CN105467094B - The detection method of external source benzoic acid in Fresh Milk - Google Patents
The detection method of external source benzoic acid in Fresh Milk Download PDFInfo
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- CN105467094B CN105467094B CN201510822516.9A CN201510822516A CN105467094B CN 105467094 B CN105467094 B CN 105467094B CN 201510822516 A CN201510822516 A CN 201510822516A CN 105467094 B CN105467094 B CN 105467094B
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- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
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Abstract
The present invention relates to a kind of isotope detection methods of external source benzoic acid in Fresh Milk.Specifically, it is a kind of technology detecting adulterated doping in food based on stable isotope technology.The present invention establishes the method that external source adds benzoic acid in detection Fresh Milk according to the natural Distillation properties of stable carbon isotope and the theory of metabolic process.It is formed by measuring the stable carbon isotope of major constituents and benzoic acid in Fresh Milk, the relational model of the carbon isotope composition of the benzoic acid and casein of naturally occurring in Fresh Milk is established, according to benzoic acid in sample and casein δ13The relationship of C values is judged.The technology is accurate and reliable, can be used for the quick detection of external source addition benzoic acid in Fresh Milk.
Description
Technical field：
The present invention relates to a kind of methods of external source addition benzoic acid (sodium benzoate is in terms of benzoic acid) in detection Fresh Milk.
The Applied research fields for belonging to stable isotope technology, particularly as being δ according to Fresh Milk itself13C features judge fresh ox
In breast whether containing external source addition benzoic acid.
Background technology：
Fresh Milk is a kind of nutrition-balanced full price food, has other food that can not substitute in the diet structure of people
Effect, the China Nian Lai dairy industry and dairy industry are developed rapidly.However, Fresh Milk yield sharp increase is same
When, the quality security problem of Fresh Milk, which protrudes, to be come, it has also become government agencies at all levels and consumer's focus of attention, especially
Melamine event causes very big fear of the consumer to illegal adding ingredient in Fresh Milk, causes consumer to domestic fresh
The trust crisis of milk quality safety.Benzoic acid (sodium benzoate is using in terms of benzoic acid) is as allowing in GB2760-2011 to use
Food additives are widely used in the fresh-keeping of acid food, as preservative to extend Food Shelf-life, however not by it
It is included in the row of the permission scope of application of Fresh Milk.The method of benzoic acid mainly has gas-chromatography in currently used detection food
Method [Abdol-Samad Abedi, Abdorreza Mohammadi, Ebrahim Azadniya, et al.Simultaneous
determination of sorbic and benzoic acids in milk products using an optimized
Microextraction technique followed by gas chromatography, 2014], HPLC methods
[Bahruddin Saad, Md.Fazlul Bari, Muhammad Idiris Saleh, et al.Simultaneous
determination of preservatives(benzoic acid,sorbic acid,methylparaben and
propylparaben)in foodstuffs using high-performance liquid chromatography,
2005；Isabel M.P.L.V.O.Ferreira, Eul á lia Mendes, Paula Brito, et al.Simultaneous
Determination of benzoic and sorbic acids in quince jam by HPLC, 2000], ion color
Spectrometry [Zong-Hua Wang, Jian-Fei Xia, Fu-Yong Zhao, et al.Determination of benzoic
acid inmilk by solid-phase extraction and ion chromatography with
Conductivity detection, 2013] and GC-MS methods [C.De Luca, S.Passi,
E.Quattrucci.Simultaneous determination of sorbic acid,benzoic acid and
parabens in foods:A new gas chromatography‐mass spectrometry technique
adopted in a survey on Italian foods and beverages[J].Food Additives&
Contaminants, 1995], China's standard GB/T/T5009.29-2003 adopts gas chromatography and liquid chromatography conduct
The official method that benzoic acid measures in food, and Standard of analytical methods GB21703-2010 has only formulated benzene first in breast and dairy products
The liquid chromatography of acidity test.According to WHO Report, there are benzoic acid, i.e. benzene first for many animals and plants itself in nature
Acid is a kind of natural component in food (including cow's milk), however existing method can only measure the content of benzoic acid in product, sentence
Determine the regulation whether benzoic acid content in Related product meets GB 2760, but production can not be come from by benzoic acid in judgement product
Therefore product itself are built in the presence of still external source addition, the content requirement that benzoic acid is especially had no in the national standard of dairy products
The detection technique of external source addition benzoic acid is a research emphasis of current Fresh Milk security fields in vertical Fresh Milk.
Invention content
The purpose of the present invention is to provide external source addition benzoic acid in a kind of effectively detection Fresh Milk, (sodium benzoate is with benzene
Formic acid meter) method.
The technical scheme is that：
According to the regularity of distribution of stable carbon isotope in nature, with the δ of benzoic acid13C is research object, with Fresh Milk
The δ of middle casein13Endogenous indexes of the C as benzoic acid, by establishing benzoic acid and δ in casein13The mathematical model of C, root
According to δ in benzoic acid in measuring samples and casein13C features are added to judge whether benzoic acid comes from external source.
Specifically, this method includes：
A. selection has δ13C gradients, the of a sort genuine piece Fresh Milk that is not added with benzoic acid, measure its casein and
The stable carbon isotope ratio delta of benzoic acid13CCaseinAnd δ13CBenzoic acid,
B. the δ of this kind of Fresh Milk is established13CCaseinWith δ13CBenzoic acidBetween function δ13CBenzoic acid=a δ13CCasein+ b,
C. according to the used analysis method in step a, the casein of measuring samples and the Stable Carbon of benzoic acid are measured
Isotopic ratio δ13CCaseinAnd δ13CBenzoic acid measured value。
D. by the δ of measuring samples13CCaseinIt is updated in the function that step b is established, obtains δ13CBenzoic acid calculated value, and will be with δ13CBenzoic acid measured valueBe compared, to judge in measuring samples whether the benzoic acid added containing external source.
By δ in the step d13CCaseinWith δ13CBenzoic acidWhen being compared, if the absolute difference of the two is no more than 1 ‰
It can determine that Fresh Milk to be measured is free of the benzoic acid of external source addition, can determine that Fresh Milk to be measured if absolute difference is more than 1 ‰
Benzoic acid containing external source addition (sodium benzoate is in terms of benzoic acid).
Above-mentioned Fresh Milk is for fresh cow milk or by the Fresh Milk after pasteurization.
In the above method, Fresh Milk casein and benzoic acid δ13Any side known in the art can be used in the measurement of C values
Method.
The beneficial outcomes of the present invention
1. first passage stable carbon isotope technique of the present invention carries out the detection of external source addition benzoic acid in Fresh Milk, make
Application of the stable isotope technology in Fresh Milk security fields is obtained to be possibly realized.
2. the present invention is by founding mathematical models, when application, need to only measure the δ in the casein and benzoic acid of measuring samples13C simplifies the decision procedure of method, is not required to rely on database, the source of benzoic acid in Fresh Milk is contributed to detect.
Specific implementation mode
Embodiment 1
1. measuring the δ of the casein and benzoic acid of fresh cow milk A, B, C respectively13C values, the results are shown in Table 1.
1 fresh cow milk δ of table13C value measurement results
| Fresh cow milk | A | B | C |
| δ13CCasein(‰) | -17.52 | -17.30 | -16.59 |
| δ13CBenzoic acid(‰) | -30.38 | -30.12 | -26.57 |
As shown in Table 1, in three fresh cow milk samples without containing external source addition benzoic acid, but its in benzoic acid δ13C
Value is but and non-constant, therefore cannot set the δ of the benzoic acid of naturally occurring in cow's milk13C Distribution value ranges.According to stable isotope
Natural fractional theoretical, source or identical two substances of precursor substance, the distribution characteristics of stable isotope exists certain
Regularity contact.Compare the δ of casein13Known to C values, it is possible to find good linear positive correlation is presented in the two, and cow's milk is obtained with this
In itself existing benzoic acid and casein δ13Relational expression between C：
δ13CBenzoic acid=4.3185* δ13CCasein+ 44.981, wherein coefficient R2=0.97.
Measure the δ of the casein and benzoic acid of measuring samples (1) and sample (2)13C values, the results are shown in Table 2.
The δ of 2 measuring samples of table13C value measurement results
| Measuring samples | Sample (1) | Sample (2) |
| δ13CCasein(‰) | -16.52 | -17.36 |
| δ13CBenzoic acid(‰) | -28.89 | -29.53 |
According to the mathematical model established in step 1, itself can be calculated in sample by the casein measured value of two samples
Existing benzoic acid δ13C values, the result calculated according to formula should be -26.36 ‰ (samples 1) and -29.98 ‰ (samples 2) respectively,
Difference with measurement result is respectively 2.53 ‰ and 0.46 ‰, thus can determine that the benzoic acid added containing external source in sample (1),
And the benzoic acid in sample (2) is in the sample existing for itself.
Embodiment 2
Measure the δ of the casein and benzoic acid of 5 measuring samples Fresh Milks a, b, c, d and e13C values (wait for sample to each
3 parts of samples of product execute experiment, and results are averaged, are added to respectively according to its benzoic acid content in wherein sample c, d and e
25%, 50% and 75% sodium benzoate).
Measurement result with according in embodiment 1 formula calculate result difference be respectively 0.51 ‰ (a), 0.48 ‰ (b),
1.35 ‰ (c), 2.62 ‰ (d) and 3.53 ‰ (e).It can determine that according to the method for the present invention as a result, in sample a and b without containing outer
The benzoic acid of source addition, and the benzoic acid containing external source in sample c, d and e, it is completely the same with practical situation.
Finally it should be noted that above example is only used to illustrate the technical scheme of the present invention and it is unrestricted, although ginseng
It is described the invention in detail according to preferred embodiment, it will be understood by those of ordinary skill in the art that, it can be to invention
Technical solution is modified or replaced equivalently, and without departing from the spirit of the technical scheme of the invention and range, should all be covered
In scope of the presently claimed invention.
Claims (8)
1. the isotope detection method of external source benzoic acid in Fresh Milk to be measured, it is characterised in that same according to the Stable Carbon of benzoic acid
Position element composition δ13C features judge the source of benzoic acid comprising following step：
1) pass of naturally occurring benzoic acid and the stable carbon isotope ratio of protein in Fresh Milk in Fresh Milk is built
It is model：δ13CBenzoic acid=a δ13CProtein+b；
2) the stable carbon isotope ratio delta of protein in sample to be tested is measured respectively13CProteinWith the stable carbon isotope of benzoic acid
Ratio delta13CBenzoic acid measured value；
3) according to the δ measured in step 2)13CProteinCalculate what naturally occurring benzoic acid in Fresh Milk to be measured should have
Stable carbon isotope forms (δ13CBenzoic acid calculated value)；
4) comparison step 2) in benzoic acid measured value δ13CBenzoic acid measured valueWith benzoic acid δ in step 3)13CBenzoic acid calculated valueIf two values is exhausted
It is naturally occurring to be no more than 1.50 ‰ benzoic acid thought in the sample to difference, is considered that external source adds if more than 1.50 ‰
Add.
2. the method according to claim 1, wherein the comparison step 2 in step 4)) in benzoic acid measured value δ13CBenzoic acid measured valueWith
Benzoic acid δ in step 3)13CBenzoic acid calculated value, think that the benzoic acid in the sample is if the absolute difference of two values is no more than 0.80 ‰
Naturally occurring is considered that external source is added if more than 0.80 ‰.
3. the method according to claim 1, wherein the comparison step 2 in step 4)) in benzoic acid measured value δ13CBenzoic acid measured valueWith
Benzoic acid δ in step 3)13CBenzoic acid calculated value, think that the benzoic acid in the sample is if the absolute difference of two values is no more than 1.00 ‰
Naturally occurring is considered that external source is added if more than 1.00 ‰.
4. method according to any one of claim 1-3, δ therein13CProteinFor δ13CCasein。
5. method according to any one of claim 1-3, wherein the Fresh Milk is the fresh milk purchased from dairy farmer.
6. method according to any one of claim 1-3, wherein the Fresh Milk is after pasteurization
Fresh Milk.
7. according to the method described in claim 4, wherein the Fresh Milk is the fresh milk purchased from dairy farmer.
8. according to the method described in claim 4, wherein the Fresh Milk is the Fresh Milk after pasteurization.
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| CN105486825B (en) * | 2015-11-24 | 2018-07-24 | 中国食品发酵工业研究院有限公司 | The isotope detection method of external source benzoic acid in dairy products |
| CN105954418A (en) * | 2016-05-25 | 2016-09-21 | 中国食品发酵工业研究院 | Method for determining delta 13C value of benzoic acid in food online |
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