CN113009002A - Sample pretreatment method containing furfural substances and method for detecting content of furfural substances - Google Patents
Sample pretreatment method containing furfural substances and method for detecting content of furfural substances Download PDFInfo
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- CN113009002A CN113009002A CN201911329097.XA CN201911329097A CN113009002A CN 113009002 A CN113009002 A CN 113009002A CN 201911329097 A CN201911329097 A CN 201911329097A CN 113009002 A CN113009002 A CN 113009002A
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 211
- 239000000126 substance Substances 0.000 title claims abstract description 129
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000002203 pretreatment Methods 0.000 title claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000706 filtrate Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 238000005374 membrane filtration Methods 0.000 claims abstract description 9
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims abstract description 5
- 235000013336 milk Nutrition 0.000 claims description 32
- 239000008267 milk Substances 0.000 claims description 32
- 210000004080 milk Anatomy 0.000 claims description 32
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 24
- 239000012528 membrane Substances 0.000 claims description 23
- 238000000746 purification Methods 0.000 claims description 20
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 18
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 18
- 235000020122 reconstituted milk Nutrition 0.000 claims description 17
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 15
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 15
- 239000011780 sodium chloride Substances 0.000 claims description 15
- 235000002639 sodium chloride Nutrition 0.000 claims description 15
- IEMMBWWQXVXBEU-UHFFFAOYSA-N 2-acetylfuran Chemical compound CC(=O)C1=CC=CO1 IEMMBWWQXVXBEU-UHFFFAOYSA-N 0.000 claims description 14
- DSMRYCOTKWYTRF-UHFFFAOYSA-N 3-methylfuran-2-carbaldehyde Chemical compound CC=1C=COC=1C=O DSMRYCOTKWYTRF-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003463 adsorbent Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 235000013365 dairy product Nutrition 0.000 claims description 12
- 239000000741 silica gel Substances 0.000 claims description 12
- 229910002027 silica gel Inorganic materials 0.000 claims description 12
- 230000010355 oscillation Effects 0.000 claims description 9
- CFNHVUGPXZUTRR-UHFFFAOYSA-N n'-propylethane-1,2-diamine Chemical compound CCCNCCN CFNHVUGPXZUTRR-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000003495 polar organic solvent Substances 0.000 claims description 4
- 239000002516 radical scavenger Substances 0.000 claims description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 4
- 238000003260 vortexing Methods 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 235000008476 powdered milk Nutrition 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims 2
- 239000012982 microporous membrane Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 49
- 239000000243 solution Substances 0.000 description 46
- 238000005173 quadrupole mass spectroscopy Methods 0.000 description 36
- 239000006228 supernatant Substances 0.000 description 32
- 239000007789 gas Substances 0.000 description 31
- 238000001228 spectrum Methods 0.000 description 31
- 238000011084 recovery Methods 0.000 description 22
- 238000004817 gas chromatography Methods 0.000 description 18
- 238000004885 tandem mass spectrometry Methods 0.000 description 15
- 238000000926 separation method Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001819 mass spectrum Methods 0.000 description 10
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 9
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000012159 carrier gas Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000001307 helium Substances 0.000 description 7
- 229910052734 helium Inorganic materials 0.000 description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 7
- 238000002552 multiple reaction monitoring Methods 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000011550 stock solution Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 208000005156 Dehydration Diseases 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000013065 commercial product Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000002372 labelling Methods 0.000 description 4
- 238000004811 liquid chromatography Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- 235000013350 formula milk Nutrition 0.000 description 2
- RMLAKANWLJKGTI-UHFFFAOYSA-N furan;propan-2-one Chemical compound CC(C)=O.C=1C=COC=1 RMLAKANWLJKGTI-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001946 ultra-performance liquid chromatography-mass spectrometry Methods 0.000 description 2
- 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
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- XBJFCYDKBDVADW-UHFFFAOYSA-N acetonitrile;formic acid Chemical compound CC#N.OC=O XBJFCYDKBDVADW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000000276 potassium ferrocyanide Substances 0.000 description 1
- 230000006920 protein precipitation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Images
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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
-
- 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
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/30—Control of physical parameters of the fluid carrier of temperature
-
- 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
- G01N30/32—Control of physical parameters of the fluid carrier of pressure or speed
-
- 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
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention relates to the technical field of analytical chemistry, and discloses a sample pretreatment method containing furfural substances and a method for detecting the content of the furfural substances, wherein the method comprises the following steps: 1) mixing a sample containing furfural substances with an organic solvent; 2) demulsifying the mixed liquid obtained in the step 1); 3) dehydrating the demulsified solution obtained in the step 2); 4) purifying the solution obtained in the step 3) after water removal; 5) and (4) performing membrane filtration on the purified solution, and collecting filtrate. The invention also provides a method for detecting the content of the furfural substances, which comprises the steps of treating a sample containing the furfural substances by adopting the treatment method, and then quantitatively analyzing the content of the furfural substances in the filtrate by using a gas chromatography-mass spectrometry combined method; the method can be used for simultaneously detecting the contents of four furfural substances, and has higher accuracy and precision of detection results.
Description
Technical Field
The invention relates to the field of analytical chemistry, in particular to a method for pretreating a sample containing furfural substances and a method for detecting the content of the furfural substances.
Background
In order to prolong the shelf life of the dairy product and ensure good mouthfeel, the dairy product needs to be subjected to heat treatment in different degrees and different modes, but Maillard reaction easily occurs during heat processing and storage to generate corresponding furfural substances, including: hydroxymethyl furfural (5-HMF), furfural (F), Methyl Furfural (MF), furan methyl ketone (FMC) and the like, thereby damaging the quality of the dairy product. The content change of the hydroxymethylfurfural is used for monitoring the processing and storage processes of the dairy products as a marker in the middle stage of the Maillard reaction. The content of other furfural substances in the dairy products indirectly determines the flavor and quality of the dairy products. Therefore, the content determination of the four furfural substances in the dairy products is of great importance to the food processing industry.
At present, the main methods for detecting four furfural substances (hydroxymethyl furfural, methyl furfural and 2-acetyl furan) in dairy products are protein precipitation and liquid-liquid extraction for pretreating samples, and the two methods have the problems of high organic reagent consumption, poor repeatability, long time consumption and the like. The content determination is carried out by methods such as High Performance Liquid Chromatography (HPLC), ultra performance liquid chromatography-mass spectrometry (UPLC-MS), Gas Chromatography (GC), gas chromatography-mass spectrometry (GC-MS) and the like. However, the existing method for simultaneously extracting the four furfural substances ensures that the recovery rate of the four furfural substances is low and the detection sensitivity of the four furfural substances is low. High Performance Liquid Chromatography (HPLC) is the most commonly used quantitative analysis method for furfural substances, but due to limitations in sensitivity and selectivity, simultaneous detection of four furfural substances has certain limitations, and generally only one furfural substance can be detected, and the detected content is low, so that the content of the four furfural substances cannot be truly reflected. In the current national standards, only the detection method for hydroxymethylfurfural (NY/T1332) -2007 is available, and the method for simultaneously detecting hydroxymethylfurfural, furfural, methylfurfural and furylmethyl ketone is still blank.
Disclosure of Invention
The invention aims to solve the problems of low accuracy and precision of detection results in the prior art, and provides a method which can detect four furfural substances simultaneously and has high accuracy and precision of detection results.
In order to achieve the above object, in a first aspect, the present invention provides a method for pretreating a sample containing a furfural substance, wherein the method comprises the following steps: 1) mixing a sample containing furfural substances with an organic solvent; 2) demulsifying the mixed liquid obtained in the step 1); 3) dehydrating the demulsified solution obtained in the step 2); 4) purifying the solution obtained in the step 3) after water removal; 5) and (4) performing membrane filtration on the purified solution, and collecting filtrate.
In a second aspect, the invention provides a method for detecting the content of furfural substances, which comprises the steps of treating a sample containing furfural substances and then quantitatively analyzing the content of furfural substances in filtrate by using a gas chromatography-mass spectrometry combined method, wherein the sample containing furfural substances is treated by using the method.
The detection method of the furfural substances provided by the invention improves the accuracy and precision of the detection results of the four furfural substances. The reason for this is probably because the method of the present invention obtains higher recovery rates for the four furfural substances in the sample processing process, and combines the gas chromatography-tandem mass spectrometry technology, so that the four furfural substances can be simultaneously and quantitatively analyzed, and the accuracy and precision of the quantitative analysis result are higher. The method is particularly suitable for simultaneously detecting four furfural substances in the dairy products.
Drawings
FIG. 1a is a triple quadrupole mass spectrometry spectrum of an unlabeled sample of example 1 of the present invention;
FIG. 1b is a triple quadrupole mass spectrometry spectrum of a spiked sample of example 1 of the present invention;
FIG. 2a is a triple quadrupole mass spectrometry spectrum of an unlabeled sample of example 2 of the present invention;
FIG. 2b is a triple quadrupole mass spectrometry spectrum of a spiked sample of example 2 of the present invention;
FIG. 3a is a triple quadrupole mass spectrometry spectrum of an unlabeled sample of example 3 of the present invention;
FIG. 3b is a triple quadrupole mass spectrometry spectrum of a spiked sample of example 3 of the present invention;
FIG. 4a is a triple quadrupole mass spectrometry spectrum of an unlabeled sample of example 4 of the present invention;
FIG. 4b is a triple quadrupole mass spectrometry profile of a spiked sample of example 4 of the present invention;
FIG. 5a is a triple quadrupole mass spectrometry spectrum of an unlabeled sample of example 5 of the present invention;
FIG. 5b is a triple quadrupole mass spectrometry spectrum of a spiked sample of example 5 of the present invention;
FIG. 6a is a triple quadrupole mass spectrometry spectrum of an unlabeled sample of example 6 of the present invention;
FIG. 6b is a triple quadrupole mass spectrometry profile of a spiked sample of example 6 of the present invention;
FIG. 7a is a triple quadrupole mass spectrometry spectrum of an unlabeled sample of example 7 of the present invention;
FIG. 7b is a triple quadrupole mass spectrometry spectrum of a spiked sample of example 7 of the present invention;
FIG. 8a is a triple quadrupole mass spectrometry spectrum of an unlabeled sample of example 8 of the present invention;
FIG. 8b is a triple quadrupole mass spectrometry spectrum of a spiked sample of example 8 of the present invention;
FIG. 9a is a triple quadrupole mass spectrometry spectrum of an unlabeled sample of example 9 of the present invention;
FIG. 9b is a triple quadrupole mass spectrometry spectrum of a spiked sample of example 9 of the present invention;
FIG. 10a is a triple quadrupole mass spectrometry spectrum of an unlabeled sample of comparative example 1 of the present invention;
FIG. 10b is a triple quadrupole mass spectrometry spectrum of a spiked sample of comparative example 1 of the present invention;
FIG. 11a is a liquid chromatography profile of an unlabeled sample of comparative example 2 of the present invention;
FIG. 11b is a liquid chromatography profile of a spiked sample of comparative example 2 of the present invention;
FIG. 12a is a triple quadrupole mass spectrometry spectrum of an unlabeled sample of comparative example 3 of the present invention;
FIG. 12b is a triple quadrupole mass spectrometry profile of a spiked sample of comparative example 3 of the present invention;
in fig. 1 a-12 b, peak 1 is furfural, peak 2 is 2-acetylfuran, peak 3 is methylfurfural, and peak 4 is hydroxymethylfurfural.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a method for pretreating a sample containing furfural substances, wherein the method comprises the following steps: 1) mixing a sample containing furfural substances with an organic solvent; 2) demulsifying the mixed liquid obtained in the step 1); 3) dehydrating the demulsified solution obtained in the step 2); 4) purifying the solution obtained in the step 3) after water removal; 5) and (4) performing membrane filtration on the purified solution, and collecting filtrate.
According to the invention, the sample is not particularly limited, and the treatment method is particularly suitable for treating furfural substances in dairy products, preferably, the dairy products can be milk, milk powder or reconstituted milk.
According to the present invention, there is no particular limitation on the type of the furfural substance, and the treatment method of the present invention is particularly suitable for the detection of four substances, furfural, methylfurfural, hydroxymethylfurfural or 2-acetylfuran, and a preferred embodiment of the present invention is the simultaneous detection of four substances, furfural, methylfurfural, hydroxymethylfurfural and 2-acetylfuran.
According to the present invention, the organic solvent may be a polar organic solvent, and in order to increase the recovery rate of the furfural-like substance, the organic solvent is preferably a polar organic solvent having a boiling point of 50 to 85 ℃, and more preferably at least one of acetonitrile, methanol, ethanol, and acetone.
According to the present invention, in order to improve the recovery rate of the furfural-based substance, the amount of the organic solvent is preferably 1 to 5mL, more preferably 1 to 3mL, relative to 1g of a sample containing the furfural-based substance.
According to the present invention, the manner of mixing the sample and the organic solvent may be various manners as long as the sample and the organic solvent can be uniformly mixed, and for example, the mixing manner may be any one or a combination of several of shaking mixing, vortex mixing or stirring mixing, and the mixing manner is preferably vortex mixing in order to improve the recovery rate of the four furfural substances.
According to the present invention, preferably, the conditions of the vortex mixing include a rotation speed of 3000-.
According to the invention, in order to improve the recovery rate of the furfural substances, demulsification can be carried out after a sample containing the furfural substances is mixed with an organic solvent, and the demulsification can be carried out in a physical-chemical mode and/or a physical-mechanical mode, preferably in a physical-chemical mode and a physical-mechanical mode.
According to the invention, in order to improve the recovery rate of furfural substances, a demulsifier is preferably added to perform demulsification in a physical and chemical manner; the physical and mechanical mode is preferably filtration, ultrasonic oscillation or vortex, and the like, and more preferably ultrasonic oscillation.
According to the invention, the demulsifier can be various substances which can perform demulsification and do not influence the content determination of the furfural substances, and in order to improve the recovery rate of the furfural substances, the demulsifier is preferably inorganic salt. Wherein, the inorganic salt is preferably selected from one or more of sodium chloride, sodium acetate, sodium citrate and sodium sulfate, and is more preferably selected from sodium chloride and sodium acetate.
According to the invention, in order to further improve the recovery rate of the furfural substances, the weight ratio of the sodium chloride to the sodium acetate is preferably 1-5:1, and more preferably 2-4: 1.
According to the invention, in order to further improve the recovery rate of the furfural substances, the amount of the demulsifier is preferably 0.4-1.2g, more preferably 0.6-1g, relative to 1g of a sample containing the furfural substances.
According to the invention, in order to uniformly mix the demulsifier, the step 2) further comprises adding the demulsifier into the mixed liquid obtained in the step 1) and then performing vortex, wherein preferably, the rotation speed of the vortex is 3000-6000rpm and the time is 1-5 min.
According to the invention, the ultrasonic oscillation is carried out on the solution after the vortex in the step 2), which is more beneficial to improving the recovery rate of furfural substances, and in order to further improve the recovery rate of furfural substances, the mixed solution obtained in the step 1) is mixed with the demulsifier and then sequentially subjected to vortex and ultrasonic oscillation. Preferably, the frequency of the ultrasonic oscillation is 30-50KHz, and the time is 15-25 min.
According to the invention, the method for removing water in the step 3) comprises the step of contacting a water removing agent with the demulsified solution, wherein in order to improve the recovery rate of the furfural substances, the conditions for contacting the water removing agent with the demulsified solution comprise that the temperature is 15-25 ℃ and the time is 1-5 min.
According to the invention, in order to improve the recovery rate of the furfural substances, the amount of the water scavenger is preferably 0.5-1.2g relative to 1g of a sample containing the furfural substances.
According to the invention, in order to improve the recovery rate of the furfural substances, the water removal agent is preferably at least one of anhydrous magnesium sulfate, anhydrous sodium carbonate, anhydrous potassium carbonate and phosphorus pentoxide, and is more preferably anhydrous magnesium sulfate.
According to the invention, in order to improve the recovery rate of the furfural substances, the step 3) further comprises stirring, vortexing or oscillating the solution added with the water removing agent, preferably vortexing the solution added with the water removing agent.
According to the invention, in order to improve the recovery rate of the furfural substances, the rotation speed of the vortex in the step 3) is preferably 3000-6000rpm, and the vortex time is 1-5 min.
According to the invention, the demulsified solution obtained in the step 3) is subjected to solid-liquid separation after water removal, and the supernatant is collected, wherein the solid-liquid separation mode can be filtration, centrifugation or concentration, and the solid-liquid separation mode is preferably centrifugation in order to further improve the solid-liquid separation effect.
According to the present invention, in order to further improve the effect of solid-liquid separation, it is preferable that the centrifugation conditions include a temperature of 10 to 20 ℃, a rotation speed of 5000-.
According to the invention, the method further comprises purifying the supernatant, wherein in order to reduce the content of non-furfural substances in the supernatant, the purification is preferably adsorption purification, filtration purification or precipitation purification, and more preferably adsorption purification.
According to the invention, a preferred method of adsorption purification is to contact an adsorbent with the water-depleted solution. The contact condition of the adsorbent and the dehydrated solution comprises that the temperature is 15-25 ℃ and the time is 5-30 min.
According to the present invention, preferably, the amount of the adsorbent is 50 to 140mg relative to 1mL of the water-removed solution obtained in step 3).
According to the invention, preferably, the adsorbent is selected from any one or more of C18 bonded silica gel, N-propyl ethylene diamine (PSA), amino modified bonded silica gel, Florisil, neutral alumina, more preferably, the adsorbent is selected from C18 bonded silica gel and PSA.
More preferably, the weight ratio of the N-propylethylenediamine to the C18-bonded silica gel is 1: 2-6.
According to the present invention, water removal can be simultaneously performed during the purification process to further improve the purification effect, and therefore, preferably, the purification method further includes simultaneously contacting the adsorbent and the water removal agent with the water-removed solution. Preferably, the amount of the water scavenger used in the purification process is preferably 144-270mg relative to 1mL of the water-depleted solution obtained in step 3). The water removal agent used in the purification process may be the same as or different from the water removal agent used in the water removal process, and for example, may be at least one selected from the group consisting of anhydrous magnesium sulfate, anhydrous sodium carbonate, anhydrous potassium carbonate, and phosphorus pentoxide, and more preferably anhydrous magnesium sulfate.
According to the present invention, in order to further improve the purification effect, it is preferable that the weight ratio of the C18-bonded silica gel, the anhydrous magnesium sulfate, and the PSA is (2-6): (8-12): 1.
according to the present invention, the step 5) further comprises performing solid-liquid separation on the purified solution before membrane filtration, wherein the solid-liquid separation method may be filtration, centrifugation or concentration, and the solid-liquid separation method is preferably centrifugation in order to further enhance the effect of solid-liquid separation.
According to the present invention, in order to further improve the effect of solid-liquid separation, it is preferable that the centrifugation conditions include a temperature of 10 to 20 ℃, a rotation speed of 5000-.
According to the invention, before the gas chromatography in step 5), membrane filtration is performed on the purified solution, preferably, the membrane used for membrane filtration is selected from a nylon microporous filter membrane, a polyvinylidene fluoride membrane (VDF membrane) or a Polytetrafluoroethylene (PTFE) membrane, and more preferably, a Polytetrafluoroethylene (PTFE) membrane.
According to a preferred embodiment of the present invention, in order to further enhance the effect of membrane filtration, the pore size of the filter membrane is 0.22 μm to 0.45 μm, more preferably 0.22 μm to 0.3 μm.
In a second aspect, the invention provides a method for detecting the content of furfural substances, which comprises the steps of treating a sample containing furfural substances, and then quantitatively analyzing the content of furfural substances in filtrate by using a gas chromatography-mass spectrometry combined method, wherein the sample containing furfural substances is treated by using the method.
According to the invention, the conditions of the gas chromatography can be selected from the conditions conventional in the field, but in order to further improve the separation efficiency of the furfural substances, a preferred embodiment of the invention is as follows: the gas chromatography uses a polar column, preferably the polar column is a column Rtx-WAX, specification (30m 0.25mm 0.25 μm).
According to the invention, in order to further improve the separation effect of the gas chromatography, a preferred embodiment of the invention is that the sample injection amount of the gas chromatography is 1-2 μ L, the sample injection port temperature is 220-280 ℃, and the column flow rate is 0.8-1.2 mL/min.
According to the invention, in order to further improve the separation effect of the gas chromatography, a preferred embodiment of the invention is that the initial temperature of the gas chromatography is 50-70 ℃ and the retention time is 1-5 min.
According to the invention, in order to further improve the separation effect of the gas chromatography, a preferred embodiment of the invention is that the temperature of the gas chromatography is raised to 120-180 ℃ at a rate of 15-25 ℃/min, the temperature is kept for 1-5min, and then the temperature is raised to 200-230 ℃ at a rate of 5-15 ℃/min, and the temperature is kept for 5-10 min.
According to the invention, the mass spectrum can be a mass spectrum conventional in the field, and in order to improve the accuracy and precision of the detection of the content of the furfural substances, a triple quadrupole mass spectrum is preferred.
According to the present invention, the triple quadrupole mass spectrometry conditions can be conditions conventionally used in the art, but in order to further improve the accuracy and precision of the triple quadrupole mass spectrometry for simultaneously and quantitatively analyzing the content of four furfural substances, a preferred triple quadrupole mass spectrometry condition of the present invention comprises: the ionization mode is electron bombardment source, the ionization capacity is 70eV, the temperature of the transmission line is 230-280 ℃, and the temperature of the ion source is 200-300 ℃.
According to the invention, in order to further improve the accuracy and precision of the triple quadrupole mass spectrometry for simultaneously and quantitatively analyzing the content of the four furfural substances, a preferred triple quadrupole mass spectrometry condition of the invention further comprises selecting three pairs of parent ion-daughter ion pairs.
The present invention will be described in detail below by way of examples. In the following examples and comparative examples, various raw materials used below were all commercially available without specific description.
The milk is fresh milk of ASP company;
the milk powder is first-stage infant milk powder of Junlebao company;
the reconstituted milk is fruit granule reconstituted lactic acid milk of Mongolian company;
c18 bonded silica gel (C18) was purchased from Beijing Naixiang technology, Inc., under the designation 72750;
PSA is available from Beijing Shaxiang technology, Inc. under the designation 78925G;
the sodium chloride is purchased from chemical reagents of national medicine group, and the purity is more than or equal to 99.5 weight percent;
the anhydrous sodium acetate is purchased from chemical reagents of national medicine group, and the purity is more than or equal to 99.0 weight percent;
the anhydrous magnesium sulfate is purchased from chemical reagents of national medicine group, and the purity is 99.5 percent by weight;
the furfural standard is a commercial product of Dr. Ehretroffer GmbH company in Germany, the specification is 0.25g, and the purity is more than 95 weight percent;
the standard methylfurfural is a commercial product of Dr. Ehretroffer GmbH company in Germany, the specification is 0.25g, and the purity is more than 95 weight percent;
the standard hydroxymethyl furfural product is a product sold by Shanghai' an spectral experiment science and technology company Limited, the specification is 20mg, and the purity is more than 95 weight percent;
the 2-acetylfuran standard substance is a product sold by Shanghai' an spectral experiment science and technology GmbH, the specification is 5.0g, and the purity is more than 98 weight percent;
the gas chromatography-triple quadrupole mass spectrometry is a commercial product with the trade name of TSQ8000 of the Sammerfei company;
the high performance liquid chromatograph is a commercial product with the trade name of U3000 of the Saimei Fei company;
the PTFE membrane is a product sold in Beijing Yanxiang science and technology Limited, and the aperture of the membrane is 0.22 mu m;
column Rtx-WAX (30m 0.25mm 0.25 μm) is commercially available from Shimadzu corporation;
the liquid chromatography column was an AQ-C18 column (4.6 x 250mm, 5 μm) from Welch, USA;
the recovery rate of the added standard is as follows: taking two parts of the same sample, adding a quantitative standard substance of a component to be detected into one part of the sample to obtain a labeled sample, and simultaneously measuring the amount of the substance to be detected in the two parts of the sample by adopting the same detection method, wherein the ratio of the difference value of the measured value of the labeled sample and the measured value of the unlabeled sample to the amount of the added standard substance is the sample labeling recovery rate. The calculation formula is as follows: standard recovery ═ amount of added standard substance × 100% (standard sample measurement value-non-standard sample measurement value);
the accuracy refers to: the degree to which the measured value is close to the true value is expressed in the present invention as the recovery rate in normalized form, where normalized recovery rate is (normalized sample measured value-normalized sample measured value) ÷ amount of added standard substance × 100%;
the precision refers to: the degree of closeness of the results of the multiple measurements is expressed by calculating the Relative Standard Deviation (RSD) of the results of the 6 measurements by repeating the measurement 6 times on the filtrate after passing through the membrane in the present invention.
Example 1
Weighing two milk samples, wherein each milk sample is 5.0g, and one milk sample is added with 0.001mg of furfural standard substance, 0.001mg of methylfurfural standard substance, 0.001mg of hydroxymethylfurfural standard substance and 0.001mg of 2-acetylfuran standard substance to be used as a standard sample.
The following steps were carried out for two milk samples, respectively:
1) adding 10mL of acetonitrile into a milk sample, fully swirling for 2min at 3000rpm, and mixing;
2) adding 3g of sodium chloride and 1g of anhydrous sodium acetate into the mixed solution obtained in the step 1), fully whirling for 2min at 3000rpm, and then ultrasonically oscillating for 20min at the frequency of 40 KHz;
3) adding 3g of anhydrous magnesium sulfate into the solution obtained in the step 2), performing vortex treatment for 2min at 20 ℃ and 3000rpm, performing dehydration treatment, centrifuging the solution after dehydration for 5min at 15 ℃ and 6000rpm by using a refrigerated centrifuge, and collecting supernatant;
4) collecting 1ml of supernatant, adding 40mg of C18, 100mg of anhydrous magnesium sulfate and 10mg of PSA, purifying at 20 ℃ for 15min, centrifuging the purified solution at 5000rpm for 5min, collecting the supernatant, passing the supernatant through a 0.22-micron PTFE membrane, and collecting the filtrate for later use;
5) detecting the content of furfural substances in the filtrate collected in the step 4) by adopting gas chromatography-tandem triple quadrupole mass spectrometry, and repeatedly measuring for 6 times, wherein the conditions of the gas chromatography are as follows: using a chromatographic column Rtx-WAX of specification (30m x 0.25mm x 0.25 μm), helium (He) as carrier gas, (Ar) as collision gas, 250 ℃ as injection port temperature, constant flow mode, column flow rate of 1ml/min, gas chromatography-tandem mass spectrometry temperature programmed parameters as shown in table 1:
the mass spectrum conditions of the triple quadrupole are as follows: the ionization mode is electron bombardment source (EI), the temperature of transmission line is 280 ℃, the temperature of ion source is 300 ℃, the ionization energy is 70eV, MRM multiple reaction monitoring mode is selected, and the parameters for measuring four furfural compounds by gas chromatography-tandem mass spectrometry are shown in Table 2:
the detection spectra are shown in FIG. 1a (unlabeled sample) and FIG. 1b (labeled sample), the detection results are shown in Table 4, and the accuracy and precision of the detection results are shown in Table 5.
Example 2
Weighing 25.0g of milk powder, fully dissolving the milk powder in 180ml of ultrapure water at 37 ℃, taking the milk powder as a stock solution, weighing two stock solution samples, wherein each stock solution sample is 5.0g, and one of the two stock solution samples is added with 0.001mg of furfural standard substance, 0.001mg of methylfurfural standard substance, 0.001mg of hydroxymethylfurfural standard substance and 0.001mg of 2-acetylfuran standard substance to be taken as a standard adding sample.
Two stock solution samples were separately subjected to the following steps:
1) adding 10mL of acetonitrile into the stock solution sample, and fully swirling for 2min at 4000rpm for mixing;
2) adding 3g of sodium chloride and 1g of anhydrous sodium acetate into the mixed solution obtained in the step 1), fully whirling for 2min at 4000rpm, and then ultrasonically oscillating for 20min at the frequency of 40 KHz;
3) adding 3g of anhydrous magnesium sulfate into the solution obtained in the step 2), performing vortex for 3min at the temperature of 20 ℃ and the speed of 4000rpm, performing water removal treatment, centrifuging the solution after water removal for 5min at the temperature of 10 ℃ and the speed of 6000rpm, and collecting supernatant;
4) collecting 1ml of supernatant, adding 40mg of C18, 100mg of anhydrous magnesium sulfate and 10mg of PSA, purifying at 20 ℃ for 16min, centrifuging the purified solution at 5000rpm for 5min, collecting the supernatant, passing the supernatant through a 0.22-micron PTFE membrane, and collecting the filtrate for later use;
5) detecting the content of furfural substances in the filtrate collected in the step 4) by adopting gas chromatography-tandem triple quadrupole mass spectrometry, and repeatedly measuring for 6 times, wherein the conditions of the gas chromatography are as follows: using a chromatographic column Rtx-WAX of specification (30m x 0.25mm x 0.25 μm), helium (He) as carrier gas, (Ar) as collision gas, 250 ℃ as injection port temperature, constant flow mode, column flow rate of 1ml/min, gas chromatography-tandem mass spectrometry temperature programmed parameters as shown in table 1:
the mass spectrum conditions of the triple quadrupole are as follows: the ionization mode is electron bombardment source (EI), the temperature of transmission line is 280 ℃, the temperature of ion source is 300 ℃, the ionization energy is 70eV, MRM multiple reaction monitoring mode is selected, and the parameters for measuring four furfural compounds by gas chromatography-tandem mass spectrometry are shown in Table 2;
the detection spectra are shown in FIG. 2a (unlabeled sample) and FIG. 2b (labeled sample), the detection results are shown in Table 4, and the accuracy and precision of the detection results are shown in Table 5.
Example 3
Weighing two reconstituted milk samples, wherein each reconstituted milk sample is 5.0g, and one of the two reconstituted milk samples is added with 0.0025mg of furfural standard substance, 0.0025mg of methylfurfural standard substance, 0.0025mg of hydroxymethylfurfural standard substance and 0.0025mg of 2-acetylfuran standard substance to serve as a labeling sample.
Two reconstituted milk samples were subjected to the following steps, respectively:
1) adding 10mL of acetonitrile into the reconstituted milk sample, and fully swirling for 2min at 3500rpm for mixing;
2) adding 3g of sodium chloride and 1g of anhydrous sodium acetate into the mixed solution obtained in the step 1), fully whirling for 2min at 3500rpm, and then ultrasonically oscillating for 20min at the frequency of 40 KHz;
3) adding 3g of anhydrous magnesium sulfate into the solution obtained in the step 2), performing vortex for 3min at the temperature of 20 ℃ and the speed of 4000rpm, performing water removal treatment, centrifuging the solution after water removal for 5min at the temperature of 20 ℃ and the speed of 6000rpm, and collecting supernatant;
4) collecting 1ml of supernatant, adding 40mg of C18, 100mg of anhydrous magnesium sulfate and 10mg of PSA, purifying at 20 ℃ for 18min, centrifuging the purified solution at 5000rpm for 5min, collecting the supernatant, passing the supernatant through a 0.22-micron PTFE membrane, and collecting the filtrate for later use;
5) detecting the content of furfural substances in the filtrate collected in the step 4) by adopting gas chromatography-tandem triple quadrupole mass spectrometry, and repeatedly determining for 6 times, wherein the conditions of the gas chromatography are as follows: using a chromatographic column Rtx-WAX of specification (30m x 0.25mm x 0.25 μm), helium (He) as carrier gas, (Ar) as collision gas, 250 ℃ as injection port temperature, constant flow mode, column flow rate of 1ml/min, gas chromatography-tandem mass spectrometry temperature programmed parameters as shown in table 1:
the mass spectrum conditions of the triple quadrupole are as follows: the ionization mode is electron bombardment source (EI), the temperature of transmission line is 280 ℃, the temperature of ion source is 300 ℃, the ionization energy is 70eV, MRM multiple reaction monitoring mode is selected, and the parameters for measuring four furfural compounds by gas chromatography-tandem mass spectrometry are shown in Table 2;
the detection spectra are shown in FIG. 3a (unlabeled sample) and FIG. 3b (labeled sample), the detection results are shown in Table 4, and the accuracy and precision of the detection results are shown in Table 5.
Example 4
Weighing two reconstituted milk samples, wherein each reconstituted milk sample is 5.0g, and one of the two reconstituted milk samples is added with 0.002mg of furfural standard substance, 0.002mg of methylfurfural standard substance, 0.002mg of hydroxymethyl furfural standard substance and 0.002mg of 2-acetylfuran standard substance to serve as a labeling sample.
Two reconstituted milk samples were subjected to the following steps, respectively:
1) adding 15mL of acetonitrile into the reconstituted milk sample, fully swirling for 5min at 5000rpm, and mixing;
2) adding 4g of sodium chloride and 1g of anhydrous sodium acetate into the mixed solution obtained in the step 1), fully whirling for 1min at 5000rpm, and then ultrasonically oscillating for 25min at the frequency of 40 KHz;
3) adding 5g of anhydrous magnesium sulfate into the solution obtained in the step 2), performing vortex for 3min at 15 ℃ and 5000rpm, performing water removal treatment, centrifuging the solution after water removal for 5min at 20 ℃ and 6000rpm, and collecting supernatant;
4) collecting 1ml of supernatant, adding 20mg of C18, 80mg of anhydrous magnesium sulfate and 10mg of PSA, purifying at 15 ℃ for 5min, centrifuging the purified solution at 5000rpm for 5min, collecting the supernatant, passing the supernatant through a 0.22-micron PTFE membrane, and collecting the filtrate for later use;
5) detecting the content of furfural substances in the filtrate collected in the step 4) by adopting gas chromatography-tandem triple quadrupole mass spectrometry, and repeatedly determining for 6 times, wherein the conditions of the gas chromatography are as follows: using a chromatographic column Rtx-WAX of specification (30m x 0.25mm x 0.25 μm), helium (He) as carrier gas, (Ar) as collision gas, 250 ℃ as injection port temperature, constant flow mode, column flow rate of 1ml/min, gas chromatography-tandem mass spectrometry temperature programmed parameters as shown in table 1:
the mass spectrum conditions of the triple quadrupole are as follows: the ionization mode is electron bombardment source (EI), the temperature of transmission line is 280 ℃, the temperature of ion source is 300 ℃, the ionization energy is 70eV, MRM multiple reaction monitoring mode is selected, and the parameters for measuring four furfural compounds by gas chromatography-tandem mass spectrometry are shown in Table 2:
the detection spectra are shown in FIG. 4a (unlabeled sample) and FIG. 4b (labeled sample), the detection results are shown in Table 4, and the accuracy and precision of the detection results are shown in Table 5.
Example 5
Weighing two milk samples, wherein each milk sample is 5.0g, and one milk sample is added with 0.02mg of furfural standard substance, 0.02mg of methylfurfural standard substance, 0.02mg of hydroxymethylfurfural standard substance and 0.02mg of 2-acetylfuran standard substance to serve as a standard sample.
The following steps were carried out for two milk samples, respectively:
1) adding 5mL of acetonitrile into a milk sample, fully swirling for 5min at 4500rpm, and mixing;
2) adding 1.5g of sodium chloride and 1.5g of anhydrous sodium acetate into the mixed solution obtained in the step 1), fully whirling for 1min at 4500rpm, and then ultrasonically oscillating for 25min at 40KHz frequency;
3) adding 2.5g of anhydrous magnesium sulfate into the solution obtained in the step 2), performing vortex for 4min at the temperature of 25 ℃ and the rpm of 4500, performing dewatering treatment, centrifuging the dewatered solution for 5min at the temperature of 15 ℃ and the rpm of 6000, and collecting supernatant;
4) collecting 1ml of supernatant, adding 60mg of C18, 120mg of anhydrous magnesium sulfate and 10mg of PSA, purifying at 25 ℃ for 8min, centrifuging the purified solution at 5000rpm for 5min, collecting the supernatant, passing the supernatant through a 0.22-micron PTFE membrane, and collecting the filtrate for later use;
5) detecting the content of furfural substances in the filtrate collected in the step 4) by adopting gas chromatography-tandem triple quadrupole mass spectrometry, and repeatedly determining for 6 times, wherein the conditions of the gas chromatography are as follows: using a chromatographic column Rtx-WAX of specification (30m x 0.25mm x 0.25 μm), helium (He) as carrier gas, (Ar) as collision gas, 250 ℃ as injection port temperature, constant flow mode, column flow rate of 1ml/min, gas chromatography-tandem mass spectrometry temperature programmed parameters as shown in table 1:
the mass spectrum conditions of the triple quadrupole are as follows: the ionization mode is electron bombardment source (EI), the temperature of transmission line is 280 ℃, the temperature of ion source is 300 ℃, the ionization energy is 70eV, MRM multiple reaction monitoring mode is selected, and the parameters for measuring four furfural compounds by gas chromatography-tandem mass spectrometry are shown in Table 2:
the detection spectra are shown in FIG. 5a (unlabeled sample) and FIG. 5b (labeled sample), the detection results are shown in Table 4, and the accuracy and precision of the detection results are shown in Table 5.
Example 6
Weighing two milk samples, wherein each milk sample is 5.0g, and one milk sample is added with 0.005mg of furfural standard substance, 0.005mg of methylfurfural standard substance, 0.005mg of hydroxymethylfurfural standard substance and 0.005mg of 2-acetylfuran standard substance to serve as a standard sample.
The following steps were carried out for two milk samples, respectively:
1) adding 15mL of acetonitrile into a milk sample, fully swirling for 5min at 5000rpm, and mixing;
2) adding 5g of sodium chloride and 1g of anhydrous sodium acetate into the mixed solution obtained in the step 1), fully whirling for 5min at 5000rpm, and then ultrasonically oscillating for 15min at the frequency of 40 KHz;
3) adding 5g of anhydrous magnesium sulfate into the solution obtained in the step 2), performing vortex treatment for 5min at 25 ℃ and 5000rpm, performing dehydration treatment, centrifuging the solution after dehydration in a high-speed refrigerated centrifuge for 5min at 20 ℃ and 6000rpm, and collecting supernatant;
4) collecting 1ml of supernatant, adding 19mg of C18, 72mg of anhydrous magnesium sulfate and 9mg of PSA, purifying at 15 ℃ for 30min, centrifuging the purified solution at 5000rpm for 5min, collecting the supernatant, passing the supernatant through a 0.22 mu m PTFE membrane, and collecting the filtrate for later use;
5) detecting the content of furfural substances in the filtrate collected in the step 4) by adopting gas chromatography-tandem triple quadrupole mass spectrometry, and repeatedly determining for 6 times, wherein the conditions of the gas chromatography are as follows: using a chromatographic column Rtx-WAX of specification (30m x 0.25mm x 0.25 μm), helium (He) as carrier gas, AR as collision gas, 250 ℃ as injection port temperature, in constant flow mode, column flow of 1ml/min, gas chromatography-tandem mass spectrometry programmed temperature parameters as shown in table 1:
the mass spectrum conditions of the triple quadrupole are as follows: the ionization mode is electron bombardment source (EI), the temperature of transmission line is 280 ℃, the temperature of ion source is 300 ℃, the ionization energy is 70eV, MRM multiple reaction monitoring mode is selected, and the parameters for measuring four furfural compounds by gas chromatography-tandem mass spectrometry are shown in Table 2;
the detection spectra are shown in FIG. 6a (unlabeled sample) and FIG. 6b (labeled sample), the detection results are shown in Table 4, and the accuracy and precision of the detection results are shown in Table 5.
Example 7
Weighing two reconstituted milk samples, wherein each milk sample is 5.0g, and one of the two reconstituted milk samples is added with 0.005mg of furfural standard substance, 0.005mg of methylfurfural standard substance, 0.005mg of hydroxymethylfurfural standard substance and 0.005mg of 2-acetylfuran standard substance to serve as a labeling sample.
Two reconstituted milk samples were subjected to the following steps, respectively:
1) adding 5mL of acetonitrile into the reconstituted milk sample, and fully swirling for 5min at 6000rpm for mixing;
2) adding 1g of sodium chloride and 1g of anhydrous sodium acetate into the mixed solution obtained in the step 1), fully whirling for 5min at the temperature of 15 ℃ and the speed of 5000rpm, and then performing ultrasonic oscillation for 25min at the frequency of 40 KHz;
3) adding 3g of anhydrous magnesium sulfate into the solution obtained in the step 2), performing vortex treatment for 1min at 5000rpm, performing dewatering treatment, centrifuging the dewatered solution for 5min at 15 ℃ and 6000rpm, and collecting supernatant;
4) collecting 1ml of supernatant, adding 54mg of C18, 133mg of anhydrous magnesium sulfate and 13mg of PSA, purifying at 25 ℃ for 25min, centrifuging the purified solution at 5000rpm for 5min, collecting the supernatant, passing the supernatant through a 0.22-micron PTFE membrane, and collecting the filtrate for later use;
5) detecting the content of furfural substances in the filtrate collected in the step 4) by adopting gas chromatography-tandem triple quadrupole mass spectrometry, and repeatedly determining for 6 times, wherein the conditions of the gas chromatography are as follows: using a chromatographic column Rtx-WAX of specification (30m x 0.25mm x 0.25 μm), helium (He) as carrier gas, (Ar) as collision gas, 230 ℃ as injection port temperature, in constant flow mode, column flow rate of 1ml/min, gas chromatography-tandem mass spectrometry programmed temperature parameters as shown in table 1:
the mass spectrum conditions of the triple quadrupole are as follows: the ionization mode is electron bombardment source (EI), the temperature of transmission line is 280 ℃, the temperature of ion source is 300 ℃, the ionization energy is 70eV, MRM multiple reaction monitoring mode is selected, and the parameters for measuring four furfural compounds by gas chromatography-tandem mass spectrometry are shown in Table 2:
the detection spectra are shown in FIG. 7a (unlabeled sample) and FIG. 7b (labeled sample), the detection results are shown in Table 4, and the accuracy and precision of the detection results are shown in Table 5.
Example 8
The milk samples were obtained from the same sources as in example 1, and the experiment was carried out in the same manner as in example 1, except that sodium chloride and anhydrous sodium acetate were not added in step 2).
The detection spectra are shown in FIG. 8a (unlabeled sample) and FIG. 8b (labeled sample), the detection results are shown in Table 4, and the accuracy and precision of the detection results are shown in Table 5.
Example 9
The milk samples were obtained from the same sources as in example 1, and the experiment was carried out in the same manner as in example 1, except that no ultrasonic oscillation was carried out in step 2).
The detection spectra are shown in FIG. 9a (unlabeled sample) and FIG. 9b (labeled sample), the detection results are shown in Table 4, and the accuracy and precision of the detection results are shown in Table 5.
Comparative example 1
The source of the milk sample was the same as in example 1, and the experiment was carried out according to the method of example 1, except that the sample treatment step was carried out according to the national standard "NY/T1332-2007", and the specific steps were as follows: weighing 10.0g of sample, placing the sample in a 50mL centrifuge tube, adding 5mL of oxalic acid solution, uniformly mixing, heating in a boiling water bath for 25min, cooling to room temperature, adding 10mL of methanol, adding 3mL of potassium ferrocyanide solution and 3mL of zinc acetate solution, violently shaking, standing for 15min, diluting to the constant volume with methanol, uniformly mixing, cooling to room temperature, centrifuging for 10min under the condition of 6000r/min, taking the supernatant, passing through a 0.22 mu m PTFE membrane, and then testing on a machine.
The detection spectra are shown in FIG. 10a (unlabeled sample) and FIG. 10b (labeled sample), the detection results are shown in Table 4, and the accuracy and precision of the detection results are shown in Table 5.
Comparative example 2
The source of the milk sample was the same as in example 1, and an experiment was conducted in the same manner as in example 1 except that the gas chromatography-tandem triple quadrupole mass spectrometry was replaced with high performance liquid chromatography. Using a siemer fly U3000 liquid chromatograph (ultraviolet UV detector), detector wavelength: 280nm, mobile phase: a-0.1% aqueous formic acid solution and B-0.1% acetonitrile formic acid solution, flow rates: 1.0mL/min, column AQ-C18 column (4.6 x 250mm, 5 μm), column temperature: the conditions for gradient elution by liquid chromatography at 30 ℃ are shown in Table 3.
The detection spectra are shown in FIG. 11a (unlabeled sample) and FIG. 11b (labeled sample), the detection results are shown in Table 4, and the accuracy and precision of the detection results are shown in Table 5.
Comparative example 3
The milk sample was obtained from the same sources as in example 1, and the experiment was carried out in the same manner as in example 1, except that step 2) was not carried out.
The detection spectra are shown in FIG. 12a (unlabeled sample) and FIG. 12b (labeled sample), the detection results are shown in Table 4, and the accuracy and precision of the detection results are shown in Table 5.
TABLE 1
| Rate of temperature rise (. degree. C./min) | Temperature (. degree.C.) | Retention time (min) | |
| Initiation of | 60 | 2.00 | |
| 1 | 20 | 120 | 1.00 |
| 2 | 10 | 220 | 10.00 |
TABLE 2
TABLE 3
| Flow rate (ml/min) | A％ | B％ | |
| Initial | 0.3 | 95.0 | 5.0 |
| 10 | 0.3 | 5.0 | 95.0 |
| 18 | 0.3 | 5.0 | 95.0 |
| 18.1 | 0.3 | 95.0 | 5.0 |
| 30 | 0.3 | 95.0 | 5.0 |
TABLE 4
Note: "+" indicates that the furfural substances are detected, and "-" indicates that the furfural substances are not detected.
TABLE 5
From the above results, it can be seen that, in examples 1 to 7 of the method of the present invention, the accuracy of the detection result can be between 84% and 107.2%, and the precision is between 1.5% and 8.7%; the accuracy meets the requirement of 80-120%, the precision meets the requirement of less than 10%, and the effect is obviously better.
As can be seen by comparing the embodiment 1 with the embodiments 8 to 9, the technical scheme of the invention for demulsification by adding the demulsifier and matching with the ultrasonic oscillation mode has better technical effect.
As can be seen by comparing example 1 with comparative examples 1 to 3, the accuracy and precision of the test results of the method of the present invention are better.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A sample pretreatment method for furfural-containing substances comprises the following steps: 1) mixing a sample containing furfural substances with an organic solvent; 2) demulsifying the mixed liquid obtained in the step 1); 3) dehydrating the demulsified solution obtained in the step 2); 4) purifying the solution obtained in the step 3) after water removal; 5) and (4) performing membrane filtration on the purified solution, and collecting filtrate.
2. The method according to claim 1, wherein the sample containing furfural substances is a dairy product, preferably milk, milk powder or reconstituted milk.
3. The method according to claim 1 or 2, wherein the furfural species is at least one of furfural, methylfurfural, hydroxymethylfurfural, and 2-acetylfuran.
4. The process according to any one of claims 1 to 3, wherein the organic solvent is a polar organic solvent, preferably a polar organic solvent having a boiling point of 50-85 ℃, more preferably at least one of acetonitrile, methanol, ethanol and acetone;
preferably, the amount of the organic solvent is 1 to 5mL, preferably 1 to 3mL, relative to 1g of the sample containing the furfural-like substance.
5. The method according to any one of claims 1 to 4, wherein the mixing in step 1) comprises shaking, vortexing or stirring, preferably vortexing;
more preferably, the rotation speed of the vortex is 3000-.
6. The method according to any of claims 1-5, wherein the demulsification is performed by a physicochemical and/or a physico-mechanical means, preferably a physicochemical and a physico-mechanical means; the physical and chemical mode is more preferably to add a demulsifier for demulsification; more preferably, the physical mechanical means is ultrasonic vibration to break the emulsion.
7. The method of claim 6, wherein the emulsion breaker is an inorganic salt, preferably at least one of sodium chloride, sodium acetate, sodium citrate, and sodium sulfate, more preferably sodium chloride and sodium acetate;
further preferably, the weight ratio of the sodium chloride to the sodium acetate is 1-5: 1;
further preferably, the amount of the demulsifier is 0.4-1.2g, more preferably 0.6-1g, relative to 1g of the sample containing the furfural substances;
preferably, the frequency of the ultrasonic oscillation is 30-50KHz, and the time is 15-25 min.
8. The method of any one of claims 1-7, wherein the removing water in step 3) comprises contacting a water removal agent with the demulsified solution;
preferably, the conditions for contacting the water scavenger with the demulsified solution comprise: the temperature is 15-25 deg.C, and the time is 1-5 min;
preferably, the amount of the water removal agent is 0.5-1.2g relative to 1g of a sample containing furfural substances;
preferably, the water scavenger is at least one selected from the group consisting of anhydrous magnesium sulfate, anhydrous sodium carbonate, anhydrous potassium carbonate and phosphorus pentoxide, and more preferably anhydrous magnesium sulfate.
9. The method according to any one of claims 1 to 8, wherein the purification in step 4) comprises adsorption purification, filtration purification or precipitation purification, preferably adsorption purification;
preferably, the adsorption purification mode is to contact an adsorbent with the solution after water removal;
more preferably, the conditions for contacting the adsorbent with the water-removed solution include a temperature of 15-25 ℃ and a time of 5-30 min;
more preferably, the amount of the adsorbent is 50-140mg relative to 1mL of the water-removed solution obtained in step 3); more preferably, the adsorbent is selected from at least one of C18 bonded silica gel, N-propyl ethylene diamine, amino modified bonded silica gel, florisil, neutral alumina;
more preferably, the adsorbent is selected from the group consisting of C18-bonded silica gel and N-propyl ethylenediamine;
more preferably, the weight ratio of the N-propylethylenediamine to the C18-bonded silica gel is 1: 2-6;
more preferably, the adsorption purification mode further comprises simultaneously contacting the adsorbent and a water removal agent with the water-removed solution;
more preferably, the amount of the water removal agent in the purification process is preferably 144-270mg relative to 1mL of the solution obtained in the step 3) after water removal;
more preferably, C18-bonded silica gel, N-propylethylenediamine and anhydrous magnesium sulfate are simultaneously contacted with the water-removed solution;
more preferably, the weight ratio of the C18 bonded silica gel, the anhydrous magnesium sulfate and the N-propylethylenediamine is (2-6): (8-12): 1.
10. the process according to claim 1 or 2, wherein the membrane used for the membrane filtration in step 5) is selected from a nylon microporous membrane, a polyvinylidene fluoride membrane or a polytetrafluoroethylene membrane, preferably a polytetrafluoroethylene membrane;
preferably, the pore size of the filter membrane is 0.22-0.45 μm.
11. A method for detecting the content of furfural substances, which comprises the steps of treating a sample containing the furfural substances and then quantitatively analyzing the content of the furfural substances in filtrate by using a gas chromatography-mass spectrometry combination method, and is characterized in that the sample containing the furfural substances is treated by using the method as claimed in any one of claims 1 to 10.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113447581A (en) * | 2021-06-23 | 2021-09-28 | 中国食品药品检定研究院 | Method for detecting microcystin in algae food and raw materials for producing algae food |
| CN115032315A (en) * | 2022-05-18 | 2022-09-09 | 贵州茅台酒股份有限公司 | Method for detecting furfural in rice husk |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013253061A (en) * | 2012-06-08 | 2013-12-19 | Mitsubishi Chemicals Corp | Method for purifying furfural and method for producing furan |
| CN104122343A (en) * | 2014-07-07 | 2014-10-29 | 河南省科学院能源研究所有限公司 | Method for gas chromatographic quantitative detection on furfural prepared through hydrochloric acid method |
| CN104142372A (en) * | 2014-07-17 | 2014-11-12 | 中国石油化工股份有限公司 | Method for detecting furfuryl alcohol content in furfural biological hydrogenation reaction liquid |
| CN108318601A (en) * | 2018-04-24 | 2018-07-24 | 汕头市天悦科技创新研究院有限公司 | A kind of liquid chromatography detecting method of furfural and 5 hydroxymethyl furfural |
| CN109187784A (en) * | 2018-09-11 | 2019-01-11 | 中山出入境检验检疫局检验检疫技术中心 | A kind of headspace solid-phase microextraction of sea-buckthorn volatile oil compositions-gas chromatography mass spectrometry determination method |
| CN109781883A (en) * | 2019-01-17 | 2019-05-21 | 江南大学 | A method of based on QuEChERS- dispersive liquid-liquid microextraction trace detection 5 hydroxymethyl furfural |
| CN110133155A (en) * | 2019-06-24 | 2019-08-16 | 中国烟草总公司郑州烟草研究院 | A kind of gas chromatography tandem mass spectrometry analysis method of essence spice for cigarette |
-
2019
- 2019-12-20 CN CN201911329097.XA patent/CN113009002A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013253061A (en) * | 2012-06-08 | 2013-12-19 | Mitsubishi Chemicals Corp | Method for purifying furfural and method for producing furan |
| CN104122343A (en) * | 2014-07-07 | 2014-10-29 | 河南省科学院能源研究所有限公司 | Method for gas chromatographic quantitative detection on furfural prepared through hydrochloric acid method |
| CN104142372A (en) * | 2014-07-17 | 2014-11-12 | 中国石油化工股份有限公司 | Method for detecting furfuryl alcohol content in furfural biological hydrogenation reaction liquid |
| CN108318601A (en) * | 2018-04-24 | 2018-07-24 | 汕头市天悦科技创新研究院有限公司 | A kind of liquid chromatography detecting method of furfural and 5 hydroxymethyl furfural |
| CN109187784A (en) * | 2018-09-11 | 2019-01-11 | 中山出入境检验检疫局检验检疫技术中心 | A kind of headspace solid-phase microextraction of sea-buckthorn volatile oil compositions-gas chromatography mass spectrometry determination method |
| CN109781883A (en) * | 2019-01-17 | 2019-05-21 | 江南大学 | A method of based on QuEChERS- dispersive liquid-liquid microextraction trace detection 5 hydroxymethyl furfural |
| CN110133155A (en) * | 2019-06-24 | 2019-08-16 | 中国烟草总公司郑州烟草研究院 | A kind of gas chromatography tandem mass spectrometry analysis method of essence spice for cigarette |
Non-Patent Citations (2)
| Title |
|---|
| LUCIA GIORDANO等: "Quantitative analysis of 2-furfural and 5-methylfurfural in different", 《JOURNAL OF CHROMATOGRAPHY》 * |
| 万博恺等: "顶空固相微萃取结合GC-MS 测定酱油中的羟甲基糠醛", 《现代食品科技》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113447581A (en) * | 2021-06-23 | 2021-09-28 | 中国食品药品检定研究院 | Method for detecting microcystin in algae food and raw materials for producing algae food |
| CN115032315A (en) * | 2022-05-18 | 2022-09-09 | 贵州茅台酒股份有限公司 | Method for detecting furfural in rice husk |
| CN115032315B (en) * | 2022-05-18 | 2023-09-01 | 贵州茅台酒股份有限公司 | Detection method of furfural in chaff |
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