CN109001330A - A kind of natural cod-liver oil Adulteration identification method based on finger-print - Google Patents
A kind of natural cod-liver oil Adulteration identification method based on finger-print Download PDFInfo
- Publication number
- CN109001330A CN109001330A CN201810984049.3A CN201810984049A CN109001330A CN 109001330 A CN109001330 A CN 109001330A CN 201810984049 A CN201810984049 A CN 201810984049A CN 109001330 A CN109001330 A CN 109001330A
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- China
- Prior art keywords
- acid
- liver oil
- sample
- finger
- cod
- 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.)
- Pending
Links
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- 238000001228 spectrum Methods 0.000 claims abstract description 18
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- UWHZIFQPPBDJPM-BQYQJAHWSA-N trans-vaccenic acid Chemical compound CCCCCC\C=C\CCCCCCCCCC(O)=O UWHZIFQPPBDJPM-BQYQJAHWSA-N 0.000 claims description 5
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
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Abstract
The present invention relates to health food detection technique fields, and in particular to a kind of natural cod-liver oil adulteration detection method based on fatty acid fingerprint map analyzing and similarity evaluation.Rapid identification can be carried out to adulterated fish oil in natural cod-liver oil and vegetable oil using this method, step includes: the collection of (1) sample；(2) preparation of fatty acid methyl ester reference substance solution；(3) derivatization treatment before sample column；(4) gas chromatography-mass spectrography measures fatty acid finger-print；(5) natural cod-liver oil fatty acid compares (standard) fingerprint map construction；(6) fingerprint spectrum method is verified；(7) listing sample fingerprint similarity is calculated and is evaluated；(8) the adulterated judgement of natural cod-liver oil.
Description
Technical field
The present invention relates to health food detection technique fields, and in particular to one kind is based on fatty acid fingerprint map analyzing and phase
Like the natural cod-liver oil adulteration detection method of degree evaluation, for the quality control of natural cod-liver oil and Adulteration identification provide it is a kind of newly
Detection technique.
Background technique
Natural cod-liver oil is a kind of fat oil extracted from deep-sea fish liver, mostlys come from the liver of gadus, therefore
Claim cod-liver oil.Natural fish liver obtained from being extracted in the gadus liver caught in the deep-sea cold water of the states such as the Norway from high latitude
Oil is pure, pollution-free, Quality Safety, reliable, the deep favor by global consumer of product.Natural cod-liver oil had both contained dimension life abundant
Plain A and D3, and containing rice -3 polyunsaturated fatty acid of coffee in Europe abundant, including docosahexaenoic acid (DHA), eicosapentaenoic acid
(EPA) and parinaric acid (SDA), Europe rice -3 fatty acid of coffee have anti-inflammatory, raising immunity, reducing blood lipid, anti-atherogenic
Hardening, is effectively prevented and treated the physiological activities such as cardiovascular and cerebrovascular disease.DHA also has in addition to above-mentioned physiological activity
The effect for protecting retina, improving eyesight, promote infant intelligent development, improving memory is the important of brain and retina
Constituent, it is most important to the brain and visual acuity of infant, therefore natural cod-liver oil has the laudatory title of " liquid golden ".
High-quality natural cod-liver oil is mostly from deep-sea silver pout, and due to silver pout limits throughput, price is higher, while close
Cod-liver oil product increases year by year in the share of health-product market over year, therefore having illegal businessman is to make profit, by mixing in cod-liver oil
Enter a certain proportion of low price fish oil and vegetable oil, is identified with natural pure cod-liver oil product, is sold, seriously disturbed at high price
Random cod-liver oil market order, damages the interests of consumer.Existing quality control method only measures vitamin A, vitamin D3、
DHA and EPA content, this 4 kinds of index ingredients can be by being artificially added synthesis vitamin A and D3, the ethyl ester type DHA of concentration and
EPA is required with touching the mark, therefore the quality control method for only relying only on index components content measurement can not accurately identify adulterated cod-liver oil,
In consideration of it, establishing scientific and effective Adulteration identification method as important topic urgently to be solved in cod-liver oil healthy development of market.
Fingerprint pattern technology is the most scientific effective hand for the multicomponent natural drug quality control generally acknowledged in the world at present
One of section, has been widely applied in traditional Chinese medicine quality control field.Finger-print can Efficient Characterization natural materials complicated ingredient
It is a kind of synthesis, quantifiable identification of means with the relationship of its quality.Contained a variety of saturations and unsaturation in natural cod-liver oil
Fatty acid is its main constituents, and composition is stablized, and has stronger characteristic, meets the requirement of finger-print foundation.This
Invention measures finger-print after being effectively separated fatty acid each in cod-liver oil using GC-MS joint technology, choose domestic and international
The representative cod liver oil soft capsule of different manufacturing enterprises, different sources and oral liquid as sample, import " in
2012 editions softwares of medicine chromatographic fingerprinting similarity evaluation system " generate cod-liver oil and compare (standard) finger-print, with control
Finger-print is standard, calculates listing cod-liver oil sample fingerprint similarity, gained similarity value combination fish oil, vegetable oil
Fatty acid characteristic can quickly identify behavior adulterated in cod-liver oil that the identification method is easy, reliable, can be used as natural fish liver
The important technical of oily Adulteration identification improves product quality and has great importance for specification cod-liver oil market.
Summary of the invention:
The present invention measures natural cod-liver oil fatty acid GC-MS finger-print by gas chromatography-mass spectrum (GC-MS) joint technology,
And control (standard) finger-print is established, in conjunction with fingerprint similarity assay, realize to adulterated fish in natural cod-liver oil
The Rapid identification of oil and vegetable oil.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of natural cod-liver oil adulteration detection method based on fingerprint pattern technology, the described method comprises the following steps: (1) sample
Collection；(2) preparation of fatty acid methyl ester reference substance solution；(3) derivatization treatment before sample column；(4) gas chromatography-mass spectrometry
With measurement fatty acid finger-print；(5) natural cod-liver oil fatty acid compares (standard) fingerprint map construction；(6) finger-print side
Science of law verifying；(7) listing sample fingerprint similarity is calculated and is evaluated；(8) the adulterated judgement of natural cod-liver oil；Wherein, it is adopted
Sample Derivatization Method is soda acid combination derivatization method, i.e., first carries out soap to fatty glyceride with sodium hydroxide
Change, then make catalyst with sulfuric acid and carry out esterification, is measured after being extracted with isooctane.
In the technical scheme, fatty acid is to exist as a triglyceride in natural cod-liver oil, and boiling point is high, need to be through derivative
Change processing is converted into low-boiling fatty acid methyl ester, measures convenient for GC-MS, while can also remove most of non-fat acid compound
Interference.Sample Derivatization Method of the present invention is soda acid combination derivatization method, i.e., first with sodium hydroxide pair
Fatty glyceride is saponified, then is made catalyst with sulfuric acid and carried out esterification, is measured after being extracted with isooctane.
Preferably, before step (3) sample column in derivatization treatment, processing method are as follows: weigh cod-liver oil sample 100mg
It sets in 20mL band screw socket reaction flask, adding 1.5mL mass fraction is 2% sodium hydrate methanol solution, and nitrogen charging screws bottle cap, whirlpool
30s is mixed, sets in 90 DEG C of thermostats and heats 20min, it is cooling；Adding 2mL mass fraction is 5% methanolic solution, and nitrogen charging screws
Bottle cap, whirlpool mixing 30s set in 100 DEG C of thermostats and heat 10min, cooling；2mL isooctane is added in precision, screws bottle cap, whirlpool
Mixing 1min in whirlpool gently shakes, stratification immediately plus 5mL saturated sodium chloride solution；Aspirate supernatant is transferred to equipped with a small amount of
In the test tube of anhydrous sodium sulfate, shaking dehydration takes solution after dehydration to be measured.
Preferably, in step (4) gas chromatography-mass spectrography measurement fatty acid finger-print, chromatographic mass spectrometry condition are as follows:
Instrument model: Agilent 7890B 7000C gas chromatograph-mass spectrometer (GC-MS)；Chromatographic column: Agilent DB-23 quartz capillary
Tubing string 30m × 0.25mm, 0.25 μm；Temperature program: initial temperature is 150 DEG C, is warming up to 170 DEG C with the rate of 1 DEG C/min, then
210 DEG C are warming up to the rate of 3 DEG C/min, and keeps 5min；Injector temperature: 250 DEG C；Carrier gas: high-purity helium；Flow velocity:
1.0mL/min；Sample volume: 1 μ L；Input mode: split sampling, split ratio: 100: 1；Ionization mode: EI；Electron energy:
70eV；Ion source temperature: 230 DEG C；Interface temperature: 260 DEG C；Quadrupole rod temperature: 150 DEG C；The solvent peak mute time: 4min；Entirely
Scan pattern, mass scan range m/z50-800.The natural cod-liver oil sample fatty acid measured by above-mentioned chromatographic mass spectrometry condition
24 chromatographic peaks are detected in GC-MS finger-print altogether.
Preferably, in natural cod-liver oil fatty acid control (standard) fingerprint map construction of step (5), different batches sample
After carrying out pre-treatment by step (3) respectively, sample introduction measurement obtains each sample fatty acid finger-print, selectes wherein 15 areas
Biggish shared peak shares peak as finger-print, and each shared peak primarily determines each fatty acid by NIST standard library searching
Structural information.Again by fatty acid methyl ester reference substance solution difference sample introduction measurement in step (2), chromatographic mass spectrometry figure is recorded, is passed through
Each fatty acid retention time and Information in Mass Spectra compare in reference substance and sample chromatogram mass spectrogram, realize to the final true of each shared peak
Card.By in the reference substance information of 15 shared fatty acid and mass spectrogram typing spectrum library editing machine, the natural fish of self-built complete set
Liver oil fatty acid methyl ester standard spectrum library, the spectrum library can be used for the fast qualitative of cod-liver oil fatty acid, eliminate chromatographic time drift pair
Qualitatively influence, do not need reference substance can carry out automatically it is qualitative；Shared peak is myristic acid by the successive arrangement of peak sequence
C14:0, pentadecanoic acid C15:0, palmitinic acid C16:0, palmitoleic acid C16:1, stearic acid C18:0, elaidic acid trans C18:1n-
9, oleic acid C18:1 n-9, vaccenic acid C18:1 n-7, linoleic acid C18:2n-6, alpha-linolenic acid C18:3n-3, SDA C18:4n-3,
Along 11- eicosenoic acid C20:1n-9, EPAC20:5n-3, cetoleic acid C22:1n-11, DHAC22:6n-3.
Preferably, selecting palmitinic acid as cod-liver oil fatty acid finger-print object of reference (S).
Preferably, the preparation of reference fingerprint, chooses 13 batches, representative sample, including domestic 6 enterprises
The sample of production is each 1 batch (S1-S6), and the sample of external 7 countries production is each 1 batch (S7-S13), is directed respectively into that " Chinese medicine chromatography refers to
2012 editions softwares of line map similarity evaluation system ", with S1 sample (the happy healthy Science and Technology Co., Ltd.'s production of celestial being) fingerprint image
Spectrum is fitted 13 batches of sample finger-prints through Supplements and full Peak tracking as referring to map, generates natural fish liver
Oil control (standard) finger-print (R)；Each shared peak is marked respectively by peak sequence in reference fingerprint: No. 1 peak (meat
Myristic acid)；No. 2 peaks (pentadecanoic acid)；No. 3 peaks are referring to peak (palmitinic acid)；No. 4 peaks (palmitoleic acid)；No. 5 peaks (stearic acid)；6
Number peak (elaidic acid)；No. 7 peaks (oleic acid)；No. 8 peaks (vaccenic acid)；No. 9 peaks (linoleic acid)；No. 10 peaks (alpha-linolenic acid)；No. 11 peaks
(SDA)；No. 12 peaks (along 11- eicosenoic acid)；No. 13 peaks (EPA)；No. 14 peaks (cetoleic acid)；No. 15 peaks (DHA).
Preferably, simulation test is carried out to the degree for mixing fish oil in the adulterated judgement of the natural cod-liver oil of step (8), if
10%, 20%, 30%, 40%, 50% 5 horizontal fish oil is mixed in meter cod-liver oil sample, carries out finger-print survey respectively
It is fixed, and the fingerprint similarity of each adulterated level is calculated, to quickly identify the adulterated fish oil of cod-liver oil.
Preferably, the preparation of (2) fatty acid methyl ester reference substance solution: precision weighs methyl myristate, 15 respectively
Alkanoic acid methyl esters, methyl hexadecanoate, Methyl palmitoleinate, methyl stearate, elaidic acid methyl esters, methyl oleate, vaccenic acid methyl esters, Asia
Methyl oleate, methyl linolenate, SDA methyl esters, suitable 11- eicosenoic acid methyl esters, EPA methyl esters, cetoleic acid methyl esters, DHA methyl esters
Reference substance is set in right amount in 25mL brown volumetric flask, is added isooctane to dissolve and is diluted to scale, and every 1mL difference fatty acids first is made
The control stock solution of ester 2mg；Each fatty acid methyl ester control stock solution 1mL of accurate absorption sets 10mL brown volumetric flask respectively
In, add isooctane to be diluted to scale, the reference substance solution of every 1mL difference fatty acids methyl esters 0.2mg is made, is used for fatty acid methyl
The self-built spectrum library of ester and qualitative confirmation.
Preferably, (7) listing sample fingerprint similarity calculates and evaluation is using " chromatographic fingerprints of Chinese materia medica phase
Like degree evaluation system " 2012 editions softwares, using reference fingerprint as standard, to the listing sample fatty acid fingerprint image of different batches
The similarity of spectrum is calculated.
The beneficial effects of the present invention are: the present invention first to the cod-liver oil samples of domestic and international different manufacturers and the place of production into
Row fatty acid GC-MS determining fingerprint pattern, then by Chinese Pharmacopoeia Commission recommend " chromatographic fingerprints of Chinese materia medica similarity is commented
2012 editions softwares of valence system " are fitted finger-print, establish the reference fingerprint comprising 15 shared peaks.By will be to
The finger-print that identification sample measures by the same method imports similarity evaluation software, calculates similarity, gained similarity value combination fish
Oily, vegetable oil fatty acid characteristic can quickly identify behavior adulterated in cod-liver oil that the identification method can be used as natural fish
The important technical of liver oil quality control and Adulteration identification, method of the invention are easy, accurate, it can be achieved that natural fish is listed
The Adulteration identification of liver oil product.
Detailed description of the invention
Fig. 1 is natural cod-liver oil fatty acid total ion chromatogram of the invention.
Fig. 2 is 13 batches of cod-liver oil fatty acid finger-prints and reference fingerprint (R) of the invention.
Fig. 3 is adulterated plant oil samples (sample 48) finger-print of the present invention.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further explained:
Embodiment
A kind of natural cod-liver oil Adulteration identification method based on finger-print, the described method comprises the following steps:
(1) collection of sample
The present invention collects cod-liver oil sample (including soft capsule and liquid oral) 48 batches altogether, is related to domestic 7 manufacturing enterprises,
Total 22 batches, external 7 producing countries (Norway, Iceland, Germany, Britain, the U.S., Canada and Australia), 16 brands
Import sample, amount to 26 batches.Reference fingerprint fitting chooses domestic 6 enterprises and 7 different producing countries with sample
Sample is each 1 batch (S1-S13), wherein the sample of a domestic production enterprise is rejected outside because of doubtful adulterated vegetable oil.
(2) prepared by reference substance solution
Fatty acid methyl ester reference substance source: 99% is all larger than purchased from U.S. Nu-chek company and Sigma company, purity respectively.
Preparation method: precision weighs methyl myristate, pentadecanoic acid methyl esters, methyl hexadecanoate, palmitoleic acid first respectively
It is ester, methyl stearate, elaidic acid methyl esters, methyl oleate, vaccenic acid methyl esters, methyl linoleate, methyl linolenate, SDA methyl esters, suitable
11- eicosenoic acid methyl esters, EPA methyl esters, cetoleic acid methyl esters, DHA methyl esters reference substance are set in right amount in 25mL brown volumetric flask, are added
Isooctane dissolves and is diluted to scale, and the control stock solution of every 1mL difference fatty acids methyl esters 2mg is made.
Each fatty acid methyl ester control stock solution 1mL of accurate absorption is set in 10mL brown volumetric flask respectively, adds isooctane dilute
Release to scale, the reference substance solution of every 1mL difference fatty acids methyl esters 0.2mg be made, for the self-built spectrum library of fatty acid methyl ester with
Qualitative confirmation.
(3) derivatization treatment before sample column
Fatty acid is to exist as a triglyceride in cod-liver oil, and boiling point is high, and low-boiling rouge need to be converted into through derivatization treatment
Fatty acid methyl esters measure convenient for GC-MS, while can also remove the interference of most of non-fat acid compound.It is of the present invention
Sample Derivatization Method is soda acid combination derivatization method, i.e., is first saponified with sodium hydroxide to fatty glyceride,
Catalyst is made with sulfuric acid again and carries out esterification, is measured after being extracted with isooctane.
Experimental method: it weighs cod-liver oil sample 100mg and sets in 20mL band screw socket reaction flask, add the 1.5mL mass fraction to be
2% sodium hydrate methanol solution, nitrogen charging screw bottle cap, and whirlpool mixing 30s sets in 90 DEG C of thermostats and heats 20min, cooling；Add
2mL mass fraction is 5% methanolic solution, and nitrogen charging screws bottle cap, and whirlpool mixing 30s sets in 100 DEG C of thermostats and heats
10min, it is cooling；2mL isooctane is added in precision, screws bottle cap, whirlpool mixing 1min, immediately plus 5mL saturated sodium chloride solution, gently
Light shaking, stratification；Aspirate supernatant is transferred in the test tube equipped with a small amount of anhydrous sodium sulfate, shaking dehydration, after taking dehydration
Solution is to be measured.
(4) acquisition of fatty acid GC-MS finger-print
By the prepare liquid sample introduction in step (3), GC-MS analysis, instrument model: Agilent 7890B 7000C gas phase color are carried out
Spectrum-mass spectrometer (Agilent company of the U.S.)；Chromatographic column: Agilent DB-23 quartz capillary column (30m × 0.25mm,
0.25μm)；Temperature program: initial temperature is 150 DEG C, is warming up to 170 DEG C with the rate of 1 DEG C/min, then with the rate of 3 DEG C/min
210 DEG C are warming up to, and keeps 5min.Injector temperature: 250 DEG C；Carrier gas: high-purity helium (purity 99.999%)；Flow velocity:
1.0mL/min；Sample volume: 1 μ L；Input mode: split sampling, split ratio: 100: 1；Ionization mode: EI；Electron energy:
70eV；Ion source temperature: 230 DEG C；Interface temperature: 260 DEG C；Quadrupole rod temperature: 150 DEG C；The solvent peak mute time: 4min；Entirely
Scan pattern, mass scan range m/z50-800 acquire sample fatty acid total ion current by above-mentioned chromatographic mass spectrometry conditional operation
24 chromatographic peaks are presented altogether, see Fig. 1 as sample finger-print for chromatogram in natural cod-liver oil fatty acid finger-print.
(5) building of natural cod-liver oil control (standard) finger-print
A. the calibration at peak is shared
After 13 batch finger-print fittings carry out pre-treatment by step (3) with sample, sample introduction measurement obtains each sample fatty acid and refers to
Line map, the chromatographic peak for choosing wherein 15 areas larger (accounting for total peak area 94%) shares peak as finger-print, each shared
Peak is retrieved by NIST standard spectrum library, in conjunction with fragment ion information, is tentatively confirmed to shared fatty acid.By step
(2) the sample introduction measurement of fatty acid methyl ester reference substance solution difference, records chromatography, mass spectrogram, passes through retention time and Information in Mass Spectra in
It compares, realizes the final confirmation to each shared peak.Above-mentioned 15 kinds of fatty acid methyl ester reference substance information and mass spectrogram are entered into respectively
It composes in the editing machine of library, chromatography can be effectively eliminated by obtaining complete natural cod-liver oil fatty acid methyl ester standard spectrum library using the spectrum library
Time drift is influenced on qualitative, can carry out fast qualitative to institute's fatty acids in cod-liver oil finger-print without reference substance.
Shared peak is myristic acid C14:0, pentadecanoic acid C15:0, palmitinic acid C16:0, palmitoleic acid by the successive arrangement of peak sequence
C16:1, stearic acid C18:0, elaidic acid trans C18:1 n-9, oleic acid C18:1 n-9, vaccenic acid C18:1 n-7, linoleic acid
C18:2n-6, alpha-linolenic acid C18: 3n-3, SDA C18:4n-3, along 11- eicosenoic acid C20:1 n-9, EPA C20:5n-3,
Cetoleic acid C22:1 n-11, DHAC22:6n-3.
B. the selection of object of reference (S)
The reference substance of finger-print is usually chosen and is easy to get, and property is stablized, and the higher index components of content are mainly used for referring to
The determination of line graphical spectrum technology parameter.DHA and EPA is index ingredient in natural cod-liver oil, but the two is polyunsaturated fat
Acid, property is unstable, the oxidizable destruction of high temperature, and response is not high in chromatogram.Palmitinic acid is in cod-liver oil fatty acid chromatography
Response highest in figure, peak area are maximum, account for the 26% of total peak area, are saturated fatty acid, and property is stablized, and with adjacent fat
The separation at sour peak is good, though not being index ingredient, is able to satisfy the requirement that finger-print stability and reproducibility are investigated, comprehensive
Analysis is closed, the present invention selects palmitinic acid as cod-liver oil fatty acid finger-print object of reference (S).
C. the preparation of reference fingerprint
The sample fatty acid finger-print representative to 13 batches, is directed respectively into that " chromatographic fingerprints of Chinese materia medica similarity is commented
2012 editions softwares of valence system " generate control (standard) through Supplements and full Peak tracking using S1 sample as referring to map
Finger-print is shown in Fig. 2.15 shared peaks are relative to the relative retention time referring to peak (S) in 13 batches of natural cod-liver oil samples
(RRT) and relative peak area (RA) statistical result is shown in Table 1.
113 batches of natural cod-liver oil of table share peak relative retention time and relative peak area statistical result
(6) fingerprint spectrum method is verified
A. precision test
S1 sample 100mg is weighed, test solution is prepared by step (3) sample-pretreating method, by step (4) chromatographic mass spectrometry item
Part continuous sample introduction 6 times, acquire finger-print.Calculate 15 shared peaks relative to referring to peak (S) relative retention time (RRT) and
RRT and RA average value and relative standard deviation (RSD) statistical result of relative peak area (RA), continuous sample introduction is shown in Table 2, can by table
Seeing, the RSD of each shared peak relative retention time is 0.021%~0.067%, the RSD of relative peak area is 0.690%~
2.864%, show that the measuring method precision is good.
2 Precision test result of table
B. repetitive test
S1 sample 100mg is weighed, totally 5 parts, test solution is prepared by step (3) sample-pretreating method respectively, by step (4)
Chromatographic mass spectrometry condition sample introduction acquires finger-print, and 15 shared peaks are relative to referring to peak (S) in every part of sample chromatogram figure of calculating
Relative retention time (RRT) and relative peak area (RA), RRT the and RA average value and relative standard deviation (RSD) system of 5 parts of samples
Meter the results are shown in Table 3.By table as it can be seen that the RSD of each shared peak relative retention time is 0.024%~0.077%, relative peak area
RSD is 0.641%~3.708%, shows that determining fingerprint pattern repeatability is good.
3 repetitive test result of table
C. stability test
Weigh S1 sample 100mg, prepare test solution by sample-pretreating method, by above-mentioned chromatographic mass spectrometry condition respectively 0,
4,8,12, sample introduction measures for 24 hours, calculates in different time points test solution 15 shared peaks relative to referring to the opposite of peak (S)
Retention time (RRT) and relative peak area (RA), RRT the and RA average value and relative standard deviation (RSD) statistics at 5 time points
It the results are shown in Table 4.By table as it can be seen that the RSD of relative retention time is 0.020%~0.089%, the RSD of relative peak area is
0.844%~2.951%, show that sample is good in internal stability for 24 hours.
4 stability test result of table
(7) fingerprint similarity is evaluated
Finger-print can characterize the correlation of substance complicated ingredient with its quality, and during characterization, similarity evaluation is risen emphatically
It acts on, cod-liver oil fatty acid method for evaluating similarity of the present invention is that " Chinese medicine color is recommended by Chinese Pharmacopoeia Commission
2012 editions softwares of spectrum fingerprint similarity evaluation system ", using reference fingerprint as standard, to the 48 of the production of domestic and international enterprise
The similarity of batch sample fatty acid finger-print is calculated, and calculated result is shown in Table 5.By table as it can be seen that 48 batch cod-liver oil produce
Similarity in product except sample 14, sample 36 and sample 48 is lower than 0.996, and the similarity of remaining 45 batch sample is in 0.996-
Between 1, there is very high similarity.
5 48 batch sample similarity calculation result of table
(8) natural cod-liver oil Adulteration identification
Usual adulterated low price fish oil and vegetable oil in natural cod-liver oil, to reduce cost.Compare the fat of cod-liver oil and fish oil
Sour finger-print finds suitable 11- eicosenoic acid in fish oil sample and cetoleic acid content far below cod-liver oil, in fish oil
EPA content be apparently higher than DHA.When adulterated fish oil in pure cod-liver oil, these above-mentioned fatty acid characteristic indexs can change
Become, the similarity decline of the finger-print and reference fingerprint that measure so as to cause adulterated cod-liver oil, calculated result becomes smaller.This
Invention carries out simulation test to the degree for mixing fish oil, design is prepared for mixing 10% in cod-liver oil, 20%, 30%, 40%,
The adulterated sample of 50% 5 horizontal fish oil measures finger-print respectively, imports software and carries out similarity calculation, calculated result is shown in
Table 6, by table as it can be seen that when it is adulterated it is horizontal >=10% when, similarity is lower than 0.996, can effectively identify adulterated behavior.Sample 14
Similarity is 0.980, and the similarity of sample 36 is 0.988, in conjunction with the variation of above-mentioned fatty acid characteristic index, can determine that sample 14
In mixed about 30% fish oil, about 20% fish oil has been mixed in sample 36.
48 similarity of sample is only 0.848, analyzes each fatty acid peak area percent in its finger-print, finds linoleic acid
Peak area percent is up to 19%, is much higher than other 47 batch sample Linoleic acid peak area percent average value (1.4%), sample
48 finger-print of product is shown in Fig. 3.Linoleic acid content height is the most important feature of vegetable oil, six kinds of most common vegetable oil (soybean oils, flower
Oil generation, corn oil, rapeseed oil, sunflower oil and sesame oil) institute's fatty acids Linoleic acid average content is about 40%.Therefore pass through
Similarity analysis, in conjunction with linoleic acid peak area percent value, it is possible to determine that adulterated vegetable oil in sample 48.With reference to European medicine
The natural cod-liver oil quality standard recorded in allusion quotation 8.0 editions and United States Pharmacopeia 39 editions, linoleic acid peak area percentage accounting limit are
0.5%~3.0%.Therefore, when in sample to be identified similarity be lower than 0.996, linoleic acid area percentage accounting is more than 3.0%,
It can adulterated vegetable oil behavior in the natural cod-liver oil of Rapid identification.
The similarity calculation result of the different adulterated levels of fish oil is mixed in 6 cod-liver oil of table
| Mix level | 0% | 10% | 20% | 30% | 40% | 50% |
| Similarity | 1.000 | 0.995 | 0.989 | 0.982 | 0.973 | 0.945 |
Present invention application GC-MS fingerprint pattern technology and fingerprint similarity appraisement system construct natural cod-liver oil fat
Acid control (standard) finger-print and adulterated cod-liver oil evaluation method, this method are easy to operate, accurate and reliable, it can be achieved that adulterated
The fast and effective identification of cod-liver oil cracks down on counterfeit goods for science and provides reliable technological means, effective specification cod-liver oil market.
Claims (9)
1. a kind of natural cod-liver oil Adulteration identification method based on finger-print, which is characterized in that the method includes following steps
It is rapid: (1) collection of sample；(2) preparation of fatty acid methyl ester reference substance solution；(3) derivatization treatment before sample column；(4) gas phase
Chromatograph-mass spectrometer coupling measures fatty acid finger-print；(5) natural cod-liver oil fatty acid compares (standard) fingerprint map construction；(6)
Fingerprint spectrum method verifying；(7) listing sample fingerprint similarity is calculated and is evaluated；(8) the adulterated judgement of natural cod-liver oil；
Wherein, used sample Derivatization Method is soda acid combination derivatization method, i.e., first sweet to fatty acid with sodium hydroxide
Grease is saponified, then is made catalyst with sulfuric acid and carried out esterification, is measured after being extracted with isooctane.
2. a kind of natural cod-liver oil Adulteration identification method based on finger-print according to claim 1, which is characterized in that
Before step (3) sample column in derivatization treatment, processing method are as follows: weigh cod-liver oil sample 100mg and set 20mL band screw socket reaction
In bottle, adding 1.5mL mass fraction is 2% sodium hydrate methanol solution, and nitrogen charging screws bottle cap, and whirlpool mixing 30s sets 90 DEG C of perseverances
20min is heated in warm device, it is cooling；Adding 2mL mass fraction is 5% methanolic solution, and nitrogen charging screws bottle cap, whirlpool mixing
30s sets in 100 DEG C of thermostats and heats 10min, cooling；2mL isooctane is added in precision, screws bottle cap, and whirlpool mixing 1min is stood
I.e. plus 5mL saturated sodium chloride solution, it gently shakes, stratification；Aspirate supernatant is transferred to equipped with a small amount of anhydrous sodium sulfate
In test tube, shaking dehydration takes solution after dehydration to be measured.
3. a kind of natural cod-liver oil Adulteration identification method based on finger-print according to claim 1, which is characterized in that
Step (4) gas chromatography-mass spectrography measures in fatty acid finger-print, chromatographic mass spectrometry condition are as follows: instrument model: Agilent
7890B 7000C gas chromatograph-mass spectrometer (GC-MS)；Chromatographic column: Agilent DB-23 quartz capillary column 30m × 0.25mm,
0.25μm；Temperature program: initial temperature is 150 DEG C, is warming up to 170 DEG C with the rate of 1 DEG C/min, then with the rate of 3 DEG C/min
210 DEG C are warming up to, and keeps 5min；Injector temperature: 250 DEG C；Carrier gas: high-purity helium；Flow velocity: 1.0mL/min；Sample volume: 1
μL；Input mode: split sampling, split ratio: 100: 1；Ionization mode: EI；Electron energy: 70eV；Ion source temperature: 230 DEG C；
Interface temperature: 260 DEG C；Quadrupole rod temperature: 150 DEG C；The solvent peak mute time: 4min；Full scan mode, mass scan range m/
z50-800。
4. a kind of natural cod-liver oil Adulteration identification method based on finger-print according to claim 1, which is characterized in that
In natural cod-liver oil fatty acid control (standard) fingerprint map construction of step (5), different batches finger-print fitting is pressed with sample
After step (3) carries out pre-treatment, sample introduction measurement obtains each sample fatty acid finger-print, and it is biggish to choose wherein 15 areas
Shared peak shares peak as finger-print, by each fatty acid information of NIST standard library searching, then uses fatty acid reference substance
Structural identification is carried out, by 15 shared peaks by the structural information after confirmation, the natural cod-liver oil fatty acid methyl of self-built complete set
Ester standard spectrum library, the spectrum library can be used for the fast qualitative of cod-liver oil fatty acid, and eliminate chromatographic time drift influences on qualitative, no
Need reference substance that can carry out automatically qualitative；Shared peak is myristic acid C14:0, pentadecanoic acid by the successive arrangement of peak sequence
C15:0, palmitinic acid C16:0, palmitoleic acid C16:1, stearic acid C18:0, elaidic acid trans C18:1 n-9, oleic acid C18:1
N-9, vaccenic acid C18:1 n-7, linoleic acid C18:2n-6, alpha-linolenic acid C18:3n-3, SDA C18:4n-3, suitable 20 carbon of 11-
Olefin(e) acid C20:1n-9, EPA C20:5n-3, cetoleic acid C22:1n-11, DHA C22:6n-3.
5. a kind of natural cod-liver oil Adulteration identification method based on finger-print according to claim 1 or 4, feature exist
In selecting palmitinic acid as cod-liver oil fatty acid finger-print object of reference (S).
6. a kind of natural cod-liver oil Adulteration identification method based on finger-print according to claim 1 or 4, feature exist
In the preparation of reference fingerprint, the sample fatty acid finger-print representative to different batches is directed respectively into " Chinese medicine
2012 editions softwares of chromatographic fingerprinting similarity evaluation system ", using S1 sample as reference map, through Supplements and full spectral peak
Matching, is fitted finger-print, generates reference fingerprint；Each shared peak is distinguished by peak sequence in reference fingerprint
It is marked: No. 1 peak (myristic acid)；No. 2 peaks (pentadecanoic acid)；No. 3 peaks are referring to peak (palmitinic acid)；No. 4 peak (palm oils
Acid)；No. 5 peaks (stearic acid)；No. 6 peaks (elaidic acid)；No. 7 peaks (oleic acid)；No. 8 peaks (vaccenic acid)；No. 9 peaks (linoleic acid)；No. 10
Peak (alpha-linolenic acid)；No. 11 peaks (SDA)；No. 12 peaks (along 11- eicosenoic acid)；No. 13 peaks (EPA)；No. 14 peak (cetenes
Acid)；No. 15 peaks (DHA).
7. a kind of natural cod-liver oil Adulteration identification method based on finger-print according to claim 1, which is characterized in that
In the adulterated judgement of the natural cod-liver oil of step (8), simulation test is carried out to the degree for mixing fish oil, designs and is mixed in cod-liver oil sample
10%, 20%, 30%, 40%, 50% 5 horizontal fish oil, carries out determining fingerprint pattern, and calculate each adulterated level respectively
Similarity, when it is adulterated it is horizontal >=10% when, similarity is lower than 0.996, adulterated behavior can be effectively identified, thus quickly to fish
The adulterated fish oil of liver oil is identified；Identification to vegetable oil is mixed, the fatty acid characterized by linoleic acid, using similarity evaluation and
Linoleic acid peak area percentage accounting analyzes the method combined, and when sample fingerprint similarity to be identified is lower than 0.996, Asia is oily
When sour peak area percent is more than 3.0%, adulterated vegetable oil in cod-liver oil sample can be quickly determined.
8. a kind of natural cod-liver oil Adulteration identification method based on finger-print according to claim 1, which is characterized in that
(2) preparation of fatty acid methyl ester reference substance solution: precision weighs methyl myristate, pentadecanoic acid methyl esters, palmitinic acid first respectively
Ester, Methyl palmitoleinate, methyl stearate, elaidic acid methyl esters, methyl oleate, vaccenic acid methyl esters, methyl linoleate, linolenic acid first
Ester, sets 25mL palm fibre along 11- eicosenoic acid methyl esters, EPA methyl esters, cetoleic acid methyl esters, DHA methyl esters reference substance at SDA methyl esters in right amount
In color tolerance measuring bottle, add isooctane to dissolve and be diluted to scale, the control deposit that every 1mL difference fatty acids methyl esters 2mg is made is molten
Liquid；Each fatty acid methyl ester control stock solution 1mL of accurate absorption is set in 10mL brown volumetric flask respectively, and isooctane is added to be diluted to quarter
The reference substance solution of every 1mL difference fatty acids methyl esters 0.2mg is made in degree, for the self-built spectrum library of fatty acid methyl ester and qualitative true
Card.
9. a kind of natural cod-liver oil Adulteration identification method based on finger-print according to claim 1, which is characterized in that
(7) listing sample fingerprint similarity calculates and evaluation is using " similarity evaluation " 2012
Version software counts the similarity of the listing sample fatty acid finger-print of different batches using reference fingerprint as standard
It calculates.
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