CN116879439A - Method for measuring chlorate and perchlorate in raw and auxiliary materials of infant milk powder - Google Patents
Method for measuring chlorate and perchlorate in raw and auxiliary materials of infant milk powder Download PDFInfo
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- CN116879439A CN116879439A CN202310853258.5A CN202310853258A CN116879439A CN 116879439 A CN116879439 A CN 116879439A CN 202310853258 A CN202310853258 A CN 202310853258A CN 116879439 A CN116879439 A CN 116879439A
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- perchlorate
- chlorate
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- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 title claims abstract description 146
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 title claims abstract description 71
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000000843 powder Substances 0.000 title claims abstract description 40
- 235000013350 formula milk Nutrition 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 30
- 239000000523 sample Substances 0.000 claims abstract description 60
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000012488 sample solution Substances 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 238000001514 detection method Methods 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 20
- 239000012528 membrane Substances 0.000 claims abstract description 17
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 claims abstract description 10
- 239000005695 Ammonium acetate Substances 0.000 claims abstract description 9
- 229940043376 ammonium acetate Drugs 0.000 claims abstract description 9
- 235000019257 ammonium acetate Nutrition 0.000 claims abstract description 9
- 238000004949 mass spectrometry Methods 0.000 claims abstract description 9
- 238000004458 analytical method Methods 0.000 claims abstract description 8
- 238000002013 hydrophilic interaction chromatography Methods 0.000 claims abstract description 8
- 238000010829 isocratic elution Methods 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims description 40
- 239000012224 working solution Substances 0.000 claims description 30
- 239000012086 standard solution Substances 0.000 claims description 19
- 239000008267 milk Substances 0.000 claims description 12
- 239000004627 regenerated cellulose Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 10
- 238000004811 liquid chromatography Methods 0.000 claims description 9
- 235000013336 milk Nutrition 0.000 claims description 9
- 210000004080 milk Anatomy 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 108010046377 Whey Proteins Proteins 0.000 claims description 7
- 102000007544 Whey Proteins Human genes 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 6
- 239000005862 Whey Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000004519 grease Substances 0.000 claims description 6
- 239000008101 lactose Substances 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 6
- 238000012544 monitoring process Methods 0.000 claims description 6
- 238000004445 quantitative analysis Methods 0.000 claims description 6
- 108090000623 proteins and genes Proteins 0.000 claims description 5
- 102000004169 proteins and genes Human genes 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 4
- 238000004451 qualitative analysis Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 238000012360 testing method Methods 0.000 abstract description 12
- 238000002414 normal-phase solid-phase extraction Methods 0.000 abstract description 7
- 238000000746 purification Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000012071 phase Substances 0.000 abstract description 4
- 235000013305 food Nutrition 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 238000002347 injection Methods 0.000 description 12
- 239000007924 injection Substances 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 229910021642 ultra pure water Inorganic materials 0.000 description 11
- 239000012498 ultrapure water Substances 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- 230000010355 oscillation Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 239000011550 stock solution Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 239000003651 drinking water Substances 0.000 description 4
- 235000020188 drinking water Nutrition 0.000 description 4
- 235000018102 proteins Nutrition 0.000 description 4
- 229940080281 sodium chlorate Drugs 0.000 description 4
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011002 quantification Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical group O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002552 multiple reaction monitoring Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012113 quantitative test Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 241001089723 Metaphycus omega Species 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000105 evaporative light scattering detection Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 235000008476 powdered milk Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 235000020185 raw untreated milk Nutrition 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- YZHUMGUJCQRKBT-UHFFFAOYSA-M sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 235000021119 whey protein Nutrition 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
-
- 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
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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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
- G01N30/86—Signal analysis
- G01N30/8624—Detection of slopes or peaks; baseline correction
- G01N30/8631—Peaks
-
- 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
- G01N2030/3007—Control of physical parameters of the fluid carrier of temperature same temperature for whole column
-
- 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
- G01N2030/324—Control of physical parameters of the fluid carrier of pressure or speed speed, flow rate
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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 belongs to the technical field of food detection, and provides a method for determining chlorate and perchlorate in raw and auxiliary materials of infant milk powder, which adopts liquid chromatography-tandem mass spectrometry for analysis and comprises the following steps: extracting chlorate and perchlorate in a sample to be detected, and filtering the chlorate and the perchlorate by a filter membrane to obtain a sample solution; injecting the sample solution into a PC HILIC column of a liquid chromatograph, taking acetonitrile and ammonium acetate aqueous solution with the volume ratio of 20-30:80-70 as mobile phases, and performing isocratic elution when the flow rate is 0.15-0.4 ml/min to obtain an effluent; and directly carrying out mass spectrometry on the effluent liquid to obtain a detection result. The invention can realize high-accuracy, high-sensitivity and high-precision test with high efficiency and low cost without solid phase extraction and purification of the extracting solution, and greatly reduces pollution caused in the perchlorate pretreatment process, thereby having great significance in the enterprise production management process.
Description
Technical Field
The invention relates to the technical field of food detection, in particular to a method for measuring chlorate and perchlorate in raw and auxiliary materials of infant milk powder.
Background
At present, the method for measuring chlorate and perchlorate in food is mainly the method adopted in BJT 201706, and in practice, it is found that, in the extraction process, the method not only needs to use a PRiME HLB solid-phase extraction column (3 cc,150 mm), but also needs to use a gradient elution process, the dosage of the sample solution is high, the test time is long, and the cost is high when the method is applied to industrial mass detection, although related technologies, such as a mode of isocratic elution in patent CN107247105B, still needs to purify the sample solution through solid-phase extraction, the test steps are complex, and more importantly, perchlorate pollution may exist in a pretreatment container, an organic reagent and the solid-phase extraction column, so that the measured value is more easily 20 mug/kg higher than the actual value of the sample, thereby affecting the accurate quantification of the sample.
In view of this, the present invention has been proposed.
Disclosure of Invention
The invention provides a method for determining chlorate and perchlorate in raw and auxiliary materials of infant milk powder, which is used for solving the defects that in the prior art, the perchlorate pretreatment process is easy to cause pollution, the test method is long in test time, high in test cost, complex in operation, accurate in measurement and the like due to the fact that a sample solution is prepared by relying on solid-phase extraction purification extracting solution, the pretreatment of a sample is directly carried out in a sample small bottle, a senior PC HILIC column is adopted as a chromatographic column in liquid chromatography-tandem mass spectrometry, the extracting solution is not required to be subjected to solid-phase extraction purification, the sample solution can be obtained by filtering only through a filter membrane, the liquid chromatography-tandem mass spectrometry analysis is carried out, the sample injection amount is as low as 1 microliter, the consumption is small, qualitative and quantitative tests of no pollution, high accuracy, high sensitivity and high precision can be realized efficiently and low in cost by adopting an isocratic elution process, and the method has very important significance in the production management process of enterprises.
Specifically, the invention provides a method for determining chlorate and perchlorate in raw and auxiliary materials of infant milk powder, which adopts liquid chromatography-tandem mass spectrometry for analysis and comprises the following steps:
extracting chlorate and perchlorate in a sample to be detected, and filtering the chlorate and the perchlorate by a filter membrane to obtain a sample solution;
injecting the sample solution into a chromatographic column of liquid chromatography, taking acetonitrile and ammonium acetate water solution with the volume ratio of 20-30:80-70 as mobile phases, and performing isocratic elution when the flow rate is 0.15-0.4 ml/min to obtain effluent; wherein the chromatographic column is a senior hall PC HILIC column;
and directly carrying out mass spectrometry on the effluent liquid to obtain a detection result.
According to the method for measuring chlorate and perchlorate in raw and auxiliary materials of infant milk powder, when the sample to be measured is water for infant milk powder, the sample solution to be measured is obtained by directly adding mixed isotope internal standard solution into the water and filtering the mixed isotope internal standard solution by a regenerated cellulose membrane;
and/or when the sample to be detected is liquid milk, grease, protein powder, lactose, pasture, feed and whey powder, the sample solution to be detected is obtained by mixing the sample to be detected, the mixed isotope internal standard solution and a solvent, performing ultrasonic treatment, taking supernatant, filtering by a regenerated cellulose membrane, discarding the effluent of the previous 3d, collecting the subsequent filtrate, and fixing the volume; wherein the solvent corresponding to the liquid milk is acetonitrile; the solvent corresponding to the grease is acetonitrile water solution; the solvent corresponding to the protein powder, lactose, pasture, feed and whey powder is ultrapure water.
According to the method for measuring chlorate and perchlorate in raw and auxiliary materials of infant milk powder, the specification of the regenerated cellulose membrane is 0.22 mu m.
According to the method for determining chlorate and perchlorate in raw and auxiliary materials of infant milk powder provided by the invention, chlorate-in-room ratio in the mixed isotope internal standard solution 18 O 3 And perchlorate-plant 18 O 4 The concentration is 500-1500 ng/mL and 200-300 ng/mL respectively.
In the test, it was found that the residual chlorate and perchlorate in the conventional glass vessel may interfere with the accuracy of the test. According to the method for measuring chlorate and perchlorate in raw and auxiliary materials of infant milk powder, provided by the invention, the extraction of the sample solution is performed in a glass sample injection vial adopted by liquid chromatography.
According to the method for measuring chlorate and perchlorate in raw and auxiliary materials of infant milk powder, provided by the invention, the sample injection amount of the sample solution to be tested injected into a chromatographic column of liquid chromatography is more than 1 microliter.
According to the method for measuring chlorate and perchlorate in raw and auxiliary materials of infant milk powder, which is provided by the invention, an ion source adopted in mass spectrometry is an electrospray ion source (ESI source), scanning is performed in a negative ion mode, and data are collected in a multi-reaction monitoring (MRM) mode.
According to the method for determining chlorate and perchlorate in raw and auxiliary materials of infant milk powder, provided by the invention, the detection result comprises a qualitative analysis result, and the qualitative analysis is as follows:
preparing a plurality of mixed solutions with known concentrations and containing chlorate and perchlorate, and taking the mixed solutions as a mixed standard working solution I;
performing liquid chromatography-tandem mass spectrometry analysis by taking the mixed standard working solution I as a sample to be tested to obtain chromatographic retention time and relative ion abundance (the percentage relative to the strongest ion abundance is taken as the relative ion abundance of qualitative ions) of chlorate and perchlorate in the mixed standard working solution I;
judging whether the sample to be tested contains chlorate and perchlorate according to the following conditions:
if chromatographic peaks with consistent retention time of chlorate and perchlorate in the mixed standard working solution I are detected in the sample to be detected, and compared with the relative ion abundance of the corresponding qualitative ions in the mixed standard working solution I with equivalent concentration, the deviation is in a specified range, the corresponding chlorate and perchlorate can be determined to be detected in the sample; the specified range is as follows: when the relative ion abundance is > 50%, the allowable relative deviation is ±20%, when the relative ion abundance is 20% -50%, the allowable relative deviation is ±25%, when the relative ion abundance is 10% -20%, the allowable relative deviation is ±30%, and when the relative ion abundance is less than or equal to 10%, the allowable relative deviation is ±50%.
According to the method for measuring chlorate and perchlorate in raw and auxiliary materials of infant milk powder, provided by the invention, the detection result comprises a quantitative analysis result, and the quantitative analysis is as follows:
preparing a plurality of parts of mixed solution containing chlorate and perchlorate and having concentration gradient, and taking the mixed solution as mixed standard working solution II; wherein, all chlorates in the mixed standard working solution II 18 O 3 And perchlorate-plant 18 O 4 The concentrations were 10.0ng/mL and 2.5ng/mL, respectively;
carrying out liquid chromatography-tandem mass spectrometry analysis by taking the mixed standard working solution II as a sample to be tested to obtain a standard working curve which takes the concentration of the mixed standard working solution II as an abscissa and takes a response value corrected by an internal standard as an ordinate;
and calculating the quantitative analysis result from a standard working curve.
In practical applications, the mixed standard working solution I and the mixed standard working solution II may be used in common.
Wherein, the calculation formula of the content can be carried out according to the following formula:
wherein:
x is the content of each component to be detected in the sample to be detected, the unit of packaged drinking water is microgram per liter (mug/L), and the unit of other samples is microgram per kilogram (mug/kg);
c-the concentration of each component to be tested in the sample solution read from the standard working curve, the unit being nanograms per milliliter (ng/mL);
v-final constant volume of sample solution in milliliters (mL);
f, dilution factor in the preparation process of the sample;
m—sample weight, packaging drinking water in milliliters (mL), and other sample units in grams (g).
The calculation results are expressed as arithmetic mean of two independent measurement results obtained under the condition of repeatability, and the results retain three significant digits.
The method for determining chlorate and perchlorate in raw and auxiliary materials of infant milk powder provided by the invention comprises the following steps:
the conditions of the liquid chromatography are as follows:
chromatographic column: a senior hall PC HILIC column;
mobile phase: acetonitrile and 15-25 mmol/L ammonium acetate water solution with the volume ratio of 20-30:80-70;
flow rate: 0.15-0.4 mL/min;
column temperature: 15-45 DEG C
And/or, the mass spectrometry conditions are:
ion source: an electrospray ion source;
the detection mode is as follows: monitoring multiple reactions;
scanning mode: scanning in a negative ion mode;
drying gas: nitrogen gas;
drying gas temperature: 300-400 ℃;
drying gas flow rate: 5-15L/min.
According to the method for determining chlorate and perchlorate in raw and auxiliary materials of infant milk powder, pretreatment is directly carried out in a glass sample injection small bottle, a senior PC HILIC column is adopted as a chromatographic column in liquid chromatography-tandem mass spectrometry, solid phase extraction purification is not needed for extracting solution, sample solution can be obtained by filtering through a filter membrane, liquid chromatography-tandem mass spectrometry analysis is carried out, the sample injection amount is as low as 1 microliter, the dosage is small, and the low-pollution, high-accuracy, high-sensitivity and high-precision test can be effectively realized at low cost by adopting an isocratic elution process, so that the method has very important significance in the production management process of enterprises.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a multi-reaction monitoring (MRM) diagram of chlorate and perchlorate standards and internal standards provided by the present invention; wherein, (a): perchlorate; (b): a perchlorate internal standard; (c): chlorate; (d): a chlorate internal standard;
FIG. 2 is a multi-reaction monitoring (MRM) diagram of a sample solution obtained from liquid milk and an internal standard provided by the invention; wherein, (a): perchlorate; (b): a perchlorate internal standard; (c): chlorate; (d): a chlorate internal standard;
FIG. 3 is a graph showing the standard working curve of perchlorate measured from a mixed standard working solution according to the present invention;
fig. 4 is a standard working curve corresponding to chlorate measured by mixing standard working solution according to the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
The following describes a method for measuring chlorate and perchlorate in raw and auxiliary materials of infant milk powder according to the present invention with reference to fig. 1 to 4.
The reagents and instruments employed in the present invention are as follows:
1. reagents and materials
1.1 reagents
1.1.1 acetonitrile (CH 3 CN): chromatographic purity.
1.1.2 ammonium acetate (CH) 3 COONH 4 ): and a liquid-mass combination stage.
1.1.3 ultrapure water (H) 2 O): the resistivity was 18.2 M.OMEGA.cm.
Note that: the above reagents should be tested for background before use.
1.2 preparation of reagents
1.2.1, 20mmol/L ammonium acetate solution: 1.54g of ammonium acetate (1.1.2) was weighed, dissolved in ultrapure water (1.1.3) and diluted to 500mL, and mixed well.
1.2.2, 50% acetonitrile in water: 250mL of acetonitrile (1.1.1) was taken, 250mL of ultrapure water (1.1.3) was added, and mixed well.
1.3, standard substance
1.3.1 sodium chlorate standard: the purity is more than 99% by adopting standard substances with certificates or high-purity reagents. Chinese names, english names, CAS registry numbers, molecular formulas, and relative molecular weights are detailed in Table 1.
1.3.2, high chlorine sodium salt standard: the purity is more than 99% by adopting standard substances with certificates or high-purity reagents. Chinese names, english names, CAS registry numbers, molecular formulas, and relative molecular weights are detailed in Table 1.
TABLE 1
| Chinese name | English name | CAS registry number | Molecular formula | Relative molecular weight |
| Sodium chlorate | Sodiumchlorate | 7775-09-9 | NaClO 3 | 106.44 |
| Sodium perchlorate | Sodiumperchlorate | 7601-89-0 | NaClO 4 | 122.45 |
1.4 isotope internal standard
1.4.1, chlorate isotope internal standard: chlorate plant 18 O 3 (200. Mu.g/mL with chlorate) 18 O 3 Ion meter, supplied by Beijing Zhengxiang, EURL-SRM Lot No. 024, containing 50 μg/mL perchlorate- 18 O 4 ) Preserving at 4 ℃.
1.5 preparation of Standard solution
1.5.1, chlorate standard stock (1 mg/mL, in terms of chlorate): accurately weighing 0.128g (accurate to 0.0001 g) of sodium chlorate, placing into a 100mL volumetric flask, dissolving with ultrapure water (1.1.5), diluting to scale, shaking, preparing into standard stock solution with concentration of 1mg/mL, and preserving at 4deg.C.
1.5.2, perchlorate standard stock solution (1 mg/mL, per perchlorate): accurately weighing 0.123g (accurate to 0.0001 g) of sodium perchlorate, placing into a 100mL volumetric flask, dissolving with ultrapure water (1.1.5), diluting to scale, shaking, preparing into standard stock solution with concentration of 1mg/mL, and preserving at 4deg.C.
1.5.3, mixing standard intermediate solution: accurately measuring 0.2mL of chlorate standard stock solution (1.5.1) and 0.1mL of perchlorate standard stock solution (1.5.2), placing in the same 100mL volumetric flask, diluting to scale with ultrapure water (1.1.3), shaking uniformly to prepare mixed standard intermediate solutions with chlorate and perchlorate concentrations of 2.0 mug/mL and 1.0 mug/mL respectively, and preserving at 4 ℃.
1.5.4, mixed isotope internal standard solution: respectively accurately measuring 50 μl of chlorate isotope internal standard (1.4.1), placing in 10.0mL volumetric flask, diluting with ultrapure water (1.1.5) to scale, shaking, and making chlorate-room solution 18 O 3 Perchlorate-like material 18 O 4 The mixed isotope internal standard solutions with the concentrations of 1000ng/mL and 250ng/mL are stored at 4 ℃.
1.5.5, mixing standard working solution: the mixed standard intermediate (1.5.3) was accurately measured at 0. Mu.L, 10. Mu.L, 25. Mu.L, 50. Mu.L, 100. Mu.L, 250. Mu.L, 500. Mu.L, 1000. Mu.L, and 100. Mu.L of the mixed isotope internal standard solution (1.5.4), diluted with the ultrapure water solution (1.1.3) and fixed to a volume of 10mL, respectively, to obtain mixed standard working solutions S0, S1-S7. The chlorate concentration is as follows: 0.00ng/mL, 2.00ng/mL, 5.00ng/mL, 10.0ng/mL, 20.0ng/mL, 50.0ng/mL, 100ng/mL, 200ng/mL, perchlorate concentrations are in order: 0.00ng/mL, 1.00ng/mL, 2.50ng/mL, 5.00ng/mL, 10.0ng/mL, 25.0ng/mL, 50.0ng/mL, 1Chlorate (in the mixed standard working solution) of 00ng/mL 18 O 3 Perchlorate-like material 18 O 4 The concentration is 10.0ng/mL and 2.5ng/mL respectively, or mixed standard working solution with proper concentration is prepared according to the requirement. It is used for new preparation.
2. Apparatus and device
2.1, liquid chromatography-tandem mass spectrometer equipped with electrospray ion source (ESI source).
2.2, vortex oscillator.
2.3, a tissue masher.
2.4, a homogenizer.
2.5, electronic balance: the sensing amount is 0.0001g.
2.6, an ultrasonic constant-temperature water bath oscillator.
2.7, glass sample injection vial: 1.5mL.
Note that: 2.7 should be background tested before use.
3. Sample preparation and preservation
3.1 drinking water for production
Fully and uniformly mixing and directly taking.
3.2, liquid milk:
shaking thoroughly, taking a proper amount of representative sample, dividing into two parts, respectively placing into clean container as sample and sample, sealing, marking, and storing at 4deg.C in dark place.
3.3, whey powder, whey protein powder, grease and lactose:
mixing, taking a proper amount of representative sample, dividing into two parts, respectively placing into clean container, sealing, marking, and storing at normal temperature in dark place.
3.4, pasture, feed:
taking a proper amount of representative samples, crushing by a crusher, sieving by a 40-mesh sieve, equally dividing into two parts, respectively filling the two parts as the samples and the reserved samples into a clean container, sealing and marking, and preserving at normal temperature in a dark place.
The extraction and purification process of the sample to be tested in the invention is as follows:
(1) Process water: accurately transferring 1.0mL of sample, adding 10.0 mu L of mixed isotope internal standard solution (1.5.4), vortex oscillating for 10s, filtering with 0.22 mu m regenerated cellulose filter membrane, and taking the subsequent filtrate as sample solution for measurement by a liquid chromatography-tandem mass spectrometer.
(2) Liquid milk: accurately weighing 0.5g (accurate to 0.0001 g) of the sample, placing the sample in a 1.5mL glass sample injection vial (2.7), adding 15 mu L of mixed isotope internal standard solution (1.5.4), accurately adding 1.0mL of acetonitrile (1.1.1), performing spiral cover vortex oscillation for 10s, performing ultrasonic treatment for 5min, taking supernatant, passing through a 0.22 mu m regenerated cellulose filter membrane, discarding the front 3d effluent, and collecting the subsequent filtrate to be used as a sample solution for measurement by a liquid chromatography-tandem mass spectrometer.
(3) Protein powder, lactose, pasture, feed: accurately weighing 0.075g (0.0001 g) of the sample, placing the sample into a 1.5mL glass sample injection vial (2.7), adding 15 mu L of mixed isotope internal standard solution (1.5.4), accurately adding 0.5mL of ultrapure water (1.1.3), carrying out vortex oscillation for 5s, accurately adding 1.0mL of acetonitrile (1.1.1) firstly, carrying out vortex oscillation for 10s by a spiral cover, carrying out ultrasonic treatment for 30min, taking supernatant, passing through a 0.22 mu m regenerated cellulose filter membrane, discarding the front 3d effluent, and collecting the subsequent filtrate as a sample solution for measurement by a liquid chromatography-tandem mass spectrometer.
(4) 0.2g (accurate to 0.0001 g) of whey powder is accurately weighed and placed in a 1.5mL glass sample injection small bottle (2.7), 15 mu L of mixed isotope internal standard solution (1.5.4) is added, 0.5mL of ultrapure water (1.1.3) is accurately added, vortex oscillation is carried out for 5s, 1.0mL of acetonitrile (1.1.1) is accurately added, vortex oscillation is carried out for 10s by a spiral cover for 5min, supernatant is taken and passes through a 0.22 mu m regenerated cellulose filter membrane, the front 3d effluent is discarded, and the subsequent filtrate is collected and used as a sample solution for measurement by a liquid chromatograph-tandem mass spectrometer.
(5) Grease: accurately weighing 0.2g (accurate to 0.0001 g) of the sample, placing the sample in a 1.5mL glass sample injection vial (2.7), adding 10 mu L of mixed isotope internal standard solution (1.5.4), accurately adding 1.0mL of 50% acetonitrile water solution (1.2.2), spirally oscillating for 30s by a spiral cover, standing, taking supernatant, passing through a 0.22 mu m regenerated cellulose filter membrane, discarding the front 3d effluent, and collecting the subsequent filtrate as a sample solution for measurement by a liquid chromatograph-tandem mass spectrometer.
0.50001g and 0.50002g of raw milk (belonging to liquid milk) of an infant enterprise are respectively and accurately weighed, placed in a 1.5mL glass sample injection vial, 15 mu L of mixed isotope internal standard solution is added, 1.0mL acetonitrile is accurately added, spiral cover vortex oscillation is carried out for 10s, ultrasound is carried out for 5min, supernatant fluid is taken to pass through a 0.22 mu m regenerated cellulose filter membrane, the front 3d effluent is discarded, and subsequent filtrate is collected and used as a sample solution for liquid chromatography-tandem mass spectrometer measurement.
The detection conditions at the time of testing in a liquid chromatograph-tandem mass spectrometer are as follows:
conditions of liquid chromatography
a) Chromatographic column: the senior hall PC HILIC column (150 mm. Times.2.0 mm,5 μm).
b) Mobile phase: acetonitrile+20 mmol/L aqueous ammonium acetate (25:75, V/V);
d) Flow rate: 0.25mL/min.
e) Column temperature: 35 ℃.
f) Sample injection amount: 1 mul.
Mass spectrometry conditions
a) Ion source: electrospray ion source (ESI source).
b) The detection mode is as follows: multiple Reaction Monitoring (MRM).
c) Scanning mode: and scanning in a negative ion mode.
d) Drying gas temperature: 350 ℃ (nitrogen).
e) Drying gas flow rate: 10L/min (nitrogen).
f) Atomizer pressure: 413.8kPa (Nitrogen).
g) Data were collected using the Multiple Reaction Monitoring (MRM) mode and mass spectrometry parameters are shown in table 2.
TABLE 2
* Ion pairs were quantified.
Qualitative determination:
determination of the Mixed Standard working solution and the Condition of the test under the same test conditionsSample solution obtained from liquid milkThe obtained chromatograms are shown in fig. 1 and 2, and recordedSample solution obtained from liquid milkAnd chromatographic retention time of chlorate and perchlorate in mixed standard working solutionThe percentage relative to the strongest ion abundance is taken as the relative ion abundance of the qualitative ion. It was found that,sample solution obtained from liquid milkThe chromatographic peak with the retention time consistent with that of chlorate and perchlorate in the mixed standard working solution (1.5.5) is detected, and the deviation of the qualitative ions of the chromatographic peak is 2.1% compared with the relative abundance of the corresponding qualitative ions in the standard solution with the equivalent concentration, so that the corresponding chlorate and perchlorate are detected in the sample.
Quantitative test:
the mixed standard working solution (1.5.5) was measured under the above measurement conditions, and a standard working curve was drawn with the concentration of the mixed standard working solution as the abscissa and the response value after the internal standard correction as the ordinate, as shown in fig. 3 and 4.
According to the standard working curve, the content is calculated by using the response value corrected by the internal standard according to the internal standard method, and the calculation process is as follows:
standard working curve: y=1.328607x+0.173985
Wherein y is the peak area, x is the content of each component to be detected in the sample to be detected, wherein the chlorate peak area measured by the instrument is 5483, and x is 7.596ng/mL after being carried in; the perchlorate peak area was 656, and x was 6.965ng/mL calculated after the introduction.
The calculation results are expressed as arithmetic mean of two independent measurement results obtained under the condition of repeatability, and the results retain three significant digits.
Further, the chlorate and perchlorate contents in the liquid milk were calculated to be 7.596ng/mL and 6.965ng/mL, respectively.
Through test verification on other samples, the sensitivity, accuracy and precision of the measuring method are as follows:
(1) Sensitivity of
When the sample amount is 1.0mL, the detection limit of chlorate in the packaged drinking water is 0.6 mug/L, and the quantitative limit is 2.0 mug/L; the detection limit of perchlorate was 0.4. Mu.g/L and the quantitative limit was 1.0. Mu.g/L.
When the sample amount is 0.075g (accurate to 0.0001 g) and the constant volume is 1.5mL, the detection limit of protein powder, lactose, pasture and chlorate in feed is 6.6 mug/kg, and the quantitative limit is 20.0 mug/kg; the detection limit of perchlorate was 3.3. Mu.g/kg and the quantitative limit was 10.0. Mu.g/kg.
When the sample amount was 0.1g (accurate to 0.0001 g) and the constant volume was 1.0mL, the limit of detection of chlorate in the grease was 5.0. Mu.g/kg and the limit of quantification was 15.0. Mu.g/kg; the detection limit of perchlorate was 2.5. Mu.g/kg and the quantitative limit was 7.5. Mu.g/kg.
When the sample amount is 0.2g (accurate to 0.001 g) and the constant volume is 1.5mL, the detection limit of chlorate in whey powder milk is 5.0 mug/kg and the quantitative limit is 15.0 mug/kg; the detection limit of perchlorate was 2.5. Mu.g/kg and the quantitative limit was 7.5. Mu.g/kg.
When the sample amount was 0.5g (accurate to 0.001 g) and the constant volume was 1.5mL, the limit of detection of chlorate in the liquid milk was 1.8. Mu.g/kg and the limit of quantification was 6.0. Mu.g/kg; the detection limit of perchlorate was 1.2. Mu.g/kg and the quantitative limit was 3.0. Mu.g/kg.
(2) Accuracy of
The method is within the range of 3-1000 mug/kg of adding concentration, and the recovery rate is 80% -110%.
(3) Precision of
The absolute difference between the two independent measurements obtained under repetitive conditions must not exceed 20% of the arithmetic mean.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The method for determining chlorate and perchlorate in raw and auxiliary materials of infant milk powder is characterized by comprising the following steps of:
extracting chlorate and perchlorate in a sample to be detected, and filtering the chlorate and the perchlorate by a filter membrane to obtain a sample solution;
injecting the sample solution into a chromatographic column of liquid chromatography, taking acetonitrile and ammonium acetate water solution with the volume ratio of 20-30:80-70 as mobile phases, and performing isocratic elution when the flow rate is 0.15-0.4 ml/min to obtain effluent; wherein the chromatographic column is a senior hall PC HILIC column;
and directly carrying out mass spectrometry on the effluent liquid to obtain a detection result.
2. The method for determining chlorate and perchlorate in raw and auxiliary materials of infant milk powder according to claim 1, wherein when the sample to be determined is water for infant milk powder, the sample solution is obtained by directly adding a mixed isotope internal standard solution into the water and filtering the mixed isotope internal standard solution by a regenerated cellulose membrane;
and/or when the sample to be detected is liquid milk, grease, protein powder, lactose, pasture, feed and whey powder, the sample solution to be detected is obtained by mixing the sample to be detected, the mixed isotope internal standard solution and the solvent, performing ultrasonic treatment, taking supernatant, filtering by a regenerated cellulose membrane, discarding the effluent of the previous 3d, collecting the subsequent filtrate, and determining.
3. The method for measuring chlorate and perchlorate in raw and auxiliary materials of infant milk powder according to claim 2, wherein the regenerated cellulose membrane has a specification of 0.22 μm.
4. The method for measuring chlorate and perchlorate in raw and auxiliary materials of infant milk powder according to any one of claims 1 to 3, wherein chlorate-in-a-ball in the mixed isotope internal standard solution 18 O 3 And perchlorate-plant 18 O 4 The concentration is 500-1500 ng/mL and 200-300 ng/mL respectively.
5. The method for measuring chlorate and perchlorate in raw and auxiliary materials of infant milk powder according to any one of claims 1 to 4, wherein the extraction of the sample solution is performed in a glass sample-feeding vial used for liquid chromatography.
6. The method for measuring chlorate and perchlorate in raw and auxiliary materials of infant milk powder according to any one of claims 1 to 5, wherein the sample amount of the sample solution injected into the column of liquid chromatography is 1 microliter or more.
7. The method for determining chlorate and perchlorate in raw and auxiliary materials of infant milk powder according to any one of claims 1 to 6, wherein the ion source used in the mass spectrometry is an electrospray ion source (ESI source), scanning is performed in a negative ion mode, and data is collected in a multi-reaction monitoring (MRM) mode.
8. The method for measuring chlorate and perchlorate in raw and auxiliary materials of infant milk powder according to any one of claims 1 to 7, wherein the detection result comprises a qualitative analysis result, and the qualitative analysis is as follows:
preparing a plurality of mixed solutions with known concentrations and containing chlorate and perchlorate, and taking the mixed solutions as a mixed standard working solution I;
taking the mixed standard working solution I as a sample to be tested for carrying out the liquid chromatography-tandem mass spectrometry analysis to obtain the chromatographic retention time and the relative ion abundance of chlorate and perchlorate in the mixed standard working solution I;
judging whether the sample to be tested contains chlorate and perchlorate according to the following conditions:
if chromatographic peaks with consistent retention time of chlorate and perchlorate in the mixed standard working solution I are detected in the sample to be detected, and compared with the relative ion abundance of the corresponding qualitative ions in the mixed standard working solution I with equivalent concentration, the deviation is in a specified range, the corresponding chlorate and perchlorate can be determined to be detected in the sample; the specified range is as follows: when the relative ion abundance is > 50%, the allowable relative deviation is ±20%, when the relative ion abundance is 20% -50%, the allowable relative deviation is ±25%, when the relative ion abundance is 10% -20%, the allowable relative deviation is ±30%, and when the relative ion abundance is less than or equal to 10%, the allowable relative deviation is ±50%.
9. The method for measuring chlorate and perchlorate in raw and auxiliary materials of infant milk powder according to any one of claims 1 to 8, wherein the detection result comprises a quantitative analysis result, and the quantitative analysis is as follows:
preparing a plurality of parts of mixed solution containing chlorate and perchlorate and having concentration gradient, and taking the mixed solution as mixed standard working solution II; wherein, all chlorates in the mixed standard working solution II 18 O 3 And perchlorate-plant 18 O 4 The concentrations were 10.0ng/mL and 2.5ng/mL, respectively;
carrying out liquid chromatography-tandem mass spectrometry analysis by taking the mixed standard working solution II as a sample to be tested to obtain a standard working curve which takes the concentration of the mixed standard working solution II as an abscissa and takes a response value corrected by an internal standard as an ordinate;
and calculating the quantitative analysis result from a standard working curve.
10. The method for measuring chlorate and perchlorate in raw and auxiliary materials of infant milk powder according to any one of claims 1 to 9, comprising:
the conditions of the liquid chromatography are as follows:
chromatographic column: a senior hall PC HILIC column;
mobile phase: acetonitrile and 15-25 mmol/L ammonium acetate water solution with the volume ratio of 20-30:80-70;
flow rate: 0.15-0.4 mL/min;
column temperature: 15-45 DEG C
And/or, the mass spectrometry conditions are:
ion source: an electrospray ion source;
the detection mode is as follows: monitoring multiple reactions;
scanning mode: scanning in a negative ion mode;
drying gas: nitrogen gas;
drying gas temperature: 300-400 ℃;
drying gas flow rate: 5-15L/min.
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