CN114878710B - Method for detecting content of hydroxymethylfurfural in royal jelly and dry powder thereof - Google Patents
Method for detecting content of hydroxymethylfurfural in royal jelly and dry powder thereof Download PDFInfo
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- CN114878710B CN114878710B CN202210477234.XA CN202210477234A CN114878710B CN 114878710 B CN114878710 B CN 114878710B CN 202210477234 A CN202210477234 A CN 202210477234A CN 114878710 B CN114878710 B CN 114878710B
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 90
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229940109850 royal jelly Drugs 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000000843 powder Substances 0.000 title claims abstract description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 123
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 26
- 238000001514 detection method Methods 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000010812 external standard method Methods 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 75
- 239000000523 sample Substances 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 43
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 34
- 239000012496 blank sample Substances 0.000 claims description 24
- 239000012488 sample solution Substances 0.000 claims description 23
- 239000012086 standard solution Substances 0.000 claims description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 17
- 239000012224 working solution Substances 0.000 claims description 15
- 241000287828 Gallus gallus Species 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010828 elution Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 239000012085 test solution Substances 0.000 claims description 4
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 7
- 238000007865 diluting Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 22
- 238000000605 extraction Methods 0.000 description 18
- 102000004169 proteins and genes Human genes 0.000 description 9
- 108090000623 proteins and genes Proteins 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012670 alkaline solution Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000013558 reference substance Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000003908 quality control method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000000276 potassium ferrocyanide Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 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 2
- 239000004246 zinc acetate Substances 0.000 description 2
- QVYAWBLDJPTXHS-UHFFFAOYSA-N 5-Hydroxymethyl-2-furfural Natural products OC1=CC=C(C=O)O1 QVYAWBLDJPTXHS-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 150000002402 hexoses Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001814 protein method Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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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
-
- 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
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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
- G01N30/50—Conditioning of the sorbent material or stationary liquid
- G01N30/52—Physical parameters
- G01N30/54—Temperature
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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
- G01N30/62—Detectors specially adapted therefor
- G01N30/74—Optical detectors
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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
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- G01N30/02—Column chromatography
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention discloses a method for measuring the content of hydroxymethyl furfural in royal jelly and dry powder thereof, which comprises the steps of dissolving and diluting a sample with water and 3% ammonia water, extracting the hydroxymethyl furfural by ethyl acetate, analyzing by a high performance liquid chromatograph, and quantifying by an external standard method. The method has the detection limit of 3-6 mug/kg, the quantitative limit of 10-20 mug/kg, the recovery rate of 82-106% (n=3), the precision of 4.6-8.0% (n=3), and can meet the requirement of judging the freshness of the royal jelly and the dry royal jelly powder.
Description
Technical Field
The invention belongs to the field of food quality control, and relates to a method for detecting a freshness index-hydroxymethyl furfural in royal jelly and dry powder thereof.
Background
Royal jelly (royal jelly), which is secretion of the pharyngeal gland of young workers who cultivate larvae in honey comb, is a food for feeding larvae to become queen bee, and also a food for the life of queen bee. Years of scientific research and medical clinical practice at home and abroad prove that the royal jelly has peculiar effects on human medical treatment, health care and the like.
The Lac Regis Apis contains water 62-67%, protein 14-16%, saccharide 10-15%, lipid 2-9%, mineral 0.6-2%, and trace amount of vitamins. In production practice, if the royal jelly is stored improperly, it will produce brown stain, become sticky due to aggregation and solidification of protein, become sour, become stink and produce bubbles due to microbial contamination, seriously affecting the quality of the royal jelly.
Patent publication No. CN101363828B of 2008 proposes that the fresh grade is obtained when the content of 5-hydroxymethyl-2-furfural in royal jelly is less than or equal to 90. Mu.g/kg. The freshness index is proposed to excite the enthusiasm of enterprises to produce high-quality royal jelly to a certain extent. However, the method is operated according to the patent, because the sample is diluted 20 times, the detection limit of the method is reduced, and the detection limit of the method is 0.3mg/kg through measurement, so that the requirement of the quality control of the freshness of the royal jelly cannot be met.
Hydroxymethylfurfural is an important intermediate product of maillard reactions, which dehydrates hexoses under acidic conditions, or is formed by the reaction between an amino acid and a carbonyl compound. The journal Spectroscopy and Spectroscopy analysis 2009,29 (12): 3236-3240) indicates that the content of hydroxymethylfurfural in royal jelly is below 150 μg/kg, and the royal jelly can be considered as fresh.
In the existing literature detection method, the detection limit of the hydroxymethyl furfural in the royal jelly is 300 mug/kg, and the quantitative limit is 1mg/kg, however, in our research, the detection result shows that the hydroxymethyl furfural content of the royal jelly stored until now in 2019 at 4 ℃ is only 91 mug/kg, so that the measurement method of the hydroxymethyl furfural content in the royal jelly needs to be further studied.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for detecting the content of hydroxymethyl furfural in royal jelly and dry powder thereof. The method has the characteristics of simplicity, rapidness, accuracy and sensitivity in operation, common and easily available instruments, convenience in popularization, detection limit of the method reaches 6 mug/kg, quantitative limit of the method reaches 20 mug/kg, and strong practicability, and provides a basis for determining the freshness index of the royal jelly.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the method for detecting the content of the hydroxymethylfurfural in the royal jelly and the dry powder thereof adopts a high performance liquid chromatography method and uses an external standard method for quantification, and comprises the following steps:
1) Determining chromatographic conditions:
column packing material: octadecyl bonded silica gel;
mobile phase: mobile phase A, methanol-0.4% phosphoric acid solution, volume ratio is 0-10:90-100; the method comprises the steps of carrying out a first treatment on the surface of the Mobile phase B, methanol; detection wavelength: 285nm; column temperature: 35 ℃;
2) Preparation of test solution:
weighing a royal jelly sample or a royal jelly dry powder sample, dissolving in an ammonia water solution, extracting with ethyl acetate, evaporating an ethyl acetate layer to dryness, adding a methanol solution, and filtering with a filter membrane to obtain a sample solution containing 1.00g of sample per 1 ml;
3) Preparation of blank sample standard solution:
weighing 5 parts of blank sample, and adding a hydroxymethylfurfural standard working solution to obtain the concentration of the standard solution of the blank sample of 20 mug/L, 50 mug/L, 100 mug/L, 200 mug/L and 500 mug/L;
4) And (3) measuring:
respectively precisely sucking 20 mu L of a blank sample standard solution and 20 mu L of a sample solution, injecting into a liquid chromatograph, drawing a standard working curve by taking the concentration of the blank sample standard solution as an abscissa and the peak area of the hydroxymethylfurfural as an ordinate, and quantifying by an external standard method.
Further, the volume ratio of the mobile phase A to the methanol-0.4% phosphoric acid solution is 6:94.
Further, the alkaline solution is selected from the group consisting of aqueous ammonia, aqueous carbonate, aqueous sodium hydroxide, aqueous calcium hydroxide, such that the pH of the sample solution is = 7-8.
Further, the detection limit of the method for detecting the content of the hydroxymethylfurfural in the royal jelly and the dry powder thereof is 3-6 mug/kg, and the quantitative limit is 10-20 mug/kg.
Specifically, the method for detecting the content of the hydroxymethylfurfural in the royal jelly and the dry powder thereof adopts a high performance liquid chromatography method, and the method for quantifying by an external standard method comprises the following steps:
1) Determining chromatographic conditions:
column packing material: octadecyl bonded silica gel;
mobile phase: mobile phase A, methanol-0.4% phosphoric acid solution, volume ratio is 6:94; mobile phase B, methanol; detection wavelength: 285nm; column temperature: 35 ℃;
2) Preparation of test solution:
weighing 1.00g of a royal jelly sample or 0.50g of a royal jelly dry powder sample, accurately obtaining +/-0.001 g, adding 1.5mL of water into a 15mL plastic centrifuge tube, adding 1.5mL of 3% ammonia water solution by volume concentration into the royal jelly sample, adding 2.0mL of 3% ammonia water solution by volume concentration into the royal jelly dry powder sample, fully dissolving until no macroscopic royal jelly particles exist, adding 8mL of ethyl acetate, manually oscillating and extracting 1min, and centrifuging at a rotating speed of 4500 rpm for 5min; sucking all ethyl acetate layers into a 50mL chicken heart bottle, performing rotary evaporation in a water bath at 40 ℃ until the ethyl acetate layers are dry, adding 1mL of methanol solution with the concentration of 6% into the chicken heart bottle, ultrasonically dissolving residues, and filtering the sample solution through a 0.22 mu m filter membrane to obtain a sample solution containing 1.00g of sample per 1 mL;
3) Preparation of blank sample standard solution:
weighing 5 parts of blank samples, respectively 1.00g to be accurate to +/-0.001 g, respectively adding 0.20mL,0.50mL of 0.1mg/L of hydroxymethyl furfural standard working solution, 0.10mL,0.20mL and 0.50mL of 1mg/L of hydroxymethyl furfural standard working solution into a 15mL plastic centrifuge tube, respectively adding 1.5mL of water, adding 1.5mL of ammonia water solution with the volume concentration of 3%, fully dissolving until no macroscopic royal jelly particles are generated, adding 8mL of ethyl acetate, manually oscillating and extracting 1min, centrifugally separating at the rotating speed of 4500 r/min for 5min, sucking all ethyl acetate layers into a 50mL chicken heart bottle, rotationally evaporating to dryness in a water bath at 40 ℃, adding 1mL of 6% methanol solution into the chicken heart bottle, ultrasonically dissolving residues, and filtering the sample solution with a 0.22 mu m filter membrane to obtain a series of sample standard solutions with the concentration of 20 mu g/L, 50 mu g/L, 100 mu g/L, 200 mu g/L and 500 mu g/L;
4) And (3) measuring:
respectively precisely sucking 20 mu L of each of a standard solution of a series of blank samples and a solution of a test sample, injecting into a liquid chromatograph, drawing a standard working curve by taking standard concentration of the blank samples as an abscissa and the peak area of the hydroxymethylfurfural as an ordinate, and quantifying by an external standard method.
In order to verify the stability, accuracy, specificity and system applicability of the method for measuring the content of the hydroxymethylfurfural, a methodological verification test is carried out on the method.
1. Extraction of hydroxymethyl furfural from royal jelly
Among the existing methods for measuring the hydroxymethylfurfural, the extraction method of the hydroxymethylfurfural is mainly shown in table 1.
TABLE 1 extraction method of hydroxymethylfurfural in different samples
As can be seen from table 1 above, for samples with low protein content, light color and small soluble content, direct filtration and sample injection are mostly adopted in the literature, for samples with deep color and large soluble content, ethyl acetate extraction and C18 solid phase extraction columns are adopted for purification, and for samples with high protein content, potassium ferrocyanide/zinc acetate precipitated protein is adopted for purification.
The dry powder of Lac Regis Apis and Lac Regis Apis contains proteins up to 15% and 39%, fatty acids 3% and 10%, and trace pollen pigment, and is required to be removed. Therefore, the sample is purified by adopting a potassium ferrocyanide/zinc acetate precipitated protein method, and the hydroxymethylfurfural can be completely extracted, but the detection limit of the method is reduced because the sample is diluted 20 times, and the detection limit of the method is 0.3mg/kg through measurement, so that the requirement of the quality control of the freshness of the royal jelly cannot be met.
2. Influence of sample pH on hydroxymethylfurfural extraction
Dissolving the sample with water, extracting with organic solvent, and concentrating to improve detection limit. In practice, we found that the absolute extraction rate of hydroxymethylfurfural by this method was only 20%. Probably due to the influence of protein in the royal jelly on the extraction efficiency.
The royal jelly can be dissolved in alkaline solution, protein is dissolved in alkaline solution, and hydroxymethyl furfural in the royal jelly is extracted by ethyl acetate. The extraction efficiency of ethyl acetate on hydroxymethyl furfural in royal jelly under alkaline solution conditions of different concentrations is examined, and the results are shown in Table 2.
TABLE 2 extraction efficiency of hydroxymethylfurfural with different alkaline solution concentrations
As can be seen from table 2, the extraction efficiency of ethyl acetate on hydroxymethylfurfural in royal jelly was highest when the pH was neutral. The protein in the royal jelly is dissolved by ammonia water, so that the ethyl acetate and the hydroxymethyl furfural are fully mixed, the sample liquid is in a fine milk shape, the contact area of the ethyl acetate and the sample liquid is increased, and the extraction efficiency is improved. Obvious flocculent protein can be seen in the sample solution without ammonia water, and acetic acid and hydroxymethyl furfural can not be fully mixed, so that the extraction is affected. When the pH is in higher alkalinity, the extraction efficiency is not as good as that of a neutral sample liquid, and the hydroxymethylfurfural is possibly combined with water, sugar and protein in the sample liquid more firmly, so that the partition coefficient in ethyl acetate is reduced, and the extraction efficiency is influenced. Thus, a royal jelly sample was selectively dissolved with 1.5mL of water and 1.5mL of 3% aqueous ammonia, and a royal jelly dry powder sample was dissolved with 1.5mL of water and 2.0mL of 3% aqueous ammonia. Under different pH conditions, 1, pH= 3.8,2, pH= 7.7,3, pH= 9.6,4 and pH=7.7 royal jelly is added with 100 mug/kg of hydroxymethyl furfural, and the hydroxymethyl furfural chromatogram in the royal jelly is extracted by ethyl acetate, and is shown in figure 1.
3. Effect of solvent on extraction of hydroxymethylfurfural from Lac Regis Apis
Hydroxymethylfurfural is readily soluble in solvents such as water, acetonitrile, acetone, alcohols, ethyl acetate, dimethylformamide, benzene, diethyl ether, chloroform and the like. Alcohol, acetonitrile, acetone and dimethylformamide can be dissolved in water, so that the saccharides in the royal jelly are simultaneously extracted during the extraction, and the residue after evaporation is more in quantity and needs to be further purified, so that the use is not preferred. Diethyl ether is an easily-made chemical, is inconvenient to purchase and manage, and benzene and chloroform have certain toxicity, so ethyl acetate is selected as an extraction solvent.
After water and ammonia water are added into the royal jelly sample, the total volume is about 4.5mL, through experiments, when the amount of ethyl acetate is 4mL, the sample liquid is easy to generate an emulsifying phenomenon, when the amount of ethyl acetate is 8mL, the sample liquid cannot generate an emulsifying phenomenon, the absolute extraction rate of the hydroxymethylfurfural in the sample is above 60%, when the amount of ethyl acetate is 12mL, the sample liquid cannot generate an emulsifying phenomenon, and the absolute extraction rate of the hydroxymethylfurfural in the sample is above 75%. The dosage of 8mL ethyl acetate can meet the requirements in consideration of the dosage of the reagent and the detection sensitivity. The amount of ethyl acetate was thus selected to be 8mL.
4. Selection of mobile phase
We use methanol: 0.4% phosphoric acid 10:90,8:92 and 6:94 is the mobile phase and a chromatographic separation test is performed. When methanol: 0.4% phosphoric acid 10:90, there is an interference peak before the hydroxymethylfurfural chromatographic peak when methanol: 0.4% phosphoric acid = 8:92, there is an interference peak behind the hydroxymethylfurfural chromatographic peak, and although 2 ratios can achieve complete separation from the interference peak, the impurity peak is relatively close to the hydroxymethylfurfural chromatographic peak, and when the hydroxymethylfurfural content in the sample is high, it cannot be guaranteed that all the samples can be completely separated, and when methanol: 0.4% phosphoric acid is 6:94, no impurity peak interference exists near the hydroxymethylfurfural chromatographic peak, but the retention time of the hydroxymethylfurfural chromatographic peak is longer, and in order to ensure the detection efficiency, the hydroxymethylfurfural chromatographic peak is washed for 3min by using 100% methanol after the retention time, and then methanol is used for the reaction: 0.4% phosphoric acid is 6:94, the total time is 23min, the elution condition of the mobile phase is shown in Table 3, and the chromatogram after the mobile phase optimization is shown in FIG. 2. Wherein, 100 mug/kg of hydroxymethyl furfural is added in a blank sample, 2, the blank sample,
TABLE 3 gradient elution conditions of mobile phases
4. Linear range, recovery, precision and limit of detection of the method
Analysis method
4.1 preparation of sample solutions
Weighing 1.00g of a royal jelly sample or 0.50g of a royal jelly dry powder sample (accurate to +/-0.001 g) into a 15mL plastic centrifuge tube, adding 1.5mL of water, adding 1.5mL of 3% ammonia water solution into the royal jelly sample, adding 2.0mL of 3% ammonia water solution into the royal jelly dry powder sample, fully dissolving until no royal jelly particles are visible, adding 8mL of ethyl acetate, manually oscillating and extracting 1min, and centrifuging at a rotating speed of 4500 rpm for 5min. All ethyl acetate layers are sucked into a 50mL chicken heart bottle, water bath rotary evaporation is carried out at 40 ℃ until the ethyl acetate layers are dried, 1mL of 6% methanol solution is added into the chicken heart bottle, residues are dissolved by ultrasonic waves, and sample solution passes through a 0.22 mu m filter membrane to obtain a sample solution.
4.2 preparation of blank sample Standard solution
Weighing 1.00g of each blank sample, accurately obtaining +/-0.001 g, respectively adding 0.20mL,0.50mL of 0.1mg/L of hydroxymethylfurfural standard working solution, 0.10mL,0.20mL and 0.50mL of 1mg/L of hydroxymethylfurfural standard working solution into a 15mL plastic centrifuge tube, and performing normal operation from 4.1 'adding 1.5mL of water', thereby obtaining the blank sample standard working solution. The concentration of the corresponding standard solution series is 20 mug/L, 50 mug/L, 100 mug/L, 200 mug/L and 500 mug/L.
4.3 liquid chromatography reference conditions
Chromatographic column: c18 packed chromatography column (4.6 mm. Times.250 mm,5 μm); or an equivalent chromatographic column.
Mobile phase: mobile phase a, methanol+0.4% phosphoric acid solution = 6+94; mobile phase B, methanol. The gradient elution conditions are shown in Table 3.
Flow rate: see table 3.
Column temperature: 35 ℃.
Detection wavelength: 285nm.
Sample injection amount: 20. Mu.L.
4.4 measurement
And (3) respectively sampling a blank sample standard solution (4.2) and a sample solution (4.1), drawing a standard working curve by taking the concentration of the blank sample standard solution as an abscissa and the peak area of the hydroxymethylfurfural as an ordinate, and quantifying by an external standard method. The response value of the hydroxymethylfurfural in the blank sample standard solution and the sample solution is within the linear range of the instrument detection.
Blank substrate samples and samples were treated and assayed by analytical methods and working curves were drawn with hydroxymethylfurfural peak area versus mass concentration (x, μg/kg). The results are shown in Table 4,the hydroxymethylfurfural has good linearity within the range of 20 mu g/kg-500 mu g/kg and the correlation coefficient R 2 = 0.9983, meeting the quantitative analysis requirements. The detection limit and the quantitative limit of the method are 6 mug/kg and 20 mug/kg respectively, the recovery rate is 82% -106% (n=3), and the precision is 4.6% -8.0% (n=3).
When the sample amount, water, ammonia water and ethyl acetate are doubled, the extracting solution is concentrated and then dissolved by 1ml of methanol solution for analysis, the detection limit can be increased to 3ug/kg, and the quantitative limit is increased to 10ug/kg
TABLE 4 Linear Range, regression equation, correlation coefficient and detection Limit of hydroxymethylFurfural
20 mug/kg, 100 mug/kg and 500 mug/kg of hydroxymethyl furfural standard solution are respectively added into a blank royal jelly sample, and after treatment according to an analysis method, recovery rate experiments are carried out, and each addition level is repeatedly measured for 3 times. The results are shown in Table 5, with addition recovery rates of 94.8%, 96.7% and 102.9%, respectively, and relative standard deviations of 5.3%, 4.2% and 2.9%, respectively.
TABLE 5 standard recovery and precision of hydroxymethylfurfural in blank Lac Regis Apis
The invention relates to a method for measuring the content of hydroxymethyl furfural in royal jelly and dry powder thereof, which comprises the steps of dissolving and diluting a sample with water and 3% ammonia water, extracting the hydroxymethyl furfural by ethyl acetate, analyzing by a high performance liquid chromatograph, and quantifying by an external standard method. The detection limit of the method is 6 mug/kg, the quantitative limit is 20 mug/kg, the recovery rate is 82% -106% (n=3), the precision is 4.6% -8.0% (n=3), and the method can meet the judging requirement of the freshness of the royal jelly and the dry royal jelly powder.
The dry royal jelly powder is a product obtained by dehydrating the royal jelly, the content of the hydroxymethyl furfural is far higher than that of the royal jelly, and the content of the hydroxymethyl furfural is foreseeable to judge that the freshness of the dry royal jelly powder is more significant than that of the royal jelly.
Drawings
FIG. 1 is a chromatogram of extracting hydroxymethyl furfural from Lac Regis Apis with ethyl acetate under different pH conditions;
figure 2 is a chromatogram of hydroxymethylfurfural in a mobile phase optimized sample.
Detailed Description
The invention is further described below with reference to examples.
Example 1
Method for detecting content of hydroxymethylfurfural in royal jelly and dry powder thereof
Instrument and reagent
The Shimadzu LC-20A high performance liquid chromatograph is provided with an LC-20AVP ultraviolet detector; sartorius BS224S electronic analytical balance: a sensory amount of 0.0001g; KQ3200E ultrasonic cleaner of Kunshan ultrasonic instruments Co., ltd; SC-3612 desktop high-speed centrifuge, a limited of scientific instruments, chinese, anhui; standard substance: hydroxymethylfurfural standard, CAS:67-47-0, and the purity is more than 99%. Phosphoric acid: 85%, high-grade purity; methanol, liquid chromatography purity; 28-30% of ammonia water; ethyl acetate is analytically pure; the water accords with GB/T6682 primary water. Filter membrane, nylon 66,0.22 μm.
3% ammonia solution: 3.0mL of ammonia water was drawn and the volume was fixed with water to 100mL.
6% methanol solution: 6.0mL of methanol was drawn and the volume was fixed with water to 100mL.
0.4% phosphoric acid solution: the volume was fixed with water to 1000mL by sucking 4.0mL of phosphoric acid.
Standard stock solutions of hydroxymethylfurfural: 20mg of a hydroxymethylfurfural standard substance is weighed, methanol is added to a constant volume of 20mL to prepare 1.0mg/mL of hydroxymethylfurfural stock solution. -18 degrees for 24 months.
Hydroxymethylfurfural standard intermediate: sucking 0.1mL of hydroxymethyl furfural stock solution, and using water to fix the volume to 10mL to prepare 10mg/L of hydroxymethyl furfural standard intermediate solution, and preserving for 12 months at-18 ℃.
Hydroxymethylfurfural standard working solution i: sucking 1.0mL of hydroxymethylfurfural standard intermediate solution, and preparing 1mg/L hydroxymethylfurfural standard working solution I by using water to fix the volume to 10mL, and preserving for 12 months at-18 ℃.
Hydroxymethylfurfural standard working solution ii: sucking 1.0mL of hydroxymethyl furfural standard working solution I, and preparing 0.1mg/L of hydroxymethyl furfural standard working solution II by water to a volume of 10mL, and preserving at-18 ℃ for 12 months.
The royal jelly and royal jelly dry powder sample is provided by Hangzhou Biyantian health products Co.
1) Determining chromatographic conditions:
column packing material: octadecyl bonded silica gel;
mobile phase: mobile phase A, methanol-0.4% phosphoric acid solution, volume ratio is 6:94; mobile phase B, methanol; detection wavelength: 285nm; column temperature: 35 ℃;
2) Preparation of test solution:
weighing 1.00g of a royal jelly sample or 0.50g of a royal jelly dry powder sample, accurately obtaining +/-0.001 g, adding 1.5mL of water into a 15mL plastic centrifuge tube, adding 1.5mL of 3% ammonia water solution by volume concentration into the royal jelly sample, adding 2.0mL of 3% ammonia water solution by volume concentration into the royal jelly dry powder sample, fully dissolving until no macroscopic royal jelly particles exist, adding 8mL of ethyl acetate, manually oscillating and extracting 1min, and centrifuging at a rotating speed of 4500 rpm for 5min; sucking all ethyl acetate layers into a 50mL chicken heart bottle, performing rotary evaporation in a water bath at 40 ℃ until the ethyl acetate layers are dry, adding 1mL of methanol solution with the concentration of 6% into the chicken heart bottle, ultrasonically dissolving residues, and filtering the sample solution through a 0.22 mu m filter membrane to obtain a sample solution with the concentration of 1.00g per 1 mL;
3) Preparation of blank sample standard solution:
weighing 5 parts of blank samples, respectively 1.00g to be accurate to +/-0.001 g, respectively adding 0.20mL,0.50mL of hydroxymethyl furfural standard working solution II, 0.10mL,0.20mL and 0.50mL of hydroxymethyl furfural standard working solution I into a 15mL plastic centrifuge tube, respectively adding 1.5mL of water, respectively adding 1.5mL of 3% ammonia water solution by volume concentration, fully dissolving until no macroscopic royal jelly particles are generated, adding 8mL of ethyl acetate, manually oscillating and extracting 1min, and centrifugally separating at a rotating speed of 4500 rpm for 5min. Sucking all ethyl acetate layers into a 50mL chicken heart bottle, performing rotary evaporation in a water bath at 40 ℃ until the ethyl acetate layers are dry, adding 1mL of 6% methanol solution into the chicken heart bottle, ultrasonically dissolving residues, and filtering the sample solution through a 0.22 mu m filter membrane to obtain reference substance solutions with the concentration of 20 mu g/L, 50 mu g/L, 100 mu g/L, 200 mu g/L and 500 mu g/L;
4) And (3) measuring:
respectively precisely sucking 5 parts of reference substance solution and 20 mu L of sample solution, injecting into a liquid chromatograph, drawing a reference substance solution curve by taking the concentration of the reference substance solution as an abscissa and the peak area of the hydroxymethylfurfural as an ordinate, and quantifying a sample by using the reference substance solution curve.
11 samples of royal jelly were measured as in the examples and the results are shown in Table 6.
TABLE 6 determination results of Lac Regis Apis and Lac Regis Apis dry powder sample
From the detection condition of an actual sample, when the new pulp in 2022 is preserved at-18 ℃, the content of the hydroxymethylfurfural is below 12 mug/kg, when the royal jelly in 2021 is preserved at-18 ℃, the content of the hydroxymethylfurfural is below 33 mug/kg, and when the royal jelly is preserved at 4 ℃, the content of the hydroxymethylfurfural is between 91 and 280 mug/kg. The content of the hydroxymethyl furfural in the royal jelly is really related to the storage temperature and time.
The aqueous ammonia may be replaced with an aqueous carbonate solution, an aqueous sodium hydroxide solution or an aqueous calcium hydroxide solution as in example 1, so long as the pH of the sample solution is made to be 7-8,
example 2
The procedure of example 1 was followed except that mobile phase A was a 0.4% phosphoric acid solution.
Example 3
The procedure of example 1 was followed except that mobile phase A, methanol-0.4% phosphoric acid solution, was used at a 10:90 ratio.
Example 4
The procedure of example 1 was followed except that mobile phase A, methanol-0.4% phosphoric acid solution, was used at a 2:98 ratio.
In addition, it should be noted that all the structural, characteristic and principle changes described in the patent conception of the present invention may be made in the form of equivalent or simple changes, such as: according to the preparation method of the sample solution, the obtained sample solution adopts other instruments to carry out qualitative or quantitative analysis on the furfural content; the invention also discloses a method for preparing the same, which comprises the steps of changing the sample weighing, changing the volumes of ammonia water and ethyl acetate and the like.
Claims (1)
1. The method for detecting the content of the hydroxymethylfurfural in the royal jelly and the dry powder thereof is characterized by adopting a high performance liquid chromatography and quantifying by an external standard method, and comprises the following steps:
1) Determining chromatographic conditions:
column packing material: octadecyl bonded silica gel;
mobile phase: mobile phase A, methanol-0.4% phosphoric acid solution, volume ratio is 6:94; mobile phase B, methanol; detection wavelength: 285nm; column temperature: 35 ℃;
gradient elution conditions of mobile phase
2) Preparation of test solution:
weighing 1.00g g of a royal jelly sample or 0.50g of a dry royal jelly powder sample, accurately reaching +/-0.001 g, adding 1.5mL of mL water into a 15mL plastic centrifuge tube, adding 1.5mL of 3% ammonia water solution with volume concentration into the royal jelly sample, adding 2.0 mL% ammonia water solution with volume concentration into the dry royal jelly powder sample, fully dissolving until no macroscopic royal jelly particles are generated, adding 8mL ethyl acetate, manually oscillating and extracting for 1min, and centrifuging at a rotating speed of 4500 r/min for 5min; sucking all ethyl acetate layers into a 50mL chicken heart bottle, performing rotary evaporation in a water bath at 40 ℃ until the ethyl acetate layers are dry, adding 1mL of 6% methanol solution into the chicken heart bottle, ultrasonically dissolving residues, and filtering the sample solution through a 0.22 mu m filter membrane to obtain 1.00g of sample solution per 1 mL;
3) Preparation of blank sample standard solution:
weighing 5 parts of blank samples, namely 1.00 part of each g part, accurately obtaining +/-0.001 g part, respectively adding 0.20mL of 0.50mL of 0.1mg/L of hydroxymethyl furfural standard working solution and 0.10mL,0.20mL,0.50mL mg/L of 1mg/L of hydroxymethyl furfural standard working solution into a 15mL plastic centrifuge tube, respectively adding 1.5mL of 1. 1.5mL water, adding 1.5mL of 3% ammonia water solution in volume concentration, fully dissolving until no macroscopic royal jelly particles exist, adding 8mL ethyl acetate, manually oscillating and extracting 1min, centrifuging at a rotating speed of 4500 r/min for 5min, sucking all ethyl acetate layers into a 50mL chicken heart bottle, rotationally evaporating to dryness in a water bath at 40 ℃, adding 1mL of 6% methanol solution into the chicken heart bottle, ultrasonically dissolving residues, and filtering the sample solution with a 0.22 mu m filter membrane to obtain the blank sample standard solution with the concentration of 20 mu g/L, 50 mu g/L, 100 mu g/L, 200 mu g/L and 500 mu g/L;
4) And (3) measuring:
respectively precisely sucking 5 pairs of blank sample standard solution and 20 mu L of sample solution, injecting into a liquid chromatograph, taking the concentration of the blank sample standard solution as an abscissa, taking the hydroxymethylfurfural peak area as an ordinate, and drawing a standard working curve and quantifying by an external standard method.
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