CN111257452B - Method for detecting addition of synthetic acetic acid into Zhenjiang aromatic vinegar - Google Patents
Method for detecting addition of synthetic acetic acid into Zhenjiang aromatic vinegar Download PDFInfo
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 206
- 235000021419 vinegar Nutrition 0.000 title claims abstract description 78
- 239000000052 vinegar Substances 0.000 title claims abstract description 77
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 48
- 239000001257 hydrogen Substances 0.000 claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 45
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 17
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000523 sample Substances 0.000 claims description 59
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000013068 control sample Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 241000209094 Oryza Species 0.000 claims description 7
- 235000007164 Oryza sativa Nutrition 0.000 claims description 7
- 235000009566 rice Nutrition 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012470 diluted sample Substances 0.000 claims description 5
- 238000000053 physical method Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 238000012937 correction Methods 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000013375 chromatographic separation Methods 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 10
- 235000013305 food Nutrition 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 5
- 229960000583 acetic acid Drugs 0.000 description 47
- 235000011054 acetic acid Nutrition 0.000 description 44
- 238000004817 gas chromatography Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000004587 chromatography analysis Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 206010022998 Irritability Diseases 0.000 description 1
- 238000006935 Simonis synthesis reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000019606 astringent taste Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- -1 carboxyl hydrogen acetate Chemical compound 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000008373 pickled product Nutrition 0.000 description 1
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011782 vitamin Substances 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
- 238000005303 weighing Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
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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
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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
- G01N30/60—Construction of the column
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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
- G01N30/60—Construction of the column
- G01N30/6052—Construction of the column body
- G01N30/6073—Construction of the column body in open tubular form
- G01N30/6078—Capillaries
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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
- G01N30/72—Mass spectrometers
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Abstract
The invention relates to a method for detecting the addition of synthetic acetic acid into Zhenjiang aromatic vinegar, belonging to the field of food adulteration detection. The method comprises the following steps: (1) Removing the interference of hydrogen at the acetic acid carboxyl site and water in vinegar, and measuring the hydrogen isotope ratio of the acetic acid methyl site by using a stable isotope ratio mass spectrometer; (2) Constructing a hydrogen isotope database of Zhenjiang aromatic vinegar control samples; (3) And (5) determining the hydrogen isotope ratio of the methyl acetate site of the sample to be detected, and comparing the hydrogen isotope ratio with the Zhenjiang aromatic vinegar database to obtain a conclusion. The invention utilizes the stable isotope ratio mass spectrometer to measure the hydrogen isotope ratio, realizes the detection of the illegal addition of the synthetic acetic acid in the Zhenjiang aromatic vinegar, and solves the technical problem that the illegal addition of the synthetic acetic acid in the current Zhenjiang aromatic vinegar is difficult to detect. The invention promotes the progress of food adulteration detection technology and provides a method for evaluating the authenticity of vinegar products and detecting adulteration in future.
Description
Technical field:
the invention relates to a method for detecting illegal addition of synthetic acetic acid in Zhenjiang aromatic vinegar, belongs to the field of food adulteration detection, and can be used for food adulteration detection research and daily inspection.
The background technology is as follows:
zhenjiang aromatic vinegar is also called Zhenjiang vinegar, and is a traditional famous product in Jiangsu Zhenjiang places. According to the specification of GB/T18623-2011 "geographical sign product Zhenjiang aromatic vinegar", zhenjiang aromatic vinegar is a brewed rice vinegar with unique flavor produced in Zhenjiang region, which is prepared by adopting the special processes of traditional compound saccharification, alcohol fermentation, solid layered acetic acid fermentation, adding stir-fried rice color vinegar and the like, and aging to obtain the vinegar with strong fragrance, acid but not astringent taste.
Zhenjiang aromatic vinegar is created in 1840, and is paid out for 5 times in China to obtain gold medal prizes, superior prizes, first-class prizes and the like, and in 2018, the Zhenjiang aromatic vinegar industry produces 36.5 ten thousand tons, so that the income of main camping business is 29.81 hundred million yuan, and the same proportion is increased by 6.2%. However, in recent years, consumer nerves were picked up once for once about the counterfeiting event of Zhenjiang aromatic vinegar: in 2004, the central view report: the aromatic vinegar is so astringent that the new Jing newspaper in 2017 reports that Tianjin single-flow town makes false Zhenjiang aromatic vinegar and the like, counterfeiters commonly use low-quality edible vinegar to impersonate the Zhenjiang aromatic vinegar or add edible glacial acetic acid into the vinegar for imitation in order to pursue economic benefits, and even more, as blending proportion and blending components cannot be detected, small workshops use industrial glacial acetic acid for blending production, the counterfeited products bring great food safety risk hidden danger, seriously influence physical and mental health of consumers, but lack effective detection means.
At present, the method for identifying and synthesizing acetic acid in China is based on radioisotope in acetic acid according to GB/T22099-2008 14 C, the naturalness characteristic of the synthesized glacial acetic acid is detected, however, due to the special property and the use requirement of the radioactive isotope, the food quality monitoring department cannot detect the naturalness index, only the Shanghai complex denier university radiology institute can carry out related detection in the whole country, the technology is limited to the detection of the glacial acetic acid, and the acetic acid in the vinegar is required to be purified when the sample is analyzed, so that the difficulty of technical popularization is increased.
Foreign researches show that the synthesis of acetic acid [ Remaud, G. ] can be distinguished according to the hydrogen isotope ratio characteristics of acetic acid; guillou, c.; vallet, c.; martin, G.J.A coupled NMR and MS isotopic method for the authentication of natural vitamins.Fresenius J.Anal.Chem.1992,342,457 ], but because vinegar contains a large amount of moisture, moisture is required to be removed before measurement, and hydrogen atoms on acetic acid carboxyl groups are extremely easy to exchange with water in the environment for hydrogen isotopes, the significance and the application effect of measuring the hydrogen isotope ratio of the whole acetic acid molecule are limited. The method of analyzing stable hydrogen isotope ratios of methyl acetate sites in vinegar using point-specific fractionation-nuclear magnetic resonance (SNIF-NMR) was developed by Hermann et al, [ Hermann, a. (2001) Determination of D/H isotope ratio in acetic acid from vinegars and pickled products by H-2-NMR telescope.eur Food Res tech, 212 683-686; fauhl, C., wittkowski, R. (1996) On-line 1H-NMR to facilitate tube preparation in SNIF-NMR analysis.Z Lebensm Unters Forsch (1996), 541-545; hsieh C W, li P H, cheng J Y, et al using SNIF-NMR method to identify the adulteration of molasses spirit vinegar by synthetic acetic acid in rice vinegar [ J ]. Industrial crops and products,2013,50:904-908; perini M, paolini M, simoni M, et al, stable isotope ratio analysis for verifying the authenticity of balsamic and wine vinegar [ J ]. Journal of agricultural and food chemistry,2014,62 (32): 8197-8203], however, deuterium is low in nature (natural abundance is about 150 x 10-6), resonance frequency of deuterons is low, spectrum dispersion degree is low, sensitivity of SNIF-NMR method is low, a single sample needs long analysis time (> 8 h) to obtain satisfactory signal-to-noise ratio signal and measurement precision, and acetic acid in vinegar sample needs special device for separation and purification, analysis efficiency is low and cost is high.
The stable isotope ratio mass spectrometer has the advantages of rapidness and convenience in the aspect of measuring the stable hydrogen isotope composition characteristics of substances, and a plurality of quality monitoring departments in China are equipped with the instrument, however, in the field of Zhenjiang aromatic vinegar analysis, how to eliminate the interference of carboxyl hydrogen acetate and accurately measure the hydrogen isotope ratio of methyl sites, and defining the isotope characteristic difference between Zhenjiang aromatic vinegar and synthetic acetic acid is a precondition and key of related research and application.
The invention comprises the following steps:
in order to solve the problem that the Zhenjiang aromatic vinegar lacks a simple, quick and low-cost method for detecting the synthetic acetic acid, the invention aims to accurately detect the hydrogen isotope characteristics of the methyl acetate locus in the Zhenjiang aromatic vinegar by adopting a stable isotope technology, construct a hydrogen isotope database of the Zhenjiang aromatic vinegar, and detect whether the product contains the synthetic acetic acid based on the hydrogen isotope characteristic.
The scheme adopted by the invention is as follows: the method comprises the steps of establishing an acetate methyl site hydrogen isotope database of real Zhenjiang aromatic vinegar, analyzing the difference of acetate methyl site hydrogen isotope characteristics of a sample to be detected, and judging;
the Zhenjiang aromatic vinegar accords with the regulations of GB/T18623-2011 'Zhenjiang aromatic vinegar as a geographic sign product';
further, the method of the present invention comprises the steps of:
(1) Control sample: obtaining a real sample of Zhenjiang aromatic vinegar produced by taking rice as a raw material from a Zhenjiang aromatic vinegar production enterprise;
(2) Sample to be detected: detecting whether the marked production raw material containing the synthetic acetic acid is a Zhenjiang aromatic vinegar sample of rice;
(3) Detecting the hydrogen isotope ratio (delta D) of the methyl acetate locus in the control sample and the sample to be detected respectively;
further, the control sample is obtained from 20 batches or more of Zhenjiang aromatic vinegar in nationwide range of each year;
(4) Construction of a database of hydrogen isotope ratios of methyl acetate sites in control samples: sequentially arranging the data of the hydrogen isotope ratio of the methyl acetate site of the control sample measured in the step (3), and determining the numerical range of the hydrogen isotope ratio of the methyl acetate site according to the maximum value and the minimum value;
(5) And (3) judging the synthesized acetic acid in the sample to be tested: comparing the hydrogen isotope ratio of the methyl acetate site in the sample to be detected, which is measured in the step (3), with the numerical range of the control sample obtained in the step (4), and if the numerical value of the sample to be detected exceeds the numerical range of the step (4), synthesizing acetic acid in the sample to be detected;
further, the method for detecting the methyl acetate site hydrogen isotope ratio (δD) in the sample in the step (3) is specifically as follows:
(1) removing hydrogen at the carboxyl site of acetic acid with a chemical reagent to convert acetic acid to acetate;
(2) removing water in the sample by a physical method to obtain a solid sample;
(3) dissolving the solid sample in the previous step by using a dilute acid solution to obtain an acidified sample;
(4) properly diluting the acidified sample with an organic reagent to obtain a diluted sample;
(5) separating acetic acid and other organic reagents, a small amount of water and other hydrogen-containing compounds in the diluted sample by using a capillary chromatographic column;
(6) the acetic acid component is converted into hydrogen (H) by pyrolysis at 1420 DEG C 2 ) Determining the hydrogen isotope ratio D/H of the hydrogen by using a stable Isotope Ratio Mass Spectrometer (IRMS);
(7) and (3) carrying out data correction by using an acetic acid standard substance with a known delta D value as a reference to obtain a sample delta D.
Further, the chemical agent includes, but is not limited to, at least one of alkaline materials such as sodium hydroxide, calcium hydroxide, potassium hydroxide, etc., or carbonates such as calcium carbonate, sodium carbonate, potassium carbonate, etc.;
further, the chemical reagent is added in an amount to ensure that all acetic acid in the sample is converted to acetate; preferably calcium hydroxide;
further, the physical method includes, but is not limited to, at least one of a drying method, a chromatographic separation method, a freeze drying method;
preferably, the physical method is a freeze drying method;
further, the dilute acid solution includes, but is not limited to, at least one of dilute sulfuric acid, dilute hydrochloric acid, dilute phosphoric acid, and dilute nitric acid.
Further, the dilute acid solution is added in an amount to ensure that the excess chemical agent in the first neutralization step and the last step, and the acetate is re-acidified to generate acetic acid; preferably a dilute sulfuric acid solution;
further, the organic reagent includes, but is not limited to, at least one of ethanol, methanol, acetone, propanol, diethyl ether; preferably, the organic reagent is acetone;
further, the addition amount of the organic reagent is diluted to 1 g/L-10 g/L of acetic acid content; preferably 4-8g/L;
still further, the diluted sample is allowed to stand at a low temperature for a period of time, and then the precipitate is removed and reused for chromatographic column separation;
further, the capillary chromatography column includes, but is not limited to, a polar chromatography column, a molecular sieve chromatography column, a carbon-based bonded chromatography column, a polystyrene-divinylbenzene chromatography column, a bonded divinylbenzene/ethylene glycol dimethacrylate chromatography column; preferably a bound divinylbenzene/ethylene glycol dimethacrylate chromatography column;
preferably, the sample injection volume is 1 mu L, the temperature of a gas chromatography sample injection port is 270 ℃, the gas chromatography flow rate is constant current 1.2mL/min, the split ratio of the gas chromatography sample injection port is 20:1, and the temperature of the gas chromatography is constant at 180 ℃;
further, the temperature of the cracking module ensures the constant temperature of 1420 ℃;
further, selecting an acetic acid standard substance with a known methyl site delta D value, processing and measuring according to a pretreatment step of a sample, and finally correcting to obtain the delta D value of the methyl site of the acetic acid in the sample.
The beneficial effects are that:
the invention adopts stable isotope technology to measure the hydrogen isotope ratio of methyl acetate sites in Zhenjiang aromatic vinegar, overcomes the defect of lack of application value of the overall hydrogen isotope characteristics of acetic acid in Zhenjiang aromatic vinegar, solves the technical problem that the hydrogen isotope ratio of methyl acetate sites in Zhenjiang aromatic vinegar is difficult to measure, utilizes the characteristic difference between the hydrogen isotopes characteristics of Zhenjiang aromatic vinegar and synthetic acetic acid caused by stable isotope fractionation, realizes the detection of synthetic acetic acid in Zhenjiang aromatic vinegar by comparing real samples, and provides a new method for the authenticity identification of traditional Zhenjiang aromatic vinegar products.
The specific embodiment is as follows:
the invention is described below by means of specific embodiments. The technical means used in the present invention are methods well known to those skilled in the art unless specifically stated. Further, the embodiments should be construed as illustrative, and not limiting the scope of the invention, which is defined solely by the claims. Various changes or modifications to the materials ingredients and amounts used in these embodiments will be apparent to those skilled in the art without departing from the spirit and scope of the invention.
Example 1: determination of methyl acetate site hydrogen isotope ratio in Zhenjiang aromatic vinegar
a) Weighing 25mL Zhenjiang aromatic vinegar sample, adding 1g calcium hydroxide, vortex shaking for 2h, centrifuging at 8000rpm for 30min, and collecting supernatant;
b) Freeze-drying the supernatant in a freeze dryer, and keeping the powder for later use;
c) 15mL of sulfuric acid solution (1 moL/L) was added to the sample powder, and vortexed for 1h;
d) Adding anhydrous acetone to the dilute sulfuric acid treated sample until the acetic acid concentration is about 4g/L based on the acetic acid concentration in the original vinegar sample, standing, and taking the supernatant to be analyzed;
e) Setting the temperature of a gas chromatography sample inlet at 270 ℃, setting the flow rate of the gas chromatography at a constant flow of 1.2mL/min, setting the split ratio of the gas chromatography sample inlet at 20:1, setting the temperature raising program of the gas chromatography at a constant temperature of 180 ℃, and setting the temperature of a cracking module to ensure the constant temperature of 1420 ℃;
f) Confirming that the working environment, the air tightness and the vacuum degree of an ion chamber of the stable isotope ratio mass spectrometer meet the requirements, and then detecting H by a detecting instrument 2 The precision and stability of the medium delta D, and adjusting the ion source parameter value if necessary;
g) Pure acetic acid, water and acetone are used as experimental materials, and sample injection measurement is carried out to determine the retention time of each substance;
h) The treated sample is injected with 1 mu L, so that acetic acid is separated by a chromatographic column and then enters a high-temperature cracking device to be converted into hydrogen (H) 2 ) Post-measurement of hydrogen isotope ratio (D/H, noted as δD Measuring ) The results are shown in Table 1;
i) Acetic acid with a known hydrogen isotope ratio at the methyl site was selected as a standard substance (laboratory work standard WSD, δd was used here CH3 = -223.93%o), the results of the treatment performed by the method for treating Zhenjiang aromatic vinegar sample are shown in table 2;
j) Data correction: the measured value and the given value of the acetic acid working standard WSD have a difference of 27.66 per mill, so that the delta D value of the fruit vinegar beverage sample is known to be the measured value delta D Measuring The results obtained by subtracting 27.66%o are shown in Table 3;
TABLE 1 determination of acetic acid delta D in Zhenjiang aromatic vinegar samples Measuring (‰)
| Repeat-1 | Repeat-2 | Average value of | Standard deviation of | |
| δD Measuring | -301.99 | -304.62 | -303.31 | 1.86 |
TABLE 2 measurement results of acetic acid working Standard WSD
| Number of measurements | Repeat-1 | Repeat-2 | Average value of |
| δD Measuring (‰) | -195.48 | -197.06 | -196.27 |
TABLE 3 methyl acetate site Hydrogen isotope ratio delta D in Zhenjiang aromatic vinegar samples CH3 (‰)
| Repeat-1 | Repeat-2 | Average value of | Standard deviation of | |
| δD CH3 | -329.65 | -332.28 | -330.96 | 1.86 |
Example 2: detection example of synthetic acetic acid in Zhenjiang aromatic vinegar sample to be detected
a) Collecting Zhenjiang aromatic vinegar samples with real raw material information from a regular Zhenjiang aromatic vinegar production enterprise, wherein the total number of the samples is 20;
b) 3 samples with label information remarked as Zhenjiang aromatic vinegar are purchased from the market;
c) The methyl site hydrogen isotope ratio of acetic acid in each sample was determined as in example 1;
d) Through statistics, delta D of 20 real Zhenjiang aromatic vinegar samples CH3 (mill) distribution range is-315.21 mill to-346.87 mill;
e) Delta D of commercially available Zhenjiang aromatic vinegar sample for inspection CH3 The results are shown in Table 2.
TABLE 2 delta D values (mill) for commercially available Zhenjiang aromatic vinegar samples
| Sample numbering | Sample 1 to be detected | Sample No. 2 to be detected | 3# sample to be detected |
| Delta D value | -330.65 | -344.01 | -317.87 |
As can be seen from Table 2,3 commercial Zhenjiang aromatic vinegar samples did not contain synthetic acetic acid.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, which shall be covered by the scope of the claims of the present invention.
Claims (6)
1. The method for detecting the addition of synthetic acetic acid into Zhenjiang aromatic vinegar is characterized by comprising the following steps of:
(1) Control sample: obtaining a real sample of Zhenjiang aromatic vinegar produced by taking rice as a raw material from a Zhenjiang aromatic vinegar production enterprise;
(2) Sample to be detected: detecting whether the marked production raw material containing the synthetic acetic acid is a Zhenjiang aromatic vinegar sample of rice;
(3) Detecting the hydrogen isotope ratio delta D of the methyl acetate locus in the control sample and the sample to be detected respectively;
(4) Constructing a database by using the hydrogen isotope ratio of the methyl acetate locus in the control sample;
(5) And (3) judging the synthesized acetic acid in the sample to be tested: comparing the hydrogen isotope ratio of the methyl acetate site in the sample to be detected, which is measured in the step (3), with the delta D of the control sample obtained in the step (4), and if the value of the sample to be detected exceeds the value range of the step (4), synthesizing acetic acid in the sample to be detected;
the method for detecting the hydrogen isotope ratio delta D of the methyl acetate site in the sample in the step (3) is specifically as follows:
(1) removing hydrogen at the carboxyl site of acetic acid with a chemical reagent to convert acetic acid to acetate;
(2) removing water in the sample by a physical method to obtain a solid sample;
(3) dissolving the solid sample in the previous step by using a dilute acid solution to obtain an acidified sample;
(4) properly diluting the acidified sample with an organic reagent to obtain a diluted sample;
(5) separating acetic acid and other organic reagents, a small amount of water and other hydrogen-containing compounds in the diluted sample by using a capillary chromatographic column;
(6) the acetic acid component is decomposed and converted into hydrogen at the high temperature of 1420 ℃, and the hydrogen isotope ratio D/H of the hydrogen is measured by using a stable Isotope Ratio Mass Spectrometer (IRMS);
(7) and (3) carrying out data correction by using an acetic acid standard substance with a known delta D value as a reference to obtain a sample delta D.
2. The method for detecting the addition of synthetic acetic acid to Zhenjiang aromatic vinegar according to claim 1, wherein the Zhenjiang aromatic vinegar meets the specification of GB/T18623-2011 "Zhenjiang aromatic vinegar as a geographical sign product".
3. The method for detecting the addition of synthetic acetic acid to Zhenjiang aromatic vinegar according to claim 1, wherein the control samples are taken from not less than 20 batches of Zhenjiang aromatic vinegar nationwide every year.
4. The method for detecting the addition of synthetic acetic acid to Zhenjiang aromatic vinegar according to claim 1, wherein,
the chemical reagent comprises at least one of sodium hydroxide, calcium hydroxide, potassium hydroxide, calcium carbonate, sodium carbonate and potassium carbonate;
the physical method comprises at least one of a drying method, a chromatographic separation method and a freeze drying method;
the dilute acid solution comprises at least one of dilute sulfuric acid, dilute hydrochloric acid, dilute phosphoric acid and dilute nitric acid;
the organic reagent comprises at least one of ethanol, methanol, acetone, propanol and diethyl ether.
5. The method for detecting the addition of synthetic acetic acid to Zhenjiang aromatic vinegar according to claim 1, wherein the addition amount of the organic reagent is diluted to 1 g/L-10 g/L of acetic acid.
6. The method for detecting the addition of synthetic acetic acid to Zhenjiang aromatic vinegar according to claim 1, wherein the data correction selects an acetic acid standard substance with a known methyl site delta D value, and the acetic acid standard substance is processed and measured according to the pretreatment step of the sample, and finally the delta D value of the methyl site of the acetic acid in the sample is corrected.
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