CN112014493B - Method for identifying true and false fruit juice - Google Patents

Method for identifying true and false fruit juice Download PDF

Info

Publication number
CN112014493B
CN112014493B CN202010759754.0A CN202010759754A CN112014493B CN 112014493 B CN112014493 B CN 112014493B CN 202010759754 A CN202010759754 A CN 202010759754A CN 112014493 B CN112014493 B CN 112014493B
Authority
CN
China
Prior art keywords
fruit juice
carbon
delta
true
syrup
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010759754.0A
Other languages
Chinese (zh)
Other versions
CN112014493A (en
Inventor
徐志华
孙洪峰
陈玲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Kangshi Food Technology Co ltd
Original Assignee
Shanghai Kangshi Food Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Kangshi Food Technology Co ltd filed Critical Shanghai Kangshi Food Technology Co ltd
Priority to CN202010759754.0A priority Critical patent/CN112014493B/en
Publication of CN112014493A publication Critical patent/CN112014493A/en
Application granted granted Critical
Publication of CN112014493B publication Critical patent/CN112014493B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/72—Mass spectrometers

Abstract

The invention discloses a method for identifying the authenticity of fruit juice, wherein the fruit juice is fruit juice containing sorbitol, and the method comprises the following steps: determining a true and false distinguishing model aiming at the type of the fruit juice to be detected according to the type of the fruit juice to be detected; and judging the authenticity of the fruit juice to be detected according to the authenticity judging model of the fruit juice. The fruit juice true and false identification method provided by the invention has the advantages that the carbon isotope distribution of sorbitol is introduced to be used as an endogenous standard variable to participate in the construction of the identification model, so that the sensitivity and the accuracy of the fruit juice identification method are improved, and the defects of misjudgment caused by different production areas and varieties and incapability of identifying the addition of the carbon-3 plant syrup are overcome.

Description

Method for identifying true and false fruit juice
Technical Field
The invention relates to the field of food detection, in particular to a method for identifying the authenticity of fruit juice.
Background
The fruit is delicious and juicy, and has the characteristics of rich nutrition and the like. In recent years, with the improvement of living standard and the change of eating habits of people, the juice type drink is gradually favored by consumers. Fresh fruit juice and NFC fruit juice (non-concentrated reduced fruit juice) beverage are rather natural and healthy pronouns, but driven by economic benefits, a few illegal merchants adopt a mode of doping sugar or syrup in raw materials and finished products to obtain illegal benefits, and the illegal benefits are infringed on the benefits of consumers and are even harmful to the physical health of the consumers when the benefits are serious.
The identification of the authenticity of the food is always a hotspot and a difficulty discussed in the field of food, particularly the identification of syrup doped in fruit juice. The main sweet taste of natural fruit juice is derived from disaccharide, oligosaccharide, glucose, fructose, etc., while syrup is derived from starch hydrolysis and isomerization of C-3 and C-4 plants, and its main components are disaccharide, oligosaccharide, glucose, fructose, etc. Therefore, the identification difficulty of the adulterated fruit juice is multiplied because the plant sugar or syrup of the carbon-3 and/or the carbon-4 has extremely similar properties with the natural fruit juice.
The identification method for the current domestic and foreign mainstream true and false fruit juice is to determine the delta of the stable carbon isotope of the fruit juice13CTotal carbonAnd d is equal to the known true delta13CTotal carbonThe range is compared and judged, and after years of data accumulation and research, delta of twenty kinds of fruit and vegetable juice is given by the European Union fruit and vegetable juice society13CTotal carbonThe determination range includes delta of apple juice, pear juice, grape juice, etc13CTotal carbon. However, in practical application, because the difference of production area and variety can cause misjudgment, especially the addition of the carbon-3 plant syrup has the defect of being unidentifiable, the establishment of the identification technology with high sensitivity, short detection period and wide adaptability is very urgentAnd is important.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for identifying the authenticity of fruit juice, which overcomes the defects of low sensitivity, long detection period, poor adaptability and the like of the existing fruit juice identification method.
The invention provides a method for identifying the authenticity of fruit juice, wherein the fruit juice is fruit juice containing sorbitol, and the method comprises the following steps:
determining a true and false discrimination model aiming at the type of the fruit juice to be detected according to the type of the fruit juice to be detected;
judging the authenticity of the juice to be detected according to the authenticity judging model of the juice;
wherein, according to the type of the fruit juice of waiting to examine, confirm to this type fruit juice true and false discriminant model include:
obtaining genuine fruit juice containing the same type of fruit;
obtaining a adulterated fruit juice of plant sugar or syrup containing carbon-3 and/or carbon-4;
measuring the carbon isotope distribution delta in the genuine fruit juice and the adulterated fruit juice13CVPDBSaid carbon isotope distribution δ13CVPDBCarbon isotope distribution delta including sorbitol13CS(ii) a The carbon isotope distribution delta13CVPDBAlso included is the carbon isotope distribution δ of the total carbon13CTCarbon isotope distribution of disaccharide13CDCarbon isotope distribution of oligosaccharide delta13COSCarbon isotope distribution of glucose13CGCarbon isotope distribution of fructose13CFOne or more of;
according to the carbon isotope distribution delta13CVPDBEstablishing a true and false distinguishing model;
and measuring the carbon isotope distribution value of the juice to be detected, and substituting the carbon isotope distribution value into the discrimination model to carry out true and false discrimination.
Optionally, the obtaining of the genuine juice containing the same type of fruit comprises:
collecting fresh fruit of the same type covering one or more varieties and one or more production places, removing inedible part, preparing the edible part into fruit juice, centrifuging, and collecting supernatant to obtain the true fruit juice.
Optionally, the carbon-3 and/or carbon-4 plant sugar or syrup is: plant sugar or syrup covering one or more varieties, one or more production areas and containing carbon-3 and/or carbon-4.
Optionally, the plant-based sugar or syrup of carbon-3 is rice syrup and/or sugar beet syrup; and/or the carbon-4 plant sugar or syrup is corn syrup and/or sugar cane syrup.
Optionally, the adulterated fruit juice containing plant sugar or syrup of carbon-3 and/or carbon-4 is obtained, and the carbon isotope distribution delta in the genuine fruit juice and the adulterated fruit juice is measured13CVPDBThe method comprises the following steps:
dividing the authentic juice into three groups of samples, wherein the first group of samples is used as an authentic control group without adding any sample; adding the plant sugar or syrup with different proportions into the second group of samples and the third group of samples respectively to obtain adulterated fruit juice, and using the adulterated fruit juice as an adulterated control group; determining the carbon isotope distribution delta in the first, second and third set of samples13CVPDBThe value is obtained.
The carbon isotope distribution delta13CVPDBThe method comprises the following steps: carbon isotope distribution delta of sorbitol13CSCarbon isotope distribution of total carbon delta13CTCarbon isotope distribution of fructose13CF。
Alternatively, the carbon isotope distribution δ13CVPDBThe values were determined as follows: determining the carbon isotope distribution delta by an element analyzer tandem stable isotope mass spectrum and a liquid chromatogram tandem stable isotope mass spectrum method13CVPDBThe value is obtained.
Alternatively, the elemental analyzer tandem stable isotope mass spectrometry can be used to determine the carbon isotope distribution δ of total carbon13CT(ii) a The liquid chromatography tandem stable isotope mass spectrometry method can be used for determining the carbon isotope fraction of disaccharideCloth delta13CDCarbon isotope distribution of oligosaccharide delta13COSCarbon isotope distribution of glucose13CGCarbon isotope distribution of fructose13CFSorbitol carbon isotope distribution delta13CS。
Optionally, the determination of carbon isotope distribution δ of total carbon13CTThe method comprises the following steps:
transferring a proper amount of samples of the real control group and the adulteration control group into a tin cup with the specification of 5 multiplied by 8mm by using a needle type liquid transfer device, folding the tin cup into a small square block shape, carefully exhausting air in the tin cup in the process, and measuring delta of the samples sequentially through an element analyzer and a tandem stable isotope mass spectrometry13CT；
The carbon isotope distribution delta of the disaccharide13CDOligosaccharide carbon isotope distribution delta13COSCarbon isotope distribution delta of glucose13CGCarbon isotope distribution of fructose13CFSorbitol carbon isotope distribution delta13CSThe method comprises the following steps:
taking a proper amount of the real control group and adulterated control group samples in a 2mL chromatogram sample introduction bottle, diluting the samples to a proper multiple by using boiling deionized water, separating by using a liquid chromatogram tandem stable isotope mass spectrometry method and determining delta in the juice13CD、δ13COS、δ13CG、δ13CF、δ13CS。
Optionally, the reaction conditions for tandem stable isotope mass spectrometry using the elemental analyzer include: reaction furnace conditions: the reaction furnace is a solid CN type reaction furnace, the filler is quartz \ chromium oxide \ cobalt trioxide \ copper \ magnesium perchlorate, the furnace temperature is 980 ℃, the carrier flow rate is 100mL/min, the reference flow rate is 200mL/min, the oxygen flow rate is 175mL/min, and the oxygen injection time is 2-4 s; conditions of stable isotope mass spectrometer: the ion source voltage is 3.07KV, the carrier gas is high-purity helium gas, and the standard gas is CO2。
The conditions for mass spectrometry using liquid chromatography tandem stable isotopes include:
liquid phase separation conditions: the chromatographic column is a calcium type sugar column chromatographic column, the column temperature is 80 ℃, the mobile phase is 100% m/m deionized water, the flow rate is 350 mu L/min, a constant-flow elution mode is adopted, and the chromatographic time is 50 min; the conditions of the LC-IsoLink reaction furnace are as follows: the reactant A is 4% m/m sodium persulfate aqueous solution, the reactant B is 4% m/m phosphoric acid aqueous solution, the flow rate of the reactant A is 50 muL/min, the flow rate of the reactant B is 50 muL/min, the pressure of Carrier He gas is 2Bar, the pressure of purge He gas is 1.5Bar, and Ref CO2The gas pressure is 1.5 Bar; conditions of stable isotope mass spectrometer: the ion source voltage is 3.07KV, the carrier gas is high-purity helium, and the standard gas is CO2。
Optionally, said distribution δ according to said carbon isotopes13CVPDBThe method for establishing the true and false discrimination model includes the following steps: carbon isotope distribution delta is obtained by calculation13CVPDBAnd (4) difference values between every two variables are used for establishing a true and false discrimination model.
Optionally, the true and false distinguishing model is: y isTrue＝f1(δ13CX，δ13CY，δ13CZ……),YFalse＝f2(δ13CX，δ13CY，δ13CZ… …) when YTrue＞YFalseWhen the fruit juice is true fruit juice; when Y isTrue＜YFalseIn this case, the fruit juice is pseudo-fruit juice.
Optionally, the fruit is a rosaceous fruit.
Optionally, the same type of fruit is any one of pear, apple, pomegranate, peach, apricot and cherry.
Optionally, the fruit juice to be detected is any one of concentrated fruit juice, pure fruit juice and non-concentrated reduced fruit juice.
Compared with the prior art, the fruit juice true and false identification method provided by the embodiment of the invention has the following advantages:
the method for identifying the authenticity of the fruit juice introduces the carbon isotope distribution of the sorbitol as an endogenous standard substance to changeThe amount participates in the construction of the discrimination model, the sensitivity and the accuracy of the fruit juice discrimination method are improved, and the defects of misjudgment caused by different producing areas and varieties and incapability of identifying the addition of the carbon-3 plant syrup are overcome. In addition, the carbon isotope distribution delta of sorbitol is selected13CSIn addition, the discrimination model can be optimized and adjusted according to different types of fruits, and the carbon isotope distribution delta of total carbon can be selected13CTCarbon isotope distribution of disaccharide13CDOligosaccharide carbon isotope distribution delta13COSCarbon isotope distribution of glucose13CGCarbon isotope distribution of fructose13CFOne or more variables in the system participate in establishing the discriminant model, which is helpful for improving the stability of the discriminant model.
Further, the present invention selects the carbon isotope distribution δ of sorbitol13CSCarbon isotope distribution of total carbon δ13CTCarbon isotope distribution of fructose13CFAnd the model construction is participated, so that the discrimination model is simple and accurate.
Furthermore, by establishing a mathematical model in advance, the invention only needs to measure the carbon isotope distribution value of the juice to be detected during detection, and substitutes the carbon isotope distribution value into the discrimination model to carry out true and false discrimination, thus having simple operation.
Drawings
FIG. 1 is a flow chart of a method for identifying whether fruit juice is true or false in an embodiment of the present invention.
FIG. 2 is a LC-IRMS spectrum of a second example of a corn syrup according to the present invention.
FIG. 3 is a LC-IRMS spectrum of a second embodiment rice syrup according to the present invention.
FIG. 4 shows the LC-IRMS spectrum of a second embodiment of the pure pear juice.
FIG. 5 is a spectrum of the LC-TOFMS of the sorbitol standard according to the second embodiment of the present invention.
FIG. 6 is a diagram of the LC-TOFMS spectrum of an unknown peak contained in a second embodiment of a purified pear juice according to the present invention.
Detailed Description
As mentioned in the background art, the identification method of the genuine and fake fruit juice which is the mainstream at home and abroad at present is to determine the delta of the stable carbon isotope of the fruit juice13CTotal carbonAnd d is equal to the known true delta13CTotal carbonThe scope is compared and judged, and the European union juice society gives delta of more than twenty kinds of juice through data accumulation and research for many years13CTotal carbonThe determination range includes delta of apple juice, pear juice, grape juice, etc13CTotal carbon. However, in practical application, misjudgment can be caused due to different producing areas and varieties, and the defect that the addition of the carbon-3 plant syrup cannot be identified exists.
In order to solve the technical problems, the method for identifying the authenticity of the fruit juice provided by the invention has the advantages that the carbon isotope distribution of sorbitol is introduced to be used as an endogenous standard variable to participate in the construction of the discrimination model, so that the sensitivity and the accuracy of the fruit juice identification method are improved, and the defects of misjudgment caused by different production areas and varieties and incapability of identifying the addition of the carbon-3 plant syrup are overcome. In addition, the carbon isotope distribution of sorbitol is chosen to be delta13CSIn addition, the discrimination model can be optimized and adjusted according to different types of fruits, and the carbon isotope distribution delta of the total carbon can be selected13CTCarbon isotope distribution of disaccharide13CDOligosaccharide carbon isotope distribution delta13COSCarbon isotope distribution delta of glucose13CGCarbon isotope distribution delta of fructose13CFOne or more variables in the method participate in building the discriminant model, which is helpful for improving the stability of the discriminant model.
The present invention will be described in detail with reference to the accompanying drawings and specific embodiments so that the above objects, features and advantages of the invention can be more clearly understood.
The raw materials, samples, reagents, equipment and the like used in the method for identifying the authenticity of the fruit juice in the embodiment of the invention are all commercial products and can be purchased in the market.
Referring to fig. 1, fig. 1 is a flow chart of a method for identifying whether a fruit juice is genuine or not according to an embodiment of the present invention. The invention discloses a method for identifying the authenticity of fruit juice, which is the fruit juice containing sorbitol and comprises the following steps:
s100, determining a true and false distinguishing model aiming at the type of the fruit juice to be detected according to the type of the fruit juice to be detected;
s200, judging the truth of the fruit juice to be detected according to the truth judging model of the fruit juice;
wherein, according to the type of the fruit juice of waiting to examine, confirm to this type fruit juice true and false discriminant model include:
s101, obtaining genuine fruit juice containing the same type of fruit;
s102, obtaining adulterated fruit juice of plant sugar or syrup containing carbon-3 and/or carbon-4;
s103, measuring the carbon isotope distribution delta in the genuine juice and the adulterated juice13CVPDBThe carbon isotope distribution delta13CVPDBCarbon isotope distribution delta including sorbitol13CS(ii) a The carbon isotope distribution delta13CVPDBAlso includes the carbon isotope distribution delta of the total carbon13CTCarbon isotope distribution of disaccharide13CDOligosaccharide carbon isotope distribution delta13COSCarbon isotope distribution delta of glucose13CGCarbon isotope distribution of fructose13CFOne or more of;
s104, according to the carbon isotope distribution delta13CVPDBEstablishing a true and false distinguishing model;
and S105, determining the carbon isotope distribution value of the juice to be detected, and substituting the carbon isotope distribution value into the discrimination model to carry out true and false discrimination.
In some embodiments, said obtaining authentic juice comprising the same type of fruit comprises:
collecting fresh fruits of the same type covering one or more varieties and one or more production places, removing inedible parts, preparing juice from edible parts, centrifuging, and collecting supernatant to obtain the true fruit juice.
It should be noted that, the present invention is not limited to the number of varieties and the number of producing areas of selected fruits when collecting the same type of fruits. However, in order to improve the accuracy and stability of the discrimination model for identifying the true and false of the fruit juice and overcome the errors or mistakes caused by different producing areas and varieties, the selection range of the varieties and the producing areas can be expanded as much as possible when the discrimination model is established, and the same type of fruits of a plurality of varieties and a plurality of producing areas are selected for establishing the discrimination model. For example, in some embodiments, five varieties of the same type of fruit from different origins can be selected for use in building the discriminative model.
In some embodiments, the carbon-3 and/or carbon-4 plant based sugar or syrup is: plant sugar or syrup covering one or more varieties, one or more production areas and containing carbon-3 and/or carbon-4.
In the present invention, the number of varieties and production places of the plant sugar or syrup containing carbon-3 and/or carbon-4 are not particularly limited in the preparation of the adulterated fruit juice. However, in order to improve the accuracy and stability of the discrimination model for identifying whether the fruit juice is true or false and overcome the errors or mistakes caused by different production places and varieties, the selection range of the varieties and the production places can be expanded as much as possible when the model is established, and plant sugar or syrup containing carbon-3 and/or carbon-4 of a plurality of varieties and a plurality of production places is selected for preparing the adulterated fruit juice.
In some embodiments, the carbon-3 plant sugar or syrup is rice syrup and/or sugar beet syrup; and/or the carbon-4 plant sugar or syrup is corn syrup and/or sugar cane syrup.
In some embodiments, the adulterated fruit juice containing plant sugar or syrup containing carbon-3 and/or carbon-4 is obtained, and the carbon isotope distribution delta in the genuine fruit juice and the adulterated fruit juice is determined13CVPDBThe method comprises the following steps:
dividing said authentic juice into three groups of samples, the first group of samples being used as an authentic control group without any additions; adding the plant sugar or syrup with different proportions into the second group of samples and the third group of samples respectively to obtain adulterated fruit juice, and using the adulterated fruit juice as an adulterated control group; determining the carbon isotope distribution delta of the first, second and third set of samples13CVPDBThe value is obtained. It should be noted that when the plant sugar or syrup with different proportions is set, the reasonable subdivision concentration is beneficial to improving the discrimination accuracy of the discrimination model and is also beneficial to determining the detection limit of the method.
Wherein VPDB refers to Vienna Pee De belemnite standard, and the international standard for carbon stable isotopes generally employs VPDB, i.e., the carbon stable isotope ratio of arrow stone (Belemnite) in Chalkeedike (Pee De Formation) of southern Carolina, USA.
The contents of the disaccharide, oligosaccharide, glucose and fructose in different types of fruit juice are different, so that the statistical variable delta is calculated13CD、δ13COS、δ13CG、δ13CFThe method can be adjusted according to the actual situation, eliminates the variables with low response values, and is favorable for improving the stability of the discriminant model function on the premise of sufficient variables. In practical application, the more data participating in modeling is, the wider the data is, and the higher the model discrimination accuracy is.
In some embodiments, the carbon isotope distribution δ13CVPDBThe method comprises the following steps: carbon isotope distribution delta of sorbitol13CSCarbon isotope distribution of total carbon δ13CTCarbon isotope distribution delta of fructose13CF。
In some embodiments, the carbon isotope distribution δ13CVPDBThe measuring method comprises the following steps: determining the carbon isotope distribution delta by element analyzer tandem stable isotope mass spectrometry (EA-IRMS) and liquid chromatography tandem stable isotope mass spectrometry (LC-IRMS)13CVPDBThe value is obtained. In the specific operation, a suitable measuring instrument can be selected according to different variables, and the invention is not particularly limited.
In some embodiments, the elemental analyzer tandem stable isotope mass spectrometry can be used to determine the carbon isotope distribution δ of total carbon13CT(ii) a The liquid chromatography tandem stable isotope mass spectrometry method can be used for determining the carbon isotope distribution delta of disaccharide13CDCarbon isotope fraction of oligosaccharideCloth delta13COSCarbon isotope distribution of glucose13CGCarbon isotope distribution of fructose13CFSorbitol carbon isotope distribution delta13CS。
In some embodiments, the determination of carbon isotope distribution δ of total carbon13CTThe method comprises the following steps:
transferring a proper amount of samples of the real control group and the adulteration control group into a tin cup with the specification of 5 multiplied by 8mm by using a needle type liquid transfer device, folding the tin cup into a small square block shape, carefully exhausting air in the tin cup in the process, and measuring delta of the samples sequentially through an element analyzer and a tandem stable isotope mass spectrometry13CT；
The carbon isotope distribution delta of the disaccharide13CDOligosaccharide carbon isotope distribution delta13COSCarbon isotope distribution delta of glucose13CGCarbon isotope distribution of fructose13CFSorbitol carbon isotope distribution delta13CSThe method comprises the following steps:
taking a proper amount of the real control group and adulterated control group samples in a 2mL chromatogram sample introduction bottle, diluting the samples to a proper multiple by using boiling deionized water, separating by using a liquid chromatogram tandem stable isotope mass spectrometry method, and determining delta in the juice13CD、δ13COS、δ13CG、δ13CF、δ13CS。
In some embodiments, the conditions for tandem stable isotope mass spectrometry using the elemental analyzer include:
the conditions of the reaction furnace are as follows: the reaction furnace is a solid CN type reaction furnace, the filler is quartz \ chromium oxide \ cobalt trioxide \ copper \ magnesium perchlorate, the furnace temperature is 980 ℃, the carrier flow rate is 100mL/min, the reference flow rate is 200mL/min, the oxygen flow rate is 175mL/min, and the oxygen injection time is 2-4 s; conditions of stable isotope mass spectrometer: the ion source voltage is 3.07KV, the carrier gas is high-purity helium, and the standard gas is CO2。
In some embodiments, the conditions determined using liquid chromatography tandem stable isotope mass spectrometry include:
liquid phase separation conditions: the chromatographic column is a calcium type sugar column chromatographic column, the column temperature is 80 ℃, the mobile phase is 100% m/m deionized water, the flow rate is 350 mu L/min, a constant-current elution mode is adopted, and the chromatographic time is 50 min; the conditions of the LC-IsoLink reactor were: the reactant A is 4% m/m sodium persulfate aqueous solution, the reactant B is 4% m/m phosphoric acid aqueous solution, the flow rate of the reactant A is 50 mu L/min, the flow rate of the reactant B is 50 mu L/min, the pressure of Carrier He gas is 2Bar, the pressure of purge He gas is 1.5Bar, and Ref CO2The gas pressure is 1.5 Bar; conditions of stable isotope mass spectrometer: the ion source voltage is 3.07KV, the carrier gas is high-purity helium, and the standard gas is CO2。
In some embodiments, the δ according to the carbon isotope distribution13CVPDBThe method for establishing the true and false distinguishing model comprises the following steps: carbon isotope distribution delta is obtained by calculation13CVPDBAnd (4) difference values between every two variables are used for establishing a true and false discrimination model. The variable difference is screened out through stepwise discriminant analysis, and the screening aims to eliminate variables with large correlation and ensure the stability, accuracy and simplicity of a discriminant model.
In some embodiments, said distribution δ according to said carbon isotopes is13CVPDBThe method for establishing the true and false distinguishing model comprises the following steps: calculating to obtain delta13CT、δ13CD、δ13COS、δ13CG、δ13CF、13CSDifference between two variables, difference being in delta13C(T-D)、δ13C(T-OS)、δ13C(T-G)、δ13C(T-F)、δ13C(T-S)、δ13C(D-OS)、δ13C(D-G)、δ13C(D-F)、δ13C(D-S)、δ13C(OS-G)、δ13C(OS-F)、δ13C(OS-S)、δ13C(G-F)、δ13C(G-S)、δ13C(F-S)And representing, and then establishing a true and false discrimination model by using the variable difference.
In some embodiments, said distribution δ according to said carbon isotopes is13CVPDBThe method for establishing the true and false discrimination model includes the following steps: calculating to obtain delta13CT、δ13CF、δ13CSDifference between two variables, difference being in delta13C(T-F),δ13C(T-S),δ13C(F-S)And representing, and then establishing a true and false discrimination model by using the variable difference.
In some embodiments, the true and false discriminant model is: y isTrue＝f1(δ13CX，δ13CY，δ13CZ……),YFalse＝f2(δ13CX，δ13CY，δ13CZ… …) when YTrue＞YFalseWhen the fruit juice is true fruit juice; when Y isTrue＜YFalseIn other words, it is pseudo fruit juice. Wherein, said X, Y, Z, etc. respectively represent different carbon isotopes, in some embodiments, X, Y, Z, etc. respectively represent one of carbon isotope S of sorbitol, carbon isotope T of total carbon, carbon isotope D of disaccharide, carbon isotope OS of oligosaccharide, carbon isotope G of glucose, and carbon isotope F of fructose. In some embodiments, X, Y, Z represents the carbon isotope S of sorbitol, the carbon isotope T of total carbon, and the carbon isotope F of fructose, respectively.
In some embodiments, the fruit is a rosaceous fruit. The Rosaceae, Latin, is named Rosaceae, and comprises four subfamilies: spiraea subfamily (Spiraeoideae Agardh); maloideae (Maloideae Weber); rosaideae (rosaideae Focke) and pruneideae (pruneideae Focke).
In some embodiments, the same type of fruit is any one of pear, apple, pomegranate, peach, apricot, cherry.
In some embodiments, the fruit juice to be tested is any one of concentrated fruit juice, pure fruit juice and non-concentrated reduced fruit juice.
It should be noted that, because there are various fruit juices on the market, and the fruit juices have various compositions, and the method for identifying whether the fruit juice is true or false according to the present invention is based on the identification method proposed by the endogenous ingredients in the fruit, and therefore is not suitable for fruit juice beverages containing substances that interfere with the identification, the method for identifying the fruit juice according to the present invention is mainly suitable for fruit juices with high purity, such as concentrated fruit juices, pure fruit juices, non-concentrated reduced fruit juices (NFC fruit juices), and the like.
First embodiment
The fruit types, rice syrup and corn syrup, selected in this embodiment are only used for illustrating the embodiment of the present invention, and are not used for limiting the practical application range of the present invention, and the selection of fruits, sugar or syrup of more varieties and production areas in practical application is helpful for improving the accuracy of the discrimination model.
1. Sample collection
41 fresh pears of 5 varieties of Tangshang, crystal pears, golden pears, Huangguan pears and Xinjiang Korla bergamot pears are collected through channels of Shanghai and the like.
Typical carbon-3 and carbon-4 plant high fructose corn syrup is collected through a super-equal channel. In this example, rice syrup and corn syrup were selected as the C-3 and C-4 plant fructose syrup.
2. Sample preparation
Cleaning fresh pears, removing seeds, squeezing each fresh pear into pear juice by a juicer, and centrifuging to collect supernatant. Dividing the collected supernatant into three groups, wherein one group is used as a real control group and is refrigerated for later use; adding rice fructose syrup according to the proportion of 1% m/m, 5% m/m, 10% m/m, 20% m/m and 50% m/m, and refrigerating for later use; one group is added with corn high fructose syrup according to the proportion of 1 percent m/m, 5 percent m/m, 10 percent m/m, 20 percent m/m and 50 percent m/m, and the mixture is refrigerated for standby, and the two groups are adulterated fruit juice.
3. Sample pretreatment
(1) Transferring 0.8 μ L of the above sample into a tin cup with 5 × 8mm specification by needle type liquid transfer device, folding the tin cup into small square block, carefully exhausting air in the tin cup, and measuring delta by element analyzer tandem stable isotope mass spectrometry (EA-IRMS)13CT。
(2) Another 200 μ L of the sample was placed in a 2mL chromatography vial and diluted to the appropriate fold with boiling deionized water. Separating by liquid chromatography tandem stable isotope mass spectrometry (LC-IRMS) and determining delta in fruit juice13CD、δ13COS、δ13CG、δ13CF、13CS。
4. Instrumental testing
Sequentially determining the processed samples 3 and 1 by an element analyzer tandem stable isotope mass spectrometry (EA-IRMS) to obtain delta13CT。
The conditions for tandem stable isotope mass spectrometry using the element analyzer are as follows: the conditions of the reaction furnace are as follows: the reaction furnace is a solid CN type reaction furnace, the filler is quartz (quartz wood) \ chromic oxide (chromium oxide) \ cobalt oxide (silver cobalt-cobalt oxide) \ copper (copper) \ magnesium perchlorate), the furnace temperature is 980 ℃, the Carrier (Carrier) flow rate is 100mL/min, the Reference (Reference) flow rate is 200mL/min, the Oxygen (Oxygen) flow rate is 175mL/min, and the Oxygen (Oxygen) injection time is 2-4 s; conditions of stable isotope mass spectrometer: the ion source voltage is 3.07KV, the carrier gas is high-purity helium, and the standard gas is CO2。
The samples treated in the steps 3 and 2 are sequentially measured by liquid chromatography tandem stable isotope mass spectrometry, in the embodiment, the response value of oligosaccharide and disaccharide is low under the dilution multiple, and the delta can be caused by too low response value13CD、δ13COSThe fluctuation of the measured value is increased to influence the stability of the discrimination model, so the embodiment eliminates the fluctuation and keeps the delta with stable response value13CG、δ13CF、δ13CSThree variables participate in modeling calculations.
The conditions measured by using liquid chromatography tandem stable isotope mass spectrometry are as follows: liquid phase separation conditions: the chromatographic column is a calcium type sugar column chromatographic column, the column temperature is 80 ℃, the mobile phase is 100% m/m deionized water, the flow rate is 350 mu L/min, a constant-flow elution mode is adopted, and the chromatographic time is 50 min; LC-IsoLinkThe conditions of the reaction furnace were: the reactant A is 4% m/m sodium persulfate aqueous solution, the reactant B is 4% m/m phosphoric acid aqueous solution, the flow rate of the reactant A is 50 muL/min, the flow rate of the reactant B is 50 muL/min, the pressure of Carrier He gas is 2Bar, the pressure of purge He gas is 1.5Bar, and Ref CO2The gas pressure is 1.5 Bar; conditions of stable isotope mass spectrometer: the ion source voltage is 3.07KV, the carrier gas is high-purity helium, and the standard gas is CO2。
5. Discriminant model establishment
The data are led into SPSS statistical software, and difference values delta of three important variables are obtained through gradual discriminant analysis13C(T-F),δ13C(T-S),δ13C(F-S)Will delta13C(T-F),δ13C(T-S),δ13C(F-S)Introducing into discriminant model, and establishing discriminant model function YTrue＝-5.251+2.610δ13C(T-F)-10.771δ13C(T-S)+7.272δ13C(F-S)；YFalse＝-0.698-0.139δ13C(T-F)+0.256δ13C(T-S)-0.132δ13C(F-S). Finally, the samples with known trueness and falseness are substituted into the model for testing, and the model tests prove that 3 samples with known trueness and falseness are judged by mistake, and the judgment accuracy reaches 94.1%; and at the addition point of 1% m/m of plant syrup, the carbon-3 syrup and the carbon-4 syrup have extremely high discrimination accuracy, which indicates that the model meets the discrimination requirements of true and false fruit juice.
6. Unknown sample discrimination
Delta of unknown sample13C(T-F)，δ13C(T-S)，δ13C(F-S)Substituting the variable difference value into the discrimination model to discriminate the unknown sample when Y isTrue＞YFalseWhen the fruit juice is true fruit juice; when Y isTrue＜YFalseIn this case, the fruit juice is pseudo-fruit juice. The results show that, of the unknown samples, unknown sample 1 and unknown sample 3 are true juices, and unknown sample 2 is a false juice, and the results are shown in table 1.
TABLE 1 determination of unknown samples Table
Figure BDA0002612739960000121
Second embodiment
This example shows the carbon isotope distribution C of sorbitolSAs a verification experiment of important variables in the identification method of the present invention.
The invention relates to LC-IRMS (liquid chromatography-infrared spectrometry) measurement of relevant variables of disaccharide, oligosaccharide, glucose, fructose and sorbitol, wherein the peak emergence positions and sequences of disaccharide, oligosaccharide, glucose and fructose are reported in many documents, and the peak emergence sequences of disaccharide, oligosaccharide, glucose and fructose are elaborated in the 'application of elemental analysis/liquid chromatography-carbon isotope ratio mass spectrometry in pure apple juice adulteration identification' of Tanmun Muru and the like. And will not be described in detail herein.
The present invention has carried out the following confirmatory analysis for sorbitol.
This example uses the detection method of the first example for experiments. In this embodiment, a high performance liquid chromatography-high resolution flight mass spectrometry is adopted in a negative ion mode of an atmospheric pressure chemical ionization source (APCI), and under the liquid phase separation condition of the LC-IRMS described in the present invention, corn syrup, rice syrup, and pure pear juice are respectively measured, and the measurement results are shown in fig. 2 to fig. 4. Unlike corn syrup, rice syrup, pure pear juice was separated at the same chromatographic order and a molecular ion peak with a mass to charge ratio of 181.0703 was detected.
Molecular formula judgment is carried out in the deviation range of the mass number of 2mDa by using instrument software, and molecular formulas of molecular ion peaks are only one and are determined as C6H13O6Hydrogenating the molecular ion peak to obtain the compound molecular formula C6H14O6Substituting the molecular formula into a ChemSepder database for retrieval and matching, judging and screening suspected compounds obtained by retrieval by referring to related documents and combining professional knowledge, and locking the suspected compounds as sorbitol. Purchasing a standard substance of sorbitol, acquiring and obtaining molecular ion peaks of sorbitol under the same liquid phase condition and flight mass spectrum condition, wherein the mass-to-charge ratio of the molecular ion peaks is 181.0707, the relative deviation of mass numbers is 2.2ppm, and the standard substance conforms to the high resolutionMass spectrometry determination requirements (see fig. 5); the retention time of 35.7min was consistent with the unknown peak of 36.2min of the sample, which was confirmed to be sorbitol (see FIG. 6).
Thus, the present invention employs the carbon isotope distribution C of sorbitolSAs an important variable in the identification method of the present invention. The fruit juice true and false identification method provided by the invention has the advantages that the carbon isotope distribution of sorbitol is introduced as an endogenous standard variable to participate in the construction of the identification model, so that the sensitivity and the accuracy of the fruit juice identification method are improved, and the defects of misjudgment caused by different production places and varieties and incapability of identifying the addition of the carbon-3 plant syrup are overcome.
Although the present invention is disclosed above, the present invention is not limited thereto. Various changes and modifications may be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (8)

1. The method for identifying the authenticity of the fruit juice is characterized in that the fruit juice is the fruit juice containing sorbitol, and the method comprises the following steps:
determining a true and false discrimination model aiming at the type of the fruit juice to be detected according to the type of the fruit juice to be detected;
judging the truth of the fruit juice to be detected according to the truth judging model of the fruit juice;
wherein, according to the type of the fruit juice of waiting to examine, confirm to this type fruit juice true and false discriminant model include:
obtaining genuine fruit juice containing the same type of fruit, wherein the same type of fruit is pear;
obtaining adulterated fruit juice of plant sugar or syrup containing carbon-3 and/or carbon-4;
measuring the carbon isotope distribution delta in the genuine fruit juice and the adulterated fruit juice13CVPDBSaid carbon isotope distribution δ13CVPDBThe method comprises the following steps: carbon isotope distribution delta of sorbitol13CSCarbon isotope distribution of total carbon delta13CTCarbon isotope distribution delta of fructose13CFThe element analyzer tandem stable isotope mass spectrum can be used for determining the carbon isotope distribution delta of the total carbon13CTThe liquid chromatogram tandem stable isotope mass spectrometry method can be used for determining the carbon isotope distribution delta of fructose13CFSorbitol carbon isotope distribution delta13CS；
Wherein, the conditions for measuring by using the liquid chromatogram tandem stable isotope mass spectrum comprise:
liquid phase separation conditions: the chromatographic column is a calcium type sugar column chromatographic column, the column temperature is 80 ℃, the mobile phase is 100% m/m deionized water, the flow rate is 350 mu L/min, a constant-current elution mode is adopted, and the chromatographic time is 50 min; the conditions of the LC-IsoLink reaction furnace are as follows: the reactant A is 4% m/m sodium persulfate aqueous solution, the reactant B is 4% m/m phosphoric acid aqueous solution, the flow rate of the reactant A is 50 mu L/min, the flow rate of the reactant B is 50 mu L/min, the pressure of Carrier He gas is 2Bar, the pressure of purge He gas is 1.5Bar, and Ref CO2The gas pressure is 1.5 Bar; conditions of stable isotope mass spectrometer: the ion source voltage is 3.07KV, the carrier gas is high-purity helium, and the standard gas is CO2；
Calculating to obtain the carbon isotope distribution delta through stepwise discriminant analysis13CVPDBAnd (3) establishing a true and false discrimination model by using the difference value of the variables, wherein the true and false discrimination model is as follows: y isTrue＝f1(δ13CX，δ13CY，δ13CZ……),YFalse＝f2(δ13CX，δ13CY，δ13CZ… …), wherein X, Y, Z represents a carbon isotope S of sorbitol, a carbon isotope T of total carbon, a carbon isotope F of fructose, respectively, and when Y isTrue＞YFalseWhen the fruit juice is true fruit juice; when Y isTrue＜YFalseWhen the fruit juice is fake fruit juice;
and measuring the carbon isotope distribution value of the juice to be detected, and substituting the carbon isotope distribution value into the discrimination model to carry out true and false discrimination.
2. The method of claim 1, wherein said obtaining a genuine juice comprising a same type of fruit comprises:
collecting fresh fruit of the same type covering one or more varieties and one or more production places, removing inedible part, preparing the edible part into fruit juice, centrifuging, and collecting supernatant to obtain the true fruit juice.
3. The method for identifying the authenticity of fruit juice according to claim 1, wherein the carbon-3 and/or carbon-4 plant sugar or syrup is: plant sugar or syrup covering one or more varieties, one or more production areas and containing carbon-3 and/or carbon-4.
4. The method for identifying the authenticity of fruit juice according to claim 1, wherein the carbon-3 plant sugar or syrup is rice syrup and/or beet syrup; and/or the carbon-4 plant sugar or syrup is corn syrup and/or sugar cane syrup.
5. The method for identifying the authenticity of fruit juice according to claim 1, wherein adulterated fruit juice containing plant sugar or syrup containing carbon-3 and/or carbon-4 is obtained, and the distribution δ of carbon isotopes in said genuine fruit juice and said adulterated fruit juice is measured13CVPDBThe method comprises the following steps:
dividing said authentic juice into three groups of samples, the first group of samples being used as an authentic control group without any additions; adding the plant sugar or syrup with different proportions into the second group of samples and the third group of samples respectively to obtain adulterated fruit juice, and using the adulterated fruit juice as an adulterated control group; determining the carbon isotope distribution delta in the first, second and third set of samples13CVPDBThe value is obtained.
6. The method for identifying the authenticity of fruit juice according to claim 1, wherein said carbon isotope distribution δ of total carbon is measured13CTThe method comprises the following steps:
using a needle type pipettor to remove a proper amount of the samples of the real control group and the adulteration control groupFolding the tin cup into a small square block in a tin cup with the specification of 5 multiplied by 8mm, carefully exhausting air in the tin cup in the process, and sequentially measuring delta of the sample by an element analyzer and a tandem stable isotope mass spectrometry13CT；
The carbon isotope distribution delta of the fructose is measured13CFSorbitol carbon isotope distribution delta13CSThe method comprises the following steps:
taking a proper amount of the real control group and adulterated control group samples in a 2mL chromatogram sample introduction bottle, diluting the samples to a proper multiple by using boiling deionized water, separating by using a liquid chromatogram tandem stable isotope mass spectrometry method and determining delta in the juice13CF、δ13CS。
7. The method of claim 1, wherein the conditions for tandem stable isotope mass spectrometry using the element analyzer include:
the conditions of the reaction furnace are as follows: the reaction furnace is a solid CN type reaction furnace, the filler is quartz \ chromium oxide \ cobalt trioxide \ copper \ magnesium perchlorate, the furnace temperature is 980 ℃, the carrier flow rate is 100mL/min, the reference flow rate is 200mL/min, the oxygen flow rate is 175mL/min, and the oxygen injection time is 2-4 s; conditions of stable isotope mass spectrometer: the ion source voltage is 3.07KV, the carrier gas is high-purity helium, and the standard gas is CO2。
8. The method for identifying the authenticity of fruit juice according to claim 1, wherein the fruit juice to be detected is any one of concentrated fruit juice, pure fruit juice and non-concentrated reduced fruit juice.
CN202010759754.0A 2020-07-31 2020-07-31 Method for identifying true and false fruit juice Active CN112014493B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010759754.0A CN112014493B (en) 2020-07-31 2020-07-31 Method for identifying true and false fruit juice

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010759754.0A CN112014493B (en) 2020-07-31 2020-07-31 Method for identifying true and false fruit juice

Publications (2)

Publication Number Publication Date
CN112014493A CN112014493A (en) 2020-12-01
CN112014493B true CN112014493B (en) 2022-07-15

Family

ID=73499305

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010759754.0A Active CN112014493B (en) 2020-07-31 2020-07-31 Method for identifying true and false fruit juice

Country Status (1)

Country Link
CN (1) CN112014493B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2090022A1 (en) * 1990-09-11 1992-03-12 Susie Hawkins Mills Fruit juice plus citrus fiber
CN104215731A (en) * 2014-09-18 2014-12-17 祝伟霞 Method for distinguishing true apple juice from false apple juice by virtue of liquid chromatogram-isotope ratio mass spectrometry (LC-IRMS) determination
CN109358135A (en) * 2018-12-21 2019-02-19 江苏中谱检测有限公司 A kind of liquid chromatogram for grape juice authenticity-isotope mass spectrometry method for combined use
CN111413445A (en) * 2020-05-24 2020-07-14 中国农业科学院农业质量标准与检测技术研究所 Construction method for identifying non-concentrated reduced fruit juice and concentrated reduced fruit juice models and identification method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2090022A1 (en) * 1990-09-11 1992-03-12 Susie Hawkins Mills Fruit juice plus citrus fiber
CN104215731A (en) * 2014-09-18 2014-12-17 祝伟霞 Method for distinguishing true apple juice from false apple juice by virtue of liquid chromatogram-isotope ratio mass spectrometry (LC-IRMS) determination
CN109358135A (en) * 2018-12-21 2019-02-19 江苏中谱检测有限公司 A kind of liquid chromatogram for grape juice authenticity-isotope mass spectrometry method for combined use
CN111413445A (en) * 2020-05-24 2020-07-14 中国农业科学院农业质量标准与检测技术研究所 Construction method for identifying non-concentrated reduced fruit juice and concentrated reduced fruit juice models and identification method

Non-Patent Citations (10)

* Cited by examiner, † Cited by third party
Title
Improved detection of sugar addition to apple juices and concentrates using internal standard 13C IRMS;Eric Jarnin 等;《Analytica Chimica Acta》;19971231;第347卷;359-368 *
International Multidimensional Authenticity Specification (IMAS) Algorithm for Detection of Commercial Pomegranate Juice Adulteration;YANJUN ZHANG 等;《J. Agric. Food Chem.》;20090227;第57卷;2550-2557 *
Liquid chromatographic isolation of individual carbohydrates from environmental matrices for stable carbon analysis and radiocarbon dating;Amel Nouara 等;《Analytica Chimica Acta》;20190318;第1067卷;137-146 *
元素分析/液相色谱-碳同位素比值质谱法在纯正苹果汁掺假鉴别中的应用;谭梦茹 等;《食品安全质量检测学报》;20170531;第8卷(第5期);1565-1571 *
元素分析-碳同位素比值质谱法在纯正葡萄汁掺假鉴别中的应用;谭梦茹 等;《分析测试学报》;20160831;第35卷(第8期);1031-1035 *
掺假燕窝的元素组成分析及鉴别研究;侯真真 等;《食品工业》;20161231;第37卷(第7期);287-291 *
果汁鉴伪技术研究进展;刘学铭 等;《食品与发酵工业》;20061231;第32卷(第6期);87-91 *
稳定同位素技术在农产品产地溯源中的应用;唐甜甜 等;《食品工业科技》;20191120;全文 *
苹果汁的掺假鉴定;胡耀星 等;《食品工业科技》;19981231(第4期);69-71 *
酒石酸作为碳同位素内源标志物在食品掺假检测中的应用;张佩敏 等;《食品与发酵工业》;20181231;第44卷(第8期);258-264 *

Also Published As

Publication number Publication date
CN112014493A (en) 2020-12-01

Similar Documents

Publication Publication Date Title
CN108982692B (en) Method for distinguishing milk powder producing area by element analysis-stable isotope mass spectrum
CN111220763B (en) Application of high-content DSM as characteristic marker of linden honey
JP2011043329A (en) Method of analyzing isotope ratio of low-concentration ethanol sample
CN110702832B (en) Application of high-content 4-hydroxyquinoline as characteristic marker of jujube honey
Husáková et al. Analytical capabilities of inductively coupled plasma orthogonal acceleration time-of-flight mass spectrometry (ICP-oa-TOF-MS) for multi-element analysis of food and beverages
Mottese et al. Traceability of Opuntia ficus‐indica L. Miller by ICP‐MS multi‐element profile and chemometric approach
CN102967669A (en) Rapid measuring method for carbon acetate stable isotope in table vinegar
CN113125590A (en) Objective evaluation method for aroma quality of Yunnan red congou tea soup based on rapid gas-phase electronic nose technology
Majchrzak et al. Revealing dynamic changes of the volatile profile of food samples using PTR–MS
Gomis et al. Application of HPLC to characterization and control of individual acids in apple extracts and ciders
CN112014493B (en) Method for identifying true and false fruit juice
Rinke Tradition meets high tech for authenticity testing of fruit juices
CN111257452B (en) Method for detecting addition of synthetic acetic acid into Zhenjiang aromatic vinegar
CN111337605B (en) Method for evaluating authenticity of lotus bee pollen
Perini et al. Combination of sugar and stable isotopes analyses to detect the use of nongrape sugars in balsamic vinegar must
CN113984952B (en) Method for analyzing components of fermented soy sauce
CN111257449B (en) Method for measuring stable hydrogen isotope ratio of methyl acetate site in vinegar beverage
CN114137138A (en) Volatile component-based resolution method for Sichuan Pixian broad bean paste
CN109374803B (en) Method for detecting stevioside sweetening agent and application thereof
Yang et al. Qualitative analysis of age and brand of unblended brandy by electronic nose
Krueger Stable isotope analysis by mass spectrometry
CN114414653B (en) Cherry origin tracing method based on kernel
Guillou et al. Application of deuterium NMR and isotopic analysis to the characterization of foods and beverages
RU2809285C1 (en) Method of honey identification based on isotope mass spectrometry
Guillou et al. Isotope methods for the control of food products and beverages

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant