CN102128875A - Direct chemical ionization mass spectrometry detection method for illegal cooking oil - Google Patents
Direct chemical ionization mass spectrometry detection method for illegal cooking oil Download PDFInfo
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- CN102128875A CN102128875A CN201010598783XA CN201010598783A CN102128875A CN 102128875 A CN102128875 A CN 102128875A CN 201010598783X A CN201010598783X A CN 201010598783XA CN 201010598783 A CN201010598783 A CN 201010598783A CN 102128875 A CN102128875 A CN 102128875A
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Abstract
The invention discloses a direct chemical ionization mass spectrometry detection method for illegal cooking oil, which is characterized by comprising: (1) setting a linear trap quadrupole mass spectrometry (LTQ-MS) in an anionic or cationic detection mode, regulating a spectrometric detection scanning range, an ionization voltage and a capillary temperature, and setting the parameters of a desorption atmospheric chemical ionization (DAPCI) source; and (2) directly dripping an oil sample on a glass slide, uniformly coating, processing all spectral data into a matrix X by using a mass to charge ratio as an independent variable and the absolute abundance of a mass spectrum peak as a dependent variable, importing the matrix X into data statistic analysis software, directly performing principal component analysis (PCA) computation, and inputting the result of the computation into SIGMAPLOT for graphic display. In the invention, the method which can quickly detect and identify illegal cooking oil without pretreating a sample to be detected overcomes the drawbacks of complex and time-consuming detection operation steps and the like.
Description
Technical field
The invention belongs to the detection technique field, particularly the detection method of waste oil.
Background technology
Waste oil claims swill oil, hogwash fat again, and the source mainly contains: the oil that the food and drink waste grease extracts through simple processing; After the frying oil access times surpass regulation, the direct or reusable again oil of interpolation part green oil; The oil of processing outputs such as pork inferior, pluck and skin.Heavy metal in the waste oil and toxin severe overweight, long-term absorption can make cell function depletion, brings out multiple disease, even carcinogenic.The edible oil that illegal speculator will mix waste oil is used in the food, is difficult to differentiate from outward appearance and sense organ, and society and food security are caused very large harm.
At present, Chang Yong detection method has high performance liquid chromatography, thin-layered chromatography, conductimetric method, gas chromatography mass spectrometry method and inductively coupled plasma mass spectrometry etc.These methods generally all exist complex operation step, defective such as time-consuming, bring many inconvenience for the detection of waste oil.
Summary of the invention
Purpose of the present invention provides a kind of detection method of new waste oil, need not waste oil to be carried out the method for fast detecting and discriminating under the condition of sample pretreatment.The inventive method can be carried out fast detecting to the edible oil of waste oil and doping waste oil.
Detection method of the present invention is the analyzing and testing of carrying out the waste oil sample by the LTQ-XL molded lines ion trap mass spectrometer of routine and surface desorption atmospheric chemical ionization (DAPCI) source.
Specifically, the present invention can be divided into negative ion detecting pattern and positive ion detecting pattern.
The technical scheme of described negative ion detecting pattern is as follows:
(1) LTQ-MS is set to the negative ion detecting pattern, and the Mass Spectrometer Method sweep limit is m/z 50～400; Ionization voltage 3.6kV; The ion transfer tube temperature is 100 ℃; Each parameter of DAPCI source: the x axle is 9.9 cm, and the y axle is-2 cm, and the z axle is-5 cm, and spray point and horizontal plane angle are 43 °, and other parameter adopts LTQ-MS system Automatic Optimal;
(2) the oils sample is directly dropped on the microslide, paint 0.5-2.0 cm equably
2, thickness directly carries out mass spectrophotometry after less than 1 mm.With mass-to-charge ratio (mass range
M/z50～400) be independent variable, the absolute abundance of mass spectra peak is a dependent variable, and whole spectral datas are processed into a matrix
X, each row is represented a sample, and each classifies 1 mass-to-charge ratio value variable as.Matrix
XImport to data statistic analysis software, directly carry out PCA and calculate, result of calculation is input to mapping demonstration among the SIGMAPLOT (version 11.0).
The technical scheme of described positive ion detecting pattern is as follows:
(1) LTQ-MS is set to the positive ion detecting pattern, and the Mass Spectrometer Method sweep limit is m/z 50～400; Ionization voltage 2.7kV; The ion transfer tube temperature is 100 ℃; Each parameter of DAPCI source: the x axle is 5 cm, and the y axle is 0, and the z axle is-1cm that ion source discharge pin and horizontal plane angle are 45 °, other parameter employing LTQ-MS system Automatic Optimal;
(2) the oils sample is directly dropped on the microslide, paint 0.5-2.0 cm equably
2, thickness directly carries out mass spectrophotometry after less than 1 mm.With mass-to-charge ratio (mass range
M/z50～400) be independent variable, the absolute abundance of mass spectra peak is a dependent variable, and whole spectral datas are processed into a matrix
X, each row is represented a sample, and each classifies 1 mass-to-charge ratio value variable as.Matrix
XImport to data statistic analysis software, directly carry out PCA and calculate, result of calculation is input to mapping demonstration among the SIGMAPLOT (version 11.0).
The present invention need not the testing sample pre-service, can carry out the method for fast detecting and discriminating to waste oil, has improved detecting operation complex steps in the prior art, defective such as time-consuming.The inventive method can be carried out fast detecting to the edible oil of waste oil and doping waste oil.
Description of drawings
Fig. 1 among the figure, (a) is tea oil for the DAPCI fingerprint spectrogram of waste oil under the negative ion detecting pattern of the present invention and tea oil, (b) is waste oil.
Fig. 2 among the figure, (a) is tea oil for the DAPCI fingerprint spectrogram of waste oil under the positive ion detecting pattern of the present invention and tea oil, (b) is waste oil.
Fig. 3 is a 2-amino-1 of the present invention, the MS of ammediol m/z 90
2Spectrogram.
Fig. 4 is the MS of oleic acid m/z 281 of the present invention
nSpectrogram.
Fig. 5 is the three-dimensional score result of the DAPCI-MS data PCA of waste oil and tea oil under the use negative ion detection of the present invention, among the figure, (a): m/z 50-400; (b): m/z 77,80,90,123,151 and 179.
Fig. 6 is the three-dimensional score result of the DAPCI-MS data PCA of waste oil and tea oil under the use positive ion detection of the present invention, among the figure, (a): m/z 50-400; (b): m/z54,78,91,153,283,304,332.
Embodiment
The present invention is described in further detail below in conjunction with accompanying drawing, but the present invention not only is confined to following examples.
The mass spectrometer that embodiment of the present invention uses is the Xcalibur data handling system of U.S. Finnigan company as the LTQ-XL molded lines ion trap mass spectrometer of U.S. Finnigan company, data handling system.
Under the experiment parameter of optimizing, be recorded in the fingerprint spectrogram of waste oil and tea oil under the negative ion mode, as shown in Figure 1.From Fig. 1 as seen, the signal with remarkable intensity mainly concentrates on mass range m/z 50～200, and after signal intensity amplified certain multiple, and m/z sees less quasi-molecular ions more than 200.Because the oils sample has higher viscosity, the higher molecule of quality is difficult for by desorb, may be owing to the high concentration and relative high gas phase acidity of determinand and have the determinand of remarkable high signal intensity under negative ion mode.The existing something in common of DAPCI-MS fingerprint spectrogram of waste oil and tea oil has evident difference again.Something in common is that 2 kinds of oil all have signals such as tangible m/z 77,80,90,123,151 and 179, the power that difference is 2 kinds of oily shared signals is difference to some extent, m/z 90,123,179 signals are stronger in the waste oil, and in the oil tea oil m/z 90,123,179 signals relatively a little less than.In addition, the quantity of the more weak m/z of the signal of tea oil is obviously more than waste oil.
Under positive ion mode, under optimal experimental conditions, write down the fingerprint spectrogram of waste oil and tea oil, as shown in Figure 2.As seen from the figure, the DAPCI-MS fingerprint spectrogram something in common of waste oil and tea oil is more, and difference is less.This explanation under positive ion mode in 2 kinds of samples easily protonated material more similar, cause their DAPCI-MS fingerprint spectrogram more similar.
Under the negative ion detecting pattern, signals such as tangible m/z 77,80,90,123,151,179 and 281 are all arranged in the one-level mass spectrogram of waste oil and tea oil, select m/z 90,281 materials wherein to carry out the analysis of collision induced dissociation (CID) tandem mass spectrum, other do not give unnecessary details.At first select m/z 90 to be parent ion, collision time is 30 ms, and collision energy is 35%, and the main fragmention in the second order ms that is obtained is a m/z 60(base peak), 72, as shown in Figure 3, be respectively parent ion and lose CH
2O, H
2O or NH
3Due to, therefore preliminary definite, m/z 90 may be C
3H
9NO
2Molecular anion.Select m/z 281 to be parent ion then, collision time is 30 ms, and collision energy is 33%, and as shown in Figure 4, the main fragmention in the second order ms that is obtained is a m/z 237(base peak), 265,263,151 etc., be respectively parent ion and lose CO
2, CH
4, H
2O and C
6H
13Due to the COOH; Continue to select m/z 237 to carry out CID and analyze, main fragmention is a m/z 209(base peak in three grades of mass spectrums that obtained), 195,167 etc., be m/z 237 and lose CH
2CH
2, C
3H
6And C
5H
10The ion that the back obtains; Select m/z 209 to carry out CID again and analyze, main fragmention is the m/z193(base peak in the level Four mass spectrum that is obtained), 165 and 123 etc., ion m/z 209 loses CH after the CID cracking
4Generate fragmention m/z 193, can also lose C simultaneously
3H
8Obtain ion m/z 165 and lose C
6H
14Obtain m/z 123.Therefore preliminary definite, m/z 281 is oleic acid C
18H
34O
2The deprotonation negative ion.The feature fragment basically identical of the oleic acid of these characteristic ions and standard items shows that DAPCI can carry out qualitative detection to oils sample chemical composition.But the result that the oleic acid characteristic ion that experiment obtains and other method obtain is not quite identical, for example, uses electron impact ionization (EI) source, ionizing energy is 70 eV, 230 ℃ of interface temperatures, and the main ms fragment that obtains oleic acid m/z 282 is m/z 263,220,192,164,150,123,95,81, the 67(base peak), 55,41, the main ms fragment of the oleic acid that obtains with this paper is identical is m/ z 263 and 123, and other feature fragment is all inequality; Utilization electron spray ionisation (ESI) source, spray voltage-4kV, 300 ℃ of capillary temperatures, the principal character ion of oleic acid m/z 281 is m/z 141,127,113,111,97,95,83,71; Utilize electron spray desorption ionization (DESI) source, spray voltage-3.5～-5.0kV, capillary temperature 200-300 ℃, the main ms fragment of oleic acid m/z 281 is m/z 263,125,111,83, the main ms fragment of the oleic acid that obtains with this paper is identical is m/z 263, and other feature fragment is all inequality.Cause the reason of this phenomenon chemistry may be for different technologies ionization the time different, add the difference of ionization conditions and mass analyzer aspect, so that the form and the energy of the determinand ion that obtains may there are differences all with physical process.
Under negative ion mode, shown in Fig. 5 a, select first three major component to be used to make up model, be used for the PC1(eigenvalue of explanatory variable, 186.70), the PC2(eigenvalue, 62.79) and PC3(eigenvalue, 49.09) percentage be respectively 33.9%, 11.4% and 8.9%.Wherein, PC1 has described the direction of maximum variable in the data acquisition, and PC1 has best separating capacity for the difference between the sample, because it has correctly represented the difference of kind.Shown in Fig. 5 a, the difference of the PCA of variety classes oil is apparent.Strictly be distinguished from different types of sample,, and be distributed in identical zone from all data centralizations with a kind of oil because 2 kinds of oil bunch mutual distances are far away.PCA has confirmed that the purpose of distinguishing sample according to kind reaches.
Under the same conditions, shown in Fig. 5 b, utilize 2 kinds of oil all to have tangible m/z 77,80,90,123,151 and 179 signals to carry out PCA, select first three major component to be used to make up model, be used for the PC1(eigenvalue of explanatory variable, 2.41), the PC2(eigenvalue, 1.61) and PC3(eigenvalue, 0.84) percentage be respectively 40.2%, 26.9% and 13.9%.Therefore, these PC have represented 81.1% of approximately total variable.Wherein, PC1 has described the direction of maximum variable in the data acquisition, has best separating capacity for the difference between the sample.Shown in Fig. 5 b, the difference of the PCA of variety classes oil is apparent.Strictly be distinguished from different types of sample,, and be distributed in identical zone from all data centralizations with a kind of oil because 2 kinds of oil bunch mutual distances are far away.The raw data of this explanation DAPCI-MS gained PCA in addition helps to distinguish different types of oil, and the purpose of distinguishing the variety classes sample according to the DAPCI-MS method reaches.
Under the identical conditions, utilizing characteristic peak data such as m/z 50～400 and m/z 77,80,90,123,151,179 to carry out PCA respectively analyzes, the result is, the accumulation contribution rate of utilizing the three-dimensional score of characteristic peak gained PCA to represent first three major component has reached more than 80%.More can embody the difference between the sample.
Under positive ion mode, adopt same data processing method, utilize characteristic peak data such as m/z 50～400 and m/ z 54,78,91,153,283,304,332 to carry out PCA respectively and analyze.Shown in Fig. 6 a and 6b, more concentrated with a kind of all DATA DISTRIBUTION of oil, but the PCA of variety classes oil at certain region memory certain overlapping, the kind that two kinds of principal ingredients in the oil are described exists similar, and this feature that also shows PCA analysis result and dactylogram diagram data is consistent.
Simultaneously, experimental result also shows, under positive ion mode, also can carry out to a certain extent differentiation to two kinds of oil, but do not reach the more effective more obvious differentiation under negative ion mode, the reason that causes this situation may be that their easier deprotonations under negative ion mode form [M-H] owing to contain a large amount of acidic materials in the oils sample
-Molion, thereby reflect the chemical differences that exists in these samples better; Under positive ion mode, these acidic materials are difficult to obtain good signal, thereby are difficult to carry out in PCA result good differentiation.
In the LTQ mass spectrometer, for improving detection sensitivity and signal stabilization, it is 100 ms that setting is composed sweep time entirely, therefore, the minute of single sample is less than 1 s, so the surface desorption atmospheric chemical ionization mass spectroscopy is particularly suitable for batch samples is carried out fast detecting.The bigger problem of relative standard deviation (RSD) of representative component (as oleic acid) signal intensity in the sample when adopting auto injection then may overcome hand sampling.Experiment shows that the surface desorption atmospheric chemical ionization mass spectroscopy can be to 2-amino-1 in the oils sample, and ammediol, oleic acid etc. carries out fast qualitative analysis utilizing.
Claims (2)
1. the direct chemical ionization Mass Spectrometer Method method of a waste oil is characterized in that comprising the following step:
(1) LTQ-MS is set to the negative ion detecting pattern, and the Mass Spectrometer Method sweep limit is m/z 50～400; Ionization voltage 3.6kV; The ion transfer tube temperature is 100 ℃; Each parameter of DAPCI source: the x axle is 9.9 cm, and the y axle is-2 cm, and the z axle is-5 cm, and spray point and horizontal plane angle are 43 °, and other parameter adopts LTQ-MS system Automatic Optimal;
(2) the oils sample is directly dropped on the microslide, paint 0.5-2.0 cm equably
2, thickness directly carries out mass spectrophotometry after less than 1 mm, with mass-to-charge ratio (mass range
M/z50～400) be independent variable, the absolute abundance of mass spectra peak is a dependent variable, and whole spectral datas are processed into a matrix
X, each row is represented a sample, and each classifies 1 mass-to-charge ratio value variable as; Matrix
XImport to data statistic analysis software, directly carry out PCA and calculate, result of calculation is input to mapping demonstration among the SIGMAPLOT.
2. the direct chemical ionization Mass Spectrometer Method method of a waste oil is characterized in that comprising the following step:
(1) LTQ-MS is set to the positive ion detecting pattern, and the Mass Spectrometer Method sweep limit is m/z 50～400; Ionization voltage 2.7kV; The ion transfer tube temperature is 100 ℃; Each parameter of DAPCI source: the x axle is 5 cm, and the y axle is 0, and the z axle is-1cm that ion source discharge pin and horizontal plane angle are 45 °, other parameter employing LTQ-MS system Automatic Optimal;
(2) the oils sample is directly dropped on the microslide, paint 0.5-2.0 cm equably
2, thickness directly carries out mass spectrophotometry after less than 1 mm, with mass-to-charge ratio (mass range
M/z50～400) be independent variable, the absolute abundance of mass spectra peak is a dependent variable, and whole spectral datas are processed into a matrix
X, each row is represented a sample, and each classifies 1 mass-to-charge ratio value variable as; Matrix
XImport to data statistic analysis software, directly carry out PCA and calculate, result of calculation is input to mapping demonstration among the SIGMAPLOT.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102393426A (en) * | 2011-10-28 | 2012-03-28 | 李涛 | Identification method for illegal cooking oil |
| CN102507379A (en) * | 2011-11-16 | 2012-06-20 | 张峰 | Detection method for checking whether edible oil contains illegal cooking oil |
| CN102519918A (en) * | 2011-12-08 | 2012-06-27 | 大连理工大学 | Method for rapid detection of waste oil based on laser-induced breakdown spectroscopy |
| CN102998350A (en) * | 2012-12-10 | 2013-03-27 | 西南大学 | Method for distinguishing edible oil from swill-cooked dirty oil by electrochemical fingerprints |
| CN108776167A (en) * | 2018-06-12 | 2018-11-09 | 福建出入境检验检疫局检验检疫技术中心 | One vegetable oil discrimination method |
| CN108918648A (en) * | 2018-07-19 | 2018-11-30 | 香港浸会大学深圳研究院 | A method of identifying frying oil |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102393426A (en) * | 2011-10-28 | 2012-03-28 | 李涛 | Identification method for illegal cooking oil |
| CN102393426B (en) * | 2011-10-28 | 2014-08-20 | 李涛 | Identification method for illegal cooking oil |
| CN102507379A (en) * | 2011-11-16 | 2012-06-20 | 张峰 | Detection method for checking whether edible oil contains illegal cooking oil |
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| CN102998350A (en) * | 2012-12-10 | 2013-03-27 | 西南大学 | Method for distinguishing edible oil from swill-cooked dirty oil by electrochemical fingerprints |
| CN108776167A (en) * | 2018-06-12 | 2018-11-09 | 福建出入境检验检疫局检验检疫技术中心 | One vegetable oil discrimination method |
| CN108918648A (en) * | 2018-07-19 | 2018-11-30 | 香港浸会大学深圳研究院 | A method of identifying frying oil |
| CN108918648B (en) * | 2018-07-19 | 2020-08-11 | 香港浸会大学深圳研究院 | Method for identifying frying oil |
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