CN106124604A - The mass spectrometric analysis method of free fatty in a kind of edible oil based on Derivative - Google Patents
The mass spectrometric analysis method of free fatty in a kind of edible oil based on Derivative Download PDFInfo
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Abstract
The mass spectrometric analysis method of free fatty in a kind of edible oil based on Derivative, comprise the steps: 1) by edible oil sample solvent dilution to be measured, carry out derivative reaction after adding internal standard, obtain the sample introduction solution of testing sample, carry out mass spectral analysis；2) qualitative analysis: according to the mass-to-charge ratio in gained spectrogram, determine the quasi-molecular ion peak of corresponding free-fat acid derivative；3) quantitative analysis: fatty acid standards is configured to the standard solution of a series of concentration, derivative reaction is carried out after being separately added into internal standard, the sample introduction solution got standard samples, carry out mass spectral analysis, draw standard curve, edible oil sample to be measured is carried out quantitative analysis.It is complicated that the present invention solves edible oil mesostroma, free fatty acid content is low, it is difficult to purification and enrichment, and the difficulty that when detecting under mass spectrum negative ion mode, ionizing efficiency is low and detection sensitivity is not enough, it is achieved that the qualitative and quantitative analysis efficient, highly sensitive of free fatty in edible oil.
Description
Technical field
The present invention relates to the mass spectrometric analysis method of free fatty in a kind of edible oil based on Derivative, belong to point
Analysis detection field.
Technical background
Edible main body of oil is triglyceride (triacylglycerols, TAG account for 95%～98%), glycerol three
Ester is to be formed by 1 glycerol molecule and the condensation of 3 fatty acid molecules, fatty acid account for that triglyceride molecular weight constitutes 95% with
On.Fatty acid (Fatty acid, FA) is the aliphatic carboxylic acid that a series of length does not wait (C4～C36), is a simplest class
Lipid compounds, is the composition forming other lipids.Fatty acid plays an important role in maintenance health, fat in diet
The close phase of sickness rate of the various diseases such as the composition of fat acid and content and tumor, coronary heart disease, cardiovascular and cerebrovascular disease and senile dementia
Guan Xing.Therefore, composition and the proportioning thereof of fatty acid becomes the most important index weighing edible oil nutritive value.
Free fatty (Free fatty acid, FFA) is also known as non-esterified fatty acid (nonestesterified
Fatty acid, NEFA), it is the material of decomposing neutral fat one-tenth.Free fatty in edible oil is the hydrolysis of triglyceride
Product, also contained hydrophobic group owing to both having contained hydrophilic group in its molecule, it is intended to concentrate on the surface of edible oil, reduced table
Surface tension, increases oxygen diffusion rate in edible oil and fat, and then accelerates the oxidation of edible oil.Further, free fatty does not has
Triglyceride is stable, it is easier to causes the oxidation of oil and becomes sour, the quality of impact oil and function.In raw oil, FFAs composition can
For describing quality and the assessment oil degree of injury of expressed oil.FFA composition can be as oil product in different in moisture, temperature, oxygen-containing
Degraded parameter during amount, illumination storage and pan-fried stir-fry.
Tradition measures the method for free fatty in edible oil mainly titration measuring acid value and gas chromatography-mass spectrography
(GC-MS).The milligram number of acid value of lipids potassium hydroxide needed for free fatty in 1 gram of oils and fats of neutralization represents, is to weigh
One important indicator of oil quality.At present both at home and abroad using potassium hydroxide titration to be dissolved in ethanol to the mensuration of acid value of lipids more
In oil to phenolphthalein terminal point, although simple to operate, but be difficult to realize automated analysis, and the method needs substantial amounts of reagent, structure
Become potential environmental pollution, additionally, what titration measuring acid value obtained is free fatty acid total amount in edible oil, it is impossible to each trip
Carry out qualitative analysis from fatty acid, the content of various free fatty can not be obtained；Gas chromatography (GC) can provide food
By the qualitative and quantitative information of free fatty each in oil, but edible oil mesostroma is complicated, and free fatty acid content is low, have strong
Polarity and weak volatility, therefore the free fatty in edible oil is difficult to directly separate through GC, and sample needs to first pass through complexity
Isolated and purified process is (as in liquid-liquid extraction edible oil, free fatty or employing magnetic nanoparticle are enriched with the trip in edible oil
From fatty acid etc.), the most again the free fatty being purified is carried out esterification derivative after, just can carry out GC separation, qualitative
With the free fatty in quantitative analysis edible oil, whole process is extremely complex, loaded down with trivial details, time-consuming, and needs consuming the most organic
Solvent, additionally, the shortcoming such as the method there is also poor stability, and detection sensitivity is low.
Therefore, fatty acid analysis technology of dissociating in existing edible oil is at analysis throughput, sensitivity for analysis and accuracy
Aspect all comes with some shortcomings.
Summary of the invention
The technical problem to be solved is to provide a kind of based on derivatization for above-mentioned the deficiencies in the prior art
The mass spectrometric analysis method of free fatty in the edible oil of technology, solves edible oil mesostroma complicated, free fatty acid content
Low, it is difficult to purification and enrichment, and when free fatty detects under mass spectrum negative ion mode, ionizing efficiency is low and detects
Under-sensitive difficulty, it is achieved that the qualitative and quantitative analysis efficient, highly sensitive of free fatty in edible oil.
The present invention solves technical problem set forth above, the technical scheme used is:
In a kind of edible oil based on Derivative, the mass spectrometric analysis method of free fatty, comprises the steps:
1) by edible oil sample solvent dilution to be measured, after adding internal standard, reaction is performed the derivatization, after reaction in edible oil
Free fatty be converted into positively charged free-fat acid derivative, obtain the sample introduction solution of testing sample；
2) by step 1) the sample introduction solution of gained testing sample carries out mass spectral analysis, gathers the spectrum of free-fat acid derivative
Figure and spectral peak data；
3) qualitative analysis: according to step 2) mass-to-charge ratio in gained spectrogram, determine the standard of corresponding free-fat acid derivative
Molecular ion peak, thus the free fatty in testing sample is carried out qualitative analysis；
4) quantitative analysis: fatty acid standards solvent dilution becomes the standard solution of a series of concentration, in being separately added into
After mark, with step 1) identical under conditions of perform the derivatization reaction, after reaction, free fatty is converted into positively charged trip
From derivative of fatty acid, the sample introduction solution got standard samples；
5) a, by step 4) the sample introduction solution of gained standard sample carries out mass spectral analysis, gathers free-fat acid derivative
Spectrogram and spectral peak data, in standard solution, free fatty and interior target concentration proportion are as abscissa, and free fatty derives
Thing is vertical coordinate with the quasi-molecular ion peak intensity rate of internal standard derivant, draws standard curve；B, by step 2) gained spectrogram
In the quasi-molecular ion peak intensity rate combined standard curve of free derivative of fatty acid and internal standard derivant, to edible oil to be measured
Free fatty in sample carries out quantitative analysis.
By such scheme, described edible oil sample to be measured includes Oleum Brassicae campestris, Oleum sesami, Semen Maydis oil, Semen Lini oil, Fructus Canarii albi
Oil, perilla oil, Adeps Sus domestica, fish oil etc..
By such scheme, the derivative reagent used is that an amino (-NH is contained in one end2), the other end contains a uncle
The compound of amido, formula is expressed as: NH2-(CH2)n-NR2, wherein, n span is 2～4, and R group is methyl, ethyl
Deng.Preferably, deriving effect and Mass Spectrometer Method effect is the most ideal during n=2, such as derivative reagent selects N, N-dimethyl second
Diamidogen and N, N-diethyl ethylenediamine etc..Amino in described derivative reagent is anti-with the carboxyl generation amidatioon in free fatty
Should, the tertiary amino group of the derivative reagent other end is incorporated in free fatty, thus introduces the positive charge of an easily ionizable
Group, is converted into positively charged free-fat acid derivative by electronegative free fatty.
By such scheme, the condition of described derivative reaction is: will add internal standard after edible oil sample solvent dilution, urge
Agent vortex mixes, and is subsequently adding derivative reagent, and reaction temperature is 38～42 DEG C, and the response time is 2～10min.
By such scheme, in described derivative reaction, with deuterated hexadecanoic acid (FA16:0-d4) as internal standard, with the chloro-1-of 2-
Methyl pyridinium iodide (2-chloro-1-methylpyridinium iodide, CMPI) and triethylamine
(triethylamine, TEA) is catalyst, with N, N-diethyl ethylenediamine (N, N-diethyl-1,2-ethanediamine,
DEEA) being derivative reagent, solvent uses the organic solvents such as acetonitrile.Preferably, in derivative reaction system, the concentration of fatty acid
Being 0.5～200nmol/L, interior target concentration is 5～15nmol/L, and the concentration of catalyst of triethylamine is 0.5～0.7 μm ol/mL,
The concentration of catalyst 2-chloro-1-methyl pyridinium iodide is 0.1～0.5 μm ol/mL, derivative reagent N, N-diethyl ethylenediamine
Concentration be 0.6～1.2 μm ol/mL.
By such scheme, the present invention performs the derivatization reaction to free fatty in edible oil, and free fatty is converted into
Positively charged free-fat acid derivative, when carrying out mass spectral analysis in the positive-ion mode, free-fat acid derivative is in matter
Spectrum collision-induced cracking can produce the neutral group of a fixed mass number (if derivative reagent is N, N-diethyl ethylenediamine
Time, neutral group is NH-(CH2CH3)2, mass number is 73Da), therefore use mass spectrum neutral loss scan pattern, scanning neutrality
Missing mass number 73Da (NLS73), it is possible to the quasi-molecular ion peak of each derivative of fatty acid optionally detected, and then realize
The qualitative and quantitative analysis of free fatty in edible oil sample, as shown in figs. 10-11.
By such scheme, step 1) and step 4) gained sample introduction solution preferably through being dried, redissolution, purification etc. pretreated
Journey carries out mass spectral analysis again.Described preprocessing process be once more than, wherein, be dried and use nitrogen, helium, argon etc. to dry up；
Redissolution uses the organic solvents such as chloroform；Purification includes extraction and filtration etc., and wherein extraction uses the mixed of formic acid, water, chloroform composition
Close solution；Filter the organic facies filter membrane using aperture to be 0.1～5 μm.
By such scheme, the condition of described mass spectral analysis is: entry needle pump sample introduction, and sample introduction flow velocity is 10～30 μ L/min；
Electron spray ionisation source (Electrospray Ionization, ESI): positive ion mode；Scanning of the mass spectrum pattern: 73Da neutrality is lost
Lose scanning (73Da neutral loss scan)；Ion source gas 1 (Ion Source Gas 1, GS 1): 12kPa；Collision
Energy (collision energy, CE): 30～35eV；Remove a bunch voltage (declustering potential, DP): 70～
80eV；Entrance potential (Entrance Potential, EP): 10V；Collision cell output voltage (Collision Cell Exit
Potential, CXP): 10V；Mass range: 200～550m/z.
By such scheme, described step 4) in the condition of derivative reaction and step 1) identical；Step 4) in mass spectral analysis
Condition and step 2) identical；Described step 4) in solvent and step 1) in identical.
By such scheme, described step 4) Plays solution is the mixed solution of one or more fatty acids, and described mark
In quasi-solution, the concentration range of fatty acid is all 0.5～200nmol/L.
The present invention proposes the mass spectrometric analysis method of free fatty in a kind of edible oil based on Derivative.The party
Method uses one end to contain an amino (-NH2), the other end contains the compound of a tertiary amine groups, such as N, N-dimethyl-ethylenediamine
As derivative reagent, in edible oil, free fatty is derivative.In amino group in derivative reagent and free fatty
Carboxyl generation amidation process, the tertiary amino group of the derivative reagent other end is incorporated in free fatty, thus introduces
The positive charge group of one easily ionizable, and electronegative free fatty is converted into positively charged free fatty and derives
Thing.
Compared with prior art, the invention has the beneficial effects as follows:
1, edible oil mesostroma is complicated, and free fatty acid content is low, and traditional gas chromatography-mass spectrometry analysis method needs head
First the free fatty in edible oil is enriched with and purification, the most again the free fatty after enriching and purifying is carried out methyl ester
Changing derivative laggard row gas chromatography-mass spectrometry analysis, operating procedure is extremely complex and detection sensitivity is low.And in the present invention, excellent
Under the derivatization conditions changed, amino group in derivative reagent is specific and free fatty containing carboxylic group in edible oil
Compounds generation amidatioon is condensed, therefore without being enriched with the free fatty in edible oil sample and purification, directly
Can perform the derivatization reaction after being diluted by edible oil, the response time only needs about 5 minutes, solves edible oil mesostroma multiple
Miscellaneous, free fatty acid content is low, and traditional analysis purification and enriching step are complicated, the shortcoming of required time length.
2, the amino group in derivative reagent of the present invention is anti-with the carboxyl generation amidatioon in free fatty
Should, the tertiary amino group of the derivative reagent other end is incorporated in free fatty, thus introduces the positive charge of an easily ionizable
Group, and electronegative free fatty is converted into positively charged free-fat acid derivative, successfully achieve
Detect derivatization product under positive ion mode, improve ionizing efficiency, reduce ionization suppression, substantially increase Electrospray Mass Spectrometry spirit
Sensitivity；Meanwhile, solve that ionizing efficiency when free fatty detects under mass spectrum negative ion mode is low and detection sensitivity
Not enough difficulty, it is achieved that in edible oil, the high-sensitive detection of free fatty is analyzed.
3, after the present invention is to free fatty performs the derivatization reaction in edible oil, carries out mass spectrum in the positive-ion mode and divide
During analysis, free-fat acid derivative can produce the neutral group of a fixed mass number in MS/MS collision inducing lysis and (such as spread out
When raw reagent is N, N-diethyl ethylenediamine, neutral group is NH-(CH2CH3)2, mass number is 73Da), therefore use in mass spectrum
Property lose scan pattern, neutral missing mass number 73Da of scanning (NLS73), it is possible to each derivative of fatty acid optionally detected
Quasi-molecular ion peak.Compared to traditional method, free-fat in edible oil based on Derivative of the present invention
The mass spectrometric analysis method of acid has high selectivity to fatty acid compound free in edible oil, can be specific in edible oil
Free fatty compounds carries out high-selectivity analysis, is particularly suitable for analyzing the free acid kind in complex matrices sample
Compound.
4, the method for the present invention is simple to operate, and edible oil sample to be measured carries out derivative reaction after directly diluting, and obtains
Product, without carrying out chromatographic column separation, is directly entered mass spectrum, uses neutral loss scan to carry out point in the positive-ion mode
Analysis, method is simple and efficient, it is possible to realizes the selectivity efficient, high of free fatty, high-sensitive qualitative, quantitative in edible oil and divides
Analysis.
Accompanying drawing explanation
Fig. 1 be 16 kinds of fatty acid standards of mass spectral analysis (capric acid (10:0), lauric acid (12:0), myristic acid (14:0),
Pentadecanoic acid (15:0), palmitoleic acid (16:1), Palmic acid (16:0), linolenic acid (18:3), linoleic acid (18:2), oleic acid (18:
1), stearic acid (18:0), nonadecylic acid (19:0), eicosapentaenoic acid (EPA, 20:5), arachidonic acid (ARA, 20:4), two
Ten carbon enoic acids (20:1), arachidic acid (20:0), docosahexenoic acid (DHA, 22:6)) derivant and internal standard (deuterated hexadecane
Acid, FA16:0-d4 (IS)) derivant carries out the mass spectrum of neutral loss scan (73Da) (+NLS73Da) in the positive-ion mode
Figure；
In Fig. 2: a is the mass spectrum of the free-fat acid derivative in olive oil sample, b is free fatty in olive oil
Containing spirogram；
In Fig. 3: a is the mass spectrum of free derivative of fatty acid in Semen Lini oil sample, and b is free-fat in Semen Lini oil
Acid containing spirogram；
In Fig. 4: a is the mass spectrum of free derivative of fatty acid in perilla oil sample, and b is free fatty in perilla oil
Containing spirogram；
In Fig. 5: a is the mass spectrum of free derivative of fatty acid in Oleum sesami sample, and b is free fatty in Oleum sesami
Containing spirogram；
In Fig. 6: a is the mass spectrum of the free-fat acid derivative in Semen Maydis oil sample, b is the free-fat in Semen Maydis oil
Acid containing spirogram；
In Fig. 7: a is the mass spectrum of the free-fat acid derivative in Oleum Brassicae campestris sample, b is free fatty in Oleum Brassicae campestris
Containing spirogram；
In Fig. 8: a is the mass spectrum of the free-fat acid derivative in fish oil sample, b is the containing of free fatty in fish oil
Spirogram；
In Fig. 9: a is the mass spectrum of the free fatty of Adeps Sus domestica, b is the free fatty acid content figure of Adeps Sus domestica；
Figure 10 is free fatty derivative reaction schematic diagram；
Figure 11 is the mass spectral analysis schematic diagram of free-fat acid derivative.
Detailed description of the invention
In order to make those skilled in the art be more fully understood that technical scheme, below in conjunction with specific embodiment pair
The present invention is described in further detail.
The fatty acid abbreviation explanation used in the present invention: 10:0, capric acid；12:0, lauric acid；14:0, myristic acid；15:
0, pentadecanoic acid；16:1, palmitoleic acid；16:0, Palmic acid；18:3, linolenic acid；18:2, linoleic acid；18:1, oleic acid；18:0,
Stearic acid；19:0, nonadecylic acid；20:5, eicosapentaenoic acid；20:4, arachidonic acid；20:1, eicosenoic acid；20:0,
Arachidic acid；22:6, docosahexenoic acid；IS, internal standard: deuterated hexadecanoic acid (FA16:0-d4).
In following embodiment, mass spectral analysis condition is the 4000Q-Trap mass spectrum inspection of Applied Biosystems company of the U.S.
Survey device.
In following embodiment, the establishment step of standard curve is as follows:
1) fatty acid standards is made into isopropanol respectively the stock solution of 1mg/mL, is then diluted to respectively with acetonitrile
Concentration is 0.5nmol/L, 1nmol/L, 2nmol/L, 20nmol/L, 50nmol/L, 100nmol/L, 150nmol/L,
200nmol/L Fatty acid standards liquid；
2) take 50 μ L Fatty acid standards liquid respectively in the acetonitrile of 810 μ L, each add 10 μ L1 μm ol/L internal standards d4-16:0
After vortex 10s mixing, add the 2-chloro-1-methyl pyridinium iodide (CMPI) and 30 μ L 20 μ of 20 μ L20 μm ol/mL
Mol/mL triethylamine (TEA), vortex 60s；Then derivative reagent N, the N-diethyl ethylenediamine of 50 μ L20 μm ol/mL is added,
40 DEG C of ultrasonic 5min, derivative reaction completes；
3) by step 2) solution nitrogen after gained derivative reaction dries up, then redissolves with the chloroform of 1mL, vortex
After 30s, adding volume ratio is the formic acid of 10:90:20: water: chloroformic solution 1mL, vortex 2min, abandons upper strata solvent；Repeat this behaviour
Make 2 times, then dry up with nitrogen, and redissolve by the trifluoroacetic acid aqueous solution of 1mL, be then passed through the organic facies membrane filtration of 2 μm, marked
The sample introduction solution of quasi-sample；
4) by step 3) the sample introduction solution of gained standard sample carries out mass spectral analysis, gathers the spectrum of free-fat acid derivative
Figure and spectral peak data (see Fig. 1), in standard solution, fatty acid and interior target concentration proportion are for abscissa x, derivative of fatty acid
It is vertical coordinate y with the quasi-molecular ion peak intensity rate of internal standard derivant, draws standard curve (being shown in Table 1).
Fig. 1 be 15 kinds of fatty acid standards (10:0,12:0,14:0,15:0,16:1,16:0,18:3,18:2,18:1,
18:0,20:5,20:4,20:1,20:0,22:6) after derivative, carry out mass spectral analysis, carry out in the positive-ion mode in 73Da
Property lose (+NLS73Da) mass spectrum of scanning.
Table 1 is the standard curve of 16 kinds of free fatties, wherein with free fatty and internal standard concentration proportion as abscissa,
Free-fat acid derivative and internal standard derivative peak intensity rate are vertical coordinate.
Table 1
5) method veracity and precision: with Semen Maydis oil as representative, adds basic, normal, high concentration in sample diluting liquid
Fatty acid hybrid standard product solution, 3 samples of the parallel preparation of each concentration, characterize accurately with the response rate and relative standard deviation
Degree, the evaluation of withinday precision and day to day precision is to prepare 3 samples within 3 working days respectively, repeats sample introduction 3 times, meter
Calculate its relative standard deviation value.The computing formula of free-fat acid recovering rate is, the response rate=(sample surveyed after adding standard substance
Middle FFA content-be not added with FFA content in the actual sample that standard substance are surveyed)/actual the amount added, from table 2, testing sample
The response rate 85.3～117.6%, method repeatability in tolerance interval (RSD < 10%).
Table 2
Embodiment 1
In a kind of olive oil based on Derivative, the mass spectrometric analysis method of free fatty, comprises the steps:
1) weigh 2mg olive oil normal hexane and be diluted to 0.2mg/ml, as testing sample；
Take 60 μ L testing samples and add 830 μ L dilution in acetonitrile, be subsequently adding 10 μ L1 μm ol/L internal standard FA16:0-d4 vortexs
After 10s mixing, add 2-chloro-1-methyl pyridinium iodide (CMPI) and 30 μ L 20 μm ol/mL tri-of 20 μ L20 μm ol/mL
Ethamine (TEA), vortex 60s；Then the derivative reagent N, N-diethyl ethylenediamine (DEEA) of 50 μ L20 μm ol/mL are added, 40
DEG C ultrasonic 5min, derivative reaction completes；
Solution nitrogen after gained derivative reaction dries up, and then redissolves with the chloroform of 1mL, after vortex 30s, adds body
Long-pending than the formic acid for 10:90:20: water: chloroformic solution 1mL, vortex 2min, abandon upper strata solvent；Repeat this operation 2 times, then use nitrogen
Air-blowing is done, and redissolves by the trifluoroacetic acid aqueous solution of 1mL, is then passed through the organic facies membrane filtration of 2 μm, obtains the sample introduction of testing sample
Solution；
2) by step 1) the sample introduction solution of gained testing sample carries out mass spectral analysis, gathers the spectrum of free-fat acid derivative
Figure and spectral peak data, as shown in Figure 2；
Wherein, the condition of mass spectral analysis is: entry needle pump sample introduction, and sample introduction flow velocity is 20 μ L/min, carries out mass spectral analysis, its
Mass spectral analysis condition is Applied Biosystems company of U.S. 4000Q-Trap mass detector.Electron spray ionisation source
(Electrospray Ionization, ESI): positive ion mode；Scanning of the mass spectrum pattern: 73Da neutral loss scan (73Da
neutral lossscan)；Ion source gas 1 (Ion Source Gas 1, GS1): 12kPa；Impact energy (collision
Energy, CE): 32eV；Remove a bunch voltage (declustering potential, DP): 75eV；Entrance potential (Entrance
Potential, EP): 5V；Collision cell output voltage (Collision Cell Exit Potential, CXP): 10V；Quality model
Enclose: 210-550m/z
3) qualitative analysis: according to step 2) mass-to-charge ratio in gained spectrogram, determine the standard of corresponding free-fat acid derivative
Molecular ion peak, thus the free fatty in testing sample is carried out qualitative analysis；According to mass spectrum 2a, Fructus Canarii albi can be obtained
Oil is respectively as follows: 14:0,16:0,18:3,18:2,18:1,18:0 and 20:0 containing 8 kinds of free fatties；
4) quantitative analysis: by step 2) quasi-molecular ion of free derivative of fatty acid and internal standard derivant in gained spectrogram
Peak intensity ratio 1.401 (14:0), 1.577 (16:0), 0.012 (18:3), 0.168 (18:2), 1.622 (18:1), 1.206
(18:0) and 0.2156 (20:0), combined standard curve (table 1), the free fatty in olive oil testing sample is carried out fixed
Component analysis, obtains the content of free fatty as shown in Figure 2 b, be respectively as follows: 424.94 μ g/g (14:0), 536.70 μ g/g (16:
0), 37.63 μ g/g (18:3), 157.64 μ g/g (18:2), 1545.95 μ g/g (18:1), 562.14 μ g/g (18:0) and
11.67μg/g(20:0)。
Embodiment 2
The mass spectrometric analysis method of free fatty in a kind of Semen Lini oil based on Derivative, with embodiment 1 not
It is with part: the olive oil testing sample in embodiment 1 replaces with Semen Lini oil testing sample.
Fig. 3 a and Fig. 3 b is the mass spectrum of free derivative of fatty acid in Semen Lini oil testing sample and free fatty contains
Amount.According to mass spectrum 3a, it is known that containing 8 kinds of free fatties in Semen Lini oil testing sample, respectively 14:0,16:1,
16:0,18:3,18:2,18:1,18:0 and 20:1；Free derivative of fatty acid and internal standard in gained Semen Lini oil testing sample
The quasi-molecular ion peak intensity rate of derivant be respectively as follows: 0.200 (14:0), 0.006 (16:0), 0.122 (18:3), 0.116
(18:2), 0.199 (18:1), 0.681 (18:0) and 0.003 (20:0), combined standard curve (table 1), Semen Lini oil is treated
In test sample product, free fatty carries out quantitative analysis, obtains the content of free fatty such as Fig. 3 b institute in Semen Lini oil testing sample
Show, be respectively as follows: 112.14 μ g/g (14:0), 169.42 μ g/g (16:1), 292.42 μ g/g (16:0), 593.25 μ g/g (18:
3), 174.50 μ g/g (18:2), 244.89 μ g/g (18:1), 504.76 μ g/g (18:0) and 62.53 μ g/g (20:1).
Embodiment 3
In a kind of perilla oil based on Derivative, the mass spectrometric analysis method of free fatty, different from embodiment 1
Part is: the olive oil testing sample in embodiment 1 replaces with perilla oil testing sample.
Fig. 4 a and Fig. 4 b is mass spectrum and the free fatty acid content of free derivative of fatty acid in perilla oil testing sample.
According to mass spectrum 4a, it is known that containing 7 kinds of free fatties in perilla oil testing sample, respectively 14:0,16:0,18:3,
18:2,18:1,18:0 and 20:0；Free derivative of fatty acid and the standard of internal standard derivant in gained Semen Lini oil testing sample
Molecular ion peak intensity rate be respectively as follows: 1.151 (14:0), 1.356 (16:0), 0.284 (18:3), 0.129 (18:2),
0.106 (18:1), 0.964 (18:0) and 0.015 (20:0), combined standard curve (table 1), to perilla oil testing sample middle reaches
Carry out quantitative analysis from fatty acid, obtain the content of free fatty in perilla oil testing sample and as shown in Figure 4 b, be respectively as follows:
422.05μg/g(14:0)、457.73μg/g(16:0)、689.84μg/g(18:3)、120.83μg/g(18:2)、34.38μg/g
(18:1), 435.69 μ g/g (18:0) and 8.96 μ g/g (20:0).
Embodiment 4
In a kind of Oleum sesami based on Derivative, the mass spectrometric analysis method of free fatty, different from embodiment 1
Part is: the olive oil testing sample in embodiment 1 replaces with Oleum sesami testing sample.
Fig. 5 a and Fig. 5 b is mass spectrum and the free fatty acid content of free derivative of fatty acid in Oleum sesami testing sample.
According to mass spectrum 5a, it is known that containing 7 kinds of free fatties in Oleum sesami testing sample, respectively 14:0,16:0,18:3,
18:2,18:1,18:0 and 20:0.In gained Oleum sesami testing sample, free derivative of fatty acid divides with the standard of internal standard derivant
Daughter ion peak intensity ratio be respectively as follows: 1.327 (14:0), 1.442 (16:0), 0.013 (18:3), 0.786 (18:2), 1.435
(18:1), 1.358 (18:0) and 0.049 (20:0), combined standard curve (table 1), to fat free in Oleum sesami testing sample
Fat acid carries out quantitative analysis, obtains the content of free fatty in Oleum sesami testing sample and as shown in Figure 5 b, is respectively as follows: 479.67
μg/g(14:0)、527.95μg/g(16:0)、34.20μg/g(18:3)、1382.37μg/g(18:2)、1229.63μg/g(18:
1), 641.49 μ g/g (18:0) and 64.05 μ g/g (20:0).
Embodiment 5
In a kind of Semen Maydis oil based on Derivative, the mass spectrometric analysis method of free fatty, different from embodiment 1
Part is: the olive oil testing sample in embodiment 1 replaces with Semen Maydis oil testing sample.
Fig. 6 a and Fig. 6 b is mass spectrum and the free fatty acid content of free derivative of fatty acid in Semen Maydis oil testing sample.
According to mass spectrum 6a, it is known that containing 5 kinds of free fatties in Semen Maydis oil testing sample, respectively 14:0,16:0,18:3,
18:2 and 18:0；In gained Semen Maydis oil testing sample, free derivative of fatty acid is strong with the quasi-molecular ion peak of internal standard derivant
Degree ratio is respectively as follows: 0.848 (14:0), 0.622 (16:0), 0.005 (18:3), 0.059 (18:2) and 0.292 (18:0),
Combined standard curve (table 1), carries out quantitative analysis to free fatty in Semen Maydis oil testing sample, obtains Semen Maydis oil testing sample
The content of middle free fatty as shown in Figure 6 b, is respectively as follows: 236.04 μ g/g (14:0), 146.06 μ g/g (16:0), 15.10 μ
G/g (18:3), 65.93 μ g/g (18:2) and 124.89 μ g/g (18:0).
Embodiment 6
The mass spectrometric analysis method of free fatty in a kind of Oleum Brassicae campestris sample based on Derivative, with embodiment 1
Difference is: the olive oil testing sample in embodiment 1 replaces with Oleum Brassicae campestris testing sample.
Fig. 7 a and Fig. 7 b is mass spectrum and the free fatty acid content of free derivative of fatty acid in Oleum Brassicae campestris testing sample.
According to mass spectrum 7a, it is known that containing 7 kinds of free fatties in Oleum Brassicae campestris testing sample, respectively 14:0,16:0,18:3,
18:2,18:1,18:0 and 20:1；In gained Oleum Brassicae campestris testing sample, free derivative of fatty acid divides with the standard of internal standard derivant
Daughter ion peak intensity ratio be respectively as follows: 1.046 (14:0), 1.086 (16:0), 0.046 (18:3), 0.162 (18:2), 0.528
(18:1), 1.061 (18:0) and 0.018 (20:1), combined standard curve (table 1), to fat free in Oleum Brassicae campestris testing sample
Fat acid carries out quantitative analysis, obtains the content of free fatty in Oleum Brassicae campestris testing sample and as shown in Figure 7b, is respectively as follows: 354.80
μg/g(14:0)、335.75μg/g(16:0)、115.57μg/g(18:3)、118.20μg/g(18:2)、383.82μg/g(18:
1), 486.17 μ g/g (18:0) and 114.91 μ g/g (20:1).
Embodiment 7
The mass spectrometric analysis method of free fatty in a kind of fish oil based on Derivative, different from embodiment 1 it
Place is: the olive oil testing sample in embodiment 1 replaces with fish oil testing sample.
Fig. 8 a and Fig. 8 b is mass spectrum and the free fatty acid content of free derivative of fatty acid in fish oil testing sample.Root
According to mass spectrum 8a, it is known that containing 12 kinds of free fatties in fish oil testing sample, be respectively as follows: 14:0,16:1,16:0,18:
3,18:2,18:1,18:0,20:5,20:4,20:1,20:0 and 22:6；The free fatty of gained fish oil testing sample derives
The quasi-molecular ion peak intensity rate of thing and internal standard derivant be respectively as follows: 0.661 (14:0), 0.0903 (16:1), 1.247 (16:
0)、0.029(18:3)、0.242(18:2)、0.269(18:1)、1.097(18:0)、0.124(20:5)、0.0182(20:4)、
0.0218 (20:1), 0.0249 (20:0) and 0.0218 (22:6), combined standard curve (table 1), in fish oil testing sample
Free fatty carries out quantitative analysis, obtains the content of free fatty in fish oil testing sample and as shown in Figure 8 b, is respectively as follows:
206.45μg/g(14:0)、28.58μg/g(16:1)、482.23μg/g(16:0)、88.58μg/g(18:3)、276.23μg/g
(18:2)、136.66μg/g(18:1)、593.43μg/g(18:0)、357.76μg/g(20:5)、116.12μg/g(20:4)、
156.38 μ g/g (20:1), 30.61 μ g/g (20:0) and 116.52 μ g/g (22:6).
Embodiment 8
The mass spectrometric analysis method of free fatty in a kind of Adeps Sus domestica based on Derivative, different from embodiment 1 it
Place is: the olive oil testing sample in embodiment 1 replaces with Adeps Sus domestica testing sample.
Fig. 9 a and Fig. 9 b is mass spectrum and the free fatty acid content of free derivative of fatty acid in Adeps Sus domestica testing sample.Root
According to mass spectrum 9a, it is known that containing 9 kinds of free fatties in Adeps Sus domestica testing sample, respectively 14:0,16:1,16:0,18:3,
18:2,18:1,18:0,20:1 and 20:0；The free-fat acid derivative of gained Adeps Sus domestica testing sample and internal standard derivant
Quasi-molecular ion peak intensity rate be respectively as follows: 0.319 (14:0), 0.059 (16:1), 0.957 (16:0), 0.0209 (18:3),
0.457 (18:2), 1.200 (18:1), 0.822 (18:0), 0.0366 (20:1) and 0.0191 (20:0), combined standard curve
(table 1), carries out quantitative analysis to free fatty in Adeps Sus domestica testing sample, obtains containing of free fatty in Adeps Sus domestica testing sample
Amount as shown in figure 9b, is respectively as follows: 54.25 μ g/g (14:0), 14.54 μ g/g (16:1), 282.89 μ g/g (16:0), 65.58 μ g/
g(18:3)、428.82μg/g(18:2)、1086.41μg/g(18:1)、384.36μg/g(18:0)、191.56μg/g(20:1)
And 16.06 μ g/g (20:0).
In sum, the method for the present invention is simple to operate, and edible oil sample to be measured carries out derivative reaction after directly diluting,
The product obtained, without carrying out chromatographic column separation, is directly entered mass spectrum, uses neutral loss scan in the positive-ion mode
Being analyzed, method is simple and efficient, it is possible to realize the selectivity efficient, high of free fatty in edible oil, high-sensitive qualitative
Quantitative analysis.
The above is only the preferred embodiment of the present invention, it is noted that come for those of ordinary skill in the art
Saying, without departing from the concept of the premise of the invention, it is also possible to make some modifications and variations, these broadly fall into the present invention's
Protection domain.
Claims (10)
1. the mass spectrometric analysis method of free fatty in an edible oil based on Derivative, it is characterised in that include as follows
Step:
1) by edible oil sample solvent dilution to be measured, after adding internal standard, reaction is performed the derivatization, the trip in edible oil after reaction
It is positively charged free-fat acid derivative from convert fatty acids, obtains the sample introduction solution of testing sample；
2) by step 1) the sample introduction solution of gained testing sample carries out mass spectral analysis, gather free-fat acid derivative spectrogram and
Spectral peak data；
3) qualitative analysis: according to step 2) mass-to-charge ratio in gained spectrogram, determine the quasi-molecule of corresponding free-fat acid derivative
Quasi-molecular ions, thus the free fatty in testing sample is carried out qualitative analysis；
4) quantitative analysis: fatty acid standards solvent dilution is become the standard solution of a series of concentration, after being separately added into internal standard,
With step 1) identical under conditions of perform the derivatization reaction, after reaction, free fatty is converted into positively charged free-fat
Acid derivative, the sample introduction solution got standard samples；
5) a, by step 4) the sample introduction solution of gained standard sample carries out mass spectral analysis, gathers the spectrogram of free-fat acid derivative
With spectral peak data, in standard solution, free fatty and interior target concentration proportion are as abscissa, free-fat acid derivative with
The quasi-molecular ion peak intensity rate of internal standard derivant is vertical coordinate, draws standard curve；B, by step 2) gained spectrogram middle reaches
From the quasi-molecular ion peak intensity rate combined standard curve of derivative of fatty acid Yu internal standard derivant, to edible oil sample to be measured
In free fatty carry out quantitative analysis.
The mass spectral analysis side of free fatty in a kind of edible oil based on Derivative the most according to claim 1
Method, it is characterised in that described derivative reagent is that an amino (-NH is contained in one end2), the other end contains the chemical combination of a tertiary amine groups
Thing, formula is expressed as: NH2-(CH2)n-NR2, wherein, n span is 2～4, and R group is the alkyl that carbon number is less than 2.
The mass spectral analysis side of free fatty in a kind of edible oil based on Derivative the most according to claim 1
Method, it is characterised in that described derivative reagent selects N, N-diethyl ethylenediamine.
The mass spectral analysis side of free fatty in a kind of edible oil based on Derivative the most according to claim 1
Method, it is characterised in that the condition of described derivative reaction is: addition internal standard, catalyst after edible oil sample solvent dilution are mixed
Even, it is subsequently adding derivative reagent, reaction temperature is 38～42 DEG C, and the response time is 2～10min.
The mass spectral analysis side of free fatty in a kind of edible oil based on Derivative the most according to claim 1
Method, it is characterised in that in described derivative reaction, with deuterated hexadecanoic acid as internal standard, with 2-chloro-1-methyl pyridinium iodide
It is catalyst with triethylamine, with N, N-diethyl ethylenediamine for derivative reagent.
The mass spectral analysis side of free fatty in a kind of edible oil based on Derivative the most according to claim 5
Method, it is characterised in that in derivative reaction system, the concentration of fatty acid is 0.5～200nmol/L, interior target concentration be 5～
15nmol/L, the concentration of catalyst of triethylamine is 0.5～0.7 μm ol/mL, catalyst 2-chloro-1-methyl pyridinium iodide
Concentration is 0.1～0.5 μm ol/mL, and the concentration of derivative reagent N, N-diethyl ethylenediamine is 0.6～1.2 μm ol/mL.
The mass spectral analysis side of free fatty in a kind of edible oil based on Derivative the most according to claim 5
Method, it is characterised in that step 1) and step 4) gained sample introduction solution process is dry, redissolve, carry out mass spectral analysis the most again.
The mass spectral analysis side of free fatty in a kind of edible oil based on Derivative the most according to claim 1
Method, it is characterised in that the condition of described mass spectral analysis is: entry needle pump sample introduction, sample introduction flow velocity is 10～30 μ L/min；Electron spray
Ionization source: positive ion mode；Scanning of the mass spectrum pattern: 73Da neutral loss scan；Ion source gas 1:12kPa；Impact energy: 30～
35eV；Remove a bunch voltage: 70～80eV；Entrance potential: 5～10V；Collision cell output voltage: 5～10V；Mass range: 200～
550m/z。
The mass spectral analysis side of free fatty in a kind of edible oil based on Derivative the most according to claim 1
Method, it is characterised in that described step 4) Plays solution is the mixed solution of one or more fatty acids, and described standard solution
The concentration range of middle fatty acid is all 0.5～200nmol/L.
The mass spectral analysis side of free fatty in a kind of edible oil based on Derivative the most according to claim 1
Method, it is characterised in that described edible oil sample to be measured mainly include Oleum Brassicae campestris, Oleum sesami, Semen Maydis oil, Semen Lini oil, olive oil,
Perilla oil, Adeps Sus domestica, fish oil.
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