partition, 6 is a piston knob, 7 is a volume scale, 8 is a right purification cavity, 9 is a liquid taking port, and 10 is a liquid taking port plug;
FIG. 3 is a chromatogram of a sample to be tested having contents of 1.0. Mu.g/g of each of the paraben isomers added in example 5;
FIG. 4 is a chromatogram of a sample to be tested having contents of each of the paraben isomers added in comparative example 1 of 1.0. Mu.g/g;
FIG. 5 is a chromatogram of a sample to be tested having contents of each of the paraben isomers added in comparative example 4 of 1.0. Mu.g/g;
FIG. 6 is a chromatogram of a sample to be tested having a content of each of the paraben isomers added in comparative example 5 of 1.0. Mu.g/g;
FIG. 7 is a chromatogram of a sample to be tested having contents of each of the paraben isomers added in comparative example 6 of 1.0. Mu.g/g.
Detailed Description
The reagent specifications and instrument models involved in the examples are as follows:
methyl alcohol standard solutions (altar ink quality test) with the concentrations of propyl parahydroxybenzoate, isopropyl parahydroxybenzoate, butyl parahydroxybenzoate and isobutyl parahydroxybenzoate of 100 mug/mL respectively; methanol is chromatographic grade; c18 magnetic microsphere (particle size about 0.5-1 μm, available from Beijing future technology development Co., ltd.); the amino magnetic microsphere (particle diameter about 0.5-1 μm, surface amino content about 600nmol/mg, magnetic content 35-45%, purchased from Nanjing Xianfeng nanotechnology Co., ltd.).
Waters supercritical fluid chromatography tandem mass spectrometer; AE 163 electronic balance with a feel of 0.0001g and AE 166 electronic balance with a feel of 0.01g (Mettler company, switzerland).
In order to achieve the convenience of operation and the sorting recovery of the two magnetic microspheres, the extraction tube used in the present invention is shown in fig. 2 below, and it is known to those skilled in the art that the extraction effect can be achieved by using a common extraction device. In addition, the mixed extraction of the C18 magnetic microsphere and the aminated magnetic microsphere is also suitable for treating the sample to be detected in the invention.
The extraction tube used in the invention has a structure schematic diagram shown in fig. 2, and comprises a tube body, wherein the inner cavity of the tube body forms a purification cavity, a glass partition 5 is arranged in the middle of the tube body, and the opening and closing of the glass partition 5 can be controlled through a piston knob 6. The glass partition 5 divides the purifying cavity into a left purifying cavity 4 and a right purifying cavity 8, and the right purifying cavity 8 is provided with a volume scale 7. An extraction pipe orifice 3 is arranged on the left purification cavity 4, an extraction pipe plug 1 is matched with the extraction pipe orifice 3, and a capillary 2 is arranged in the middle of the extraction pipe plug 1; the right side purifying cavity 8 is provided with a liquid taking port 9, and a liquid taking port plug 10 is matched with the liquid taking port 9.
When the extraction tube is used, the glass partition 5 is closed through the piston knob 6, and the C18 magnetic microspheres and the amination magnetic microspheres are respectively placed in the left purifying cavity 4 and the right purifying cavity 8. Adding a sample into the left purification cavity 4 through the extraction pipe orifice 3, adding methanol for oscillation extraction, placing the left side of the extraction pipe downwards on the magnet, and adsorbing the magnetic microspheres in the left extraction pipe 4. The glass partition 5 is opened by the piston knob 6, the right side of the extraction tube is directed downward, and after the sample flows from the left extraction tube 4 to the right extraction tube 8, the glass partition 5 is closed, and the left magnet is removed. After the shaking extraction, the right side of the extraction tube was placed downward on the magnet to adsorb the magnetic microspheres in the right extraction tube 8. And then taking out the sample to be tested from the liquid taking port 9 by using a rubber head dropper for testing and analyzing.
In addition, the extraction tube plug 1 is provided with a capillary tube 2 in the middle, and the capillary tube 2 has the function of balancing the pressure in the extraction tube so as to facilitate the flow of the sample from side to side in the extraction tube.
1. The specific examples of the extraction of the parahydroxybenzoate isomer to-be-detected sample solution in the essence are as follows:
example 1
The flow of extracting the solution of the parahydroxybenzoate isomer to be measured in the essence for measuring the embodiment is shown in fig. 1, and specifically comprises the following steps:
(1) 20mgC magnetic microspheres are placed in the left purifying cavity 4, 20mg of amino magnetic microspheres are placed in the right purifying cavity 8, and plugs 1 and 10 are plugged;
(2) Weighing 0.2g essence, placing into a purifying cavity 4 at the left side of an extraction tube through an extraction tube orifice 3, adding 10mL of methanol, and extracting for 5min (the speed is 200 r/min) by shaking to obtain an extract;
(3) Standing the purifying cavity 4 on the left side of the extracting tube on a magnet for 3min;
(4) Opening a piston knob 6, allowing liquid to enter a right purifying cavity 8 through a piston, oscillating and extracting for 5min (the speed is 200 r/min), standing the right purifying cavity of the extracting tube on a magnet, and separating for 3min;
(5) And taking out the extracting solution from the liquid taking port 9 by using a disposable dropper to obtain a sample solution to be tested.
(6) Adding 2mL of methanol from the extraction pipe orifice 2, standing and separating on a magnet for 3min after oscillation, pouring the methanol out of a liquid outlet, repeatedly cleaning for 3 times, and airing the magnetic microspheres for later use.
Example 2
The difference from example 1 is that: when the sample solution to be detected is extracted, 9mL of methanol is adopted to extract 0.18g of the sample to be treated, and the dosage of the C18 magnetic microsphere and the amino magnetic microsphere is 18mg.
Example 3
The difference from example 1 is that: when the sample solution to be detected is extracted, 11mL of methanol is adopted to extract 0.22g of the sample to be treated, and the dosage of the C18 magnetic microsphere and the amino magnetic microsphere is 22mg.
Example 4
The difference from example 1 is that: the oscillation speed is 250r/min during oscillation extraction, and the time of the two oscillation extraction is 4min; the time of the two standing separation is 3min.
2. Specific examples of the method for measuring the paraben isomer in the essence of the invention are as follows:
example 5
The method for determining the paraben isomer in the essence of the present embodiment uses supercritical fluid chromatography-tandem mass spectrometry to analyze the sample solution to be tested obtained in the embodiment 1, and specifically includes the following steps:
1. preparing a sample solution to be tested: the sample solution to be tested was obtained as in example 1.
2. Preparation of mixed standard working solution: respectively transferring 0.1mL of the standard solution of the parahydroxybenzoate into the same 10mL volumetric flask, and diluting with methanol to a constant volume to prepare a mixed standard stock solution with the concentration of 1.0 mug/mL; respectively transferring a certain volume of mixed standard stock solution into a 10mL volumetric flask, diluting with methanol to a certain volume, and preparing mixed standard working solutions with different concentrations, wherein the concentration sequences are as follows: 20. 50, 100, 200, 500, 1000ng/mL.
3. Standard curve acquisition: and (3) injecting the prepared mixed standard working solutions with different concentrations into SFC-MS/MS, and quantitatively analyzing the parahydroxybenzoate by an external standard method, namely, performing linear regression analysis on the peak area (y) of each standard sample and the concentration (x) of each standard sample to obtain a standard curve, wherein the correlation coefficient is more than 0.999.
4. Analysis of the sample solution to be tested: and (3) injecting the sample solution to be detected obtained in the example 1 into SFC-MS/MS, measuring the chromatographic peak area of the parahydroxybenzoate, substituting the chromatographic peak area into a standard curve, and obtaining the content of the parahydroxybenzoate in the sample, wherein the content of each object to be detected is lower than the detection limit.
The chromatographic conditions used in the measurement are: the column was a Chiralpak IG-3column (3 mm. Times.100 mm,3 μm, japanese Dai Hill Co.); mobile phase A is supercritical CO 2 Mobile phase B is ethanol; the flow rate after mixing the two phases is 2.0mL/min; column temperature is 40 ℃;the sample injection amount is 2 mu L; the elution mode is gradient elution, and the gradient elution program is shown in table 1.
TABLE 1 gradient elution procedure
The mass spectrum conditions adopted in the measurement are as follows: the scanning mode is negative ion scanning; an electrospray ion source; the temperature of the ion source is 150 ℃; the capillary voltage is 2.6kV; the air flow of the taper hole is 70L/h; the flow rate of the desolventizing agent is 650L/h; the desolventizing gas temperature is 330 ℃; MRM parameters are shown in Table 2 using MRM mode acquisition.
Table 2 mass spectrometry conditions
* Quantification of ions
Example 6
The difference from example 5 is that: the total flow rate after mixing of the two phases was 1.8mL/min.
Example 7
The difference from example 5 is that: when SFC-MS/MS is separated, the column temperature is 35 ℃; the sample loading was 5. Mu.L.
Example 8
The difference from example 5 is that: the ion source temperature is 140 ℃; the capillary voltage is 2.4kV; the air flow of the taper hole is 60L/h; the flow rate of the desolventizing agent is 600L/h; the desolventizing gas temperature was 300 ℃.
3. Comparative example
Comparative example 1
The method for processing the sample solution to be tested in this comparative example and the analysis process and conditions of the ultra-high performance liquid chromatography-tandem mass spectrometry are the same as those of the ultra-high performance liquid chromatography-tandem mass spectrometry determination of 8 kinds of preservatives in essence (Deng Lele, etc., chinese food additives, 2019, 1:156-160). The test results are shown in Table 3. The chromatograms are shown in fig. 4, and the two groups of isomers PP and IPP, BP and IBP could not be separated by baseline.
The sample processing method of the ultra-high performance liquid chromatography-tandem mass spectrometry determination of 8 preservatives in essence is as follows: 0.5g of sample is weighed into a 50mL centrifuge tube, 20mL of methanol is added, the mixture is oscillated for 2min by a vortex at 2500r/min, then the mixture is centrifuged for 5min at 8000r/min, and the supernatant is filtered by a 0.22 mu m organic filter membrane and is analyzed by a machine.
Comparative example 2
The method for processing the sample solution to be tested in this comparative example is the same as that of the measurement by ultra-high performance liquid chromatography-tandem mass spectrometry of 8 kinds of preservatives in essence (Deng Lele et al, chinese food additives, 2019, 1:156-160). The extraction liquid is detected by adopting the condition of supercritical fluid chromatography-tandem mass spectrometry. The test results are shown in Table 3. The peak shape of the chromatogram of the comparative example is similar to that of fig. 3, but the recovery rate is lower in the comparative example compared with that of example 5, which shows that the pretreatment method of the invention can remove impurities better and reduce the interference on the detection result.
TABLE 3 recovery rates obtained by different methods
| Measurement method | Recovery (%) |
| Example 5 | 93.3-108.8 |
| Comparative example 1 | 87.5-93.5 |
| Comparative example 2 | 83.5-89.2 |
Comparative example 3
The treatment method of the sample solution to be detected in the comparative example is consistent with the invention, and the extracting solution is detected by adopting the conditions of ultra-high performance liquid chromatography-tandem mass spectrometry of 8 kinds of preservatives in essence (Deng Lele and the like, chinese food additives, 2019, 1:156-160). The peak shape of the comparative chromatogram is similar to that of fig. 4, and the two sets of isomers cannot be separated.
Comparative example 4
This comparative example differs from example 1 in that the chromatographic column used is a Viriddis BEH (2.1 mm. Times.100 mm,1.7 μm). The chromatogram is shown in FIG. 5, where the two sets of isomers cannot be separated.
Comparative example 5
This comparative example differs from example 1 in that the chromatographic column used is a Viridis HSS C18 SB (3 mm. Times.100 mm,1.8 μm). The chromatogram is shown in FIG. 6, where the two sets of isomers could not be separated.
Comparative example 6
This comparative example differs from example 1 in that the chiral column Chiralpak IC-3 (3 mm. Times.100 mm,3 μm) was used as a test. The chromatograms are shown in fig. 7, and the chromatographic peaks of the two groups of isomers are trailing and cannot be separated well.
4. Experimental example
1. Sensitivity of
Different concentrations of standard working solutions of parahydroxybenzoate were added to the blank essence samples, and after extraction and purification, SFC-MS/MS was injected to produce a concentration of 3 times signal to noise ratio (S/n=3) as the method limit of detection (LOD) and a concentration of 10 times signal to noise ratio (S/n=3) as the method limit of quantification (LOQ). The detection limit of the parahydroxybenzoate isomer measured by the measuring method is 0.020-0.026 mug/g, and the quantitative limit is 0.071-0.084 mug/g.
2. Accuracy and repeatability
And adding 1.0 mug/mL of standard solution of the parahydroxybenzoate into the blank essence sample, so that the content of the parahydroxybenzoate in the sample is 1.0 mug/g, and obtaining the sample to be detected. The content of parabens was measured by the methods of example 5 and comparative example 1, respectively. The measured PP, IPP, BP, IBP contents of example 5 were 0.94, 0.95, 0.94 and 0.96mg/kg, respectively, i.e., PP, IPP, BP, IBP was 94%, 95%, 94% and 96% labeled recovery, which indicates that the accuracy of the measurement method of the present invention was high, and the chromatograms of the samples measured by the methods of example 5 and comparative example 1 are shown in fig. 3 and 4.
To determine the reproducibility of the assay of the present invention, standard solutions of parabens isomers were added to blank essence samples, and then sample SFC-MS/MS analysis was performed as in example 5, and the experiment was repeated 5 times, and the recovery was calculated as scalar addition and measurement values, with the results shown in Table 4. As can be seen from Table 4, the recovery rate of the paraben isomer is between 93.3% and 108.8%, and the average Relative Standard Deviation (RSD) is less than 5.0%, which indicates that the recovery rate of the measurement method of the present invention is high and the repeatability is good. The standard recovery of the paraben isomer measured by the method of comparative example 1 was slightly lower (87.5% -93.5%), and separation of the isomer could not be achieved.
Table 4 recovery and repeatability of the process (n=3)
As can be seen from the measurement results of example 5 and comparative example, the pretreatment conditions used in the present invention are simple and convenient, and the extraction and purification are integrated. And aiming at the characteristics of the essence matrix, the magnetic microspheres are selected as the purifying material, so that not only can the interfering substances in the matrix be well removed, but also the recovery rate can be well obtained, and the magnetic microspheres can be repeatedly used for a plurality of times. Analysis by SFC-MS/MS and Chiralpak IG-3 chromatographic column also greatly shortens chromatographic separation time, and two groups of isomers (PP and IPP, BP and IBP) can obtain complete baseline separation. In contrast, the two groups of isomers PP and IPP, BP and IBP in the comparative example could not be baseline separated, affecting the quantitative results.
Claims (8)
1. A method for determining the paraben isomer in a fragrance comprising the steps of:
(1) Mixing and extracting essence, methanol and magnetic microspheres, magnetically adsorbing the magnetic microspheres, and separating to obtain a sample solution to be detected;
(2) Carrying out determination analysis on a sample solution to be detected by using supercritical fluid chromatography-tandem mass spectrometry; the chromatographic column of the supercritical fluid chromatography in the supercritical fluid chromatography-tandem mass spectrometry is Chiralpak IG-3;
the parahydroxybenzoate isomer is propyl parahydroxybenzoate, isopropyl parahydroxybenzoate, butyl parahydroxybenzoate and isobutyl parahydroxybenzoate; the magnetic microspheres are C18 magnetic microspheres and aminated magnetic microspheres; the dosage of the C18 magnetic microsphere and the amino magnetic microsphere is 2mg relative to each 0.02g sample; the determination conditions of the supercritical fluid chromatography in the supercritical fluid chromatography-tandem mass spectrometry are as follows: mobile phase A is supercritical CO 2 The mobile phase B is ethanol, the total flow rate after two phases are mixed is 1.8-2.0mL/min, the column temperature is 35-40 ℃, the sample injection amount is 2-5 mu L, and the elution mode is gradient elution; the determination conditions of the mass spectrum in the supercritical fluid chromatography-tandem mass spectrum are as follows: the scanning mode is anion scanning, electrospray ion source, ion source temperature is 140-150 ℃, capillary voltage is 2.4-2.6kV, taper hole air flow is 60-70L/h, desolvation air flow is 600-650L/h, desolvation air temperature is 300-330 ℃, and MRM mode collection is adopted.
2. The method for determining the paraben isomer in a fragrance according to claim 1, wherein the volume fraction of mobile phase a is reduced from 99% to 90% and then back to 99% during the gradient elution.
3. The method for determining the paraben isomer in a fragrance according to any of claims 1-2, characterized in that the amount of methanol is 9-11mL per 0.18-0.22g sample.
4. The method for determining the paraben isomer in a flavor according to claim 1, wherein the mixed extraction is performed in an extraction vessel and the magnetic adsorption is performed by standing the extraction vessel on a magnet.
5. The method for determining the paraben isomer in a fragrance according to claim 1, wherein the particle size of the C18 magnetic microspheres and the aminated magnetic microspheres is 0.5 to 1 μm.
6. The method of determining the paraben isomer in a fragrance according to claim 1, wherein the extraction is a shaking extraction.
7. The method for measuring the paraben isomer in a flavor according to claim 6, wherein the shaking extraction is performed at a shaking rate of 200-250r/min for 8-10min.
8. The method of claim 1, wherein the magnetic microspheres are reused after washing with methanol after each extraction.
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