CN108535395B - method for simultaneously and rapidly measuring 32 free fatty acids in health-care wine - Google Patents

method for simultaneously and rapidly measuring 32 free fatty acids in health-care wine Download PDF

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CN108535395B
CN108535395B CN201810201947.7A CN201810201947A CN108535395B CN 108535395 B CN108535395 B CN 108535395B CN 201810201947 A CN201810201947 A CN 201810201947A CN 108535395 B CN108535395 B CN 108535395B
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sample
detected
free fatty
fatty acids
phase
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CN108535395A (en
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高家坤
王银辉
王银磊
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Anhui Gujing Distillery Co Ltd
Anhui Ruisiweier Technology Co Ltd
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Anhui Gujing Distillery Co Ltd
Anhui Ruisiweier Technology Co Ltd
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/88Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86

Abstract

The invention discloses a method for simultaneously and rapidly determining 32 free fatty acids in health-care wines by using UPLC-QTof, wherein a wine sample to be detected is subjected to pretreatment and then is detected by an ultra-high performance phase-locked chromatograph equipped with a QTof detector to obtain a chromatogram of a sample to be detected, the sample to be detected is subjected to qualitative analysis according to selected ions, and then the sample to be detected is subjected to quantitative analysis according to a standard curve of the 32 free fatty acids.

Description

method for simultaneously and rapidly measuring 32 free fatty acids in health-care wine
Technical Field
The invention relates to a method for simultaneously and rapidly measuring 32 free fatty acids in health-care wine by using UPC2-QTof, belonging to the technical field of detection and analysis.
Background
Free fatty acids and the fatty acids that make up complex lipids all play key roles in metabolism-as the main metabolic fuel (storing and transporting energy), essential components of all cell membranes and gene regulatory factors-furthermore, dietary lipids can provide polyunsaturated fatty acids that are precursors to powerful, locally acting metabolites (such as eicosanoids.) common fatty acids of animal and plant origin are even-numbered chains, each containing 16 to 24 carbon atoms and having 0 to 6 double bonds.
After separation, fatty acids can be analyzed by typical chromatographic methods, currently gas chromatography/mass spectrometry (GC/MS) and liquid chromatography-tandem mass spectrometry (LC/MS) are used, however, these methods have their respective disadvantages, for example, GC method requires derivatization of fatty acids for hydrolysis and conversion to methyl esters, which process is not only time consuming, but also risks of fatty acid rearrangement during derivatization, making it impossible to determine whether the formed esters are from FFA or intact complex lipids.
Disclosure of Invention
In order to avoid the defects of the prior art, the invention aims to provide methods for simultaneously and rapidly determining 32 free fatty acids in the health-care wine by using UPC2-QTof, wherein the 32 free fatty acids are butyric acid, caproic acid, caprylic acid, capric acid, deca alkanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, arachidic acid, behenic acid, sperm whale acid, palmitoleic acid, 10-heptadecenoic acid, gamma-linolenic acid, linoleic acid, oleic acid, elaidic acid, arachidonic acid, homologous gamma-linolenic acid, 11-14-17-eicosatrienoic acid, 11-14-eicosadienoic acid, 11-eicosenoic acid, docosahexaenoic acid, docosadienoic acid, erucic acid and nervonic acid.
The invention discloses a method for simultaneously and rapidly measuring 32 free fatty acids in health-care wine by using UPC2-QTof, which comprises the following steps:
step 1: pretreatment
Measuring 20-50 mL of a wine sample to be measured in a 50mL plastic centrifuge tube, removing ethanol by using a nitrogen blowing instrument, stopping nitrogen blowing when 1-2 mL of residual liquid remains, transferring the residual liquid after removing the ethanol into a 5mL volumetric flask, fixing the volume by using dichloromethane, and filtering by using a 0.22 mu m needle type filter to obtain a sample to be measured;
step 2: drawing of standard curve
Preparing 32 mixed standard solutions (FFA standard mixtures: various saturated FFA standards containing C8 to C24 with even numbers of carbon atoms are purchased from Sigma company; complex model mixtures of different FFA standards (GLC-85, FFA form) are purchased from Nu-Chek Prep) by chloroform to obtain 1mg/mL stock solutions, and then diluting the stock solutions by chloroform to obtain 0.1mg/mL working mixed solutions (the concentrations of 32 free fatty acids are all 0.1 mg/mL); diluting the obtained working mixed solution with chloroform to obtain mixed standard working solutions with different concentrations, detecting by using an ultra-high performance phase-combination chromatograph equipped with a QTof detector, performing linear regression on the corresponding mass concentration of the object to be detected by using the peak area of the object to be detected to obtain linear regression equations of 32 free fatty acids, wherein the curve corresponding to each linear regression equation is the standard curve of the corresponding free fatty acid;
and (3) in the step 2, the concentration of the mixed standard working solution is 5-1000 ng/mL, and at least 5 point values with different concentrations are obtained by dilution.
The detection parameters in step 2 are set as follows:
the detection conditions of the ultra-high efficiency phase-combination chromatograph are set as follows:
the chromatographic column is a 2.1x 150mm, 1.8 μm HSS C18SB chromatographic column;
the column temperature is 3-50 ℃;
the temperature of the sample chamber is 10-20 DEG C
Mobile phase: phase A is carbon dioxide, phase B is 0.1% formic acid solution of methanol;
the flow rate is 0.2-0.5 mL/min;
the elution mode is gradient elution; gradient elution parameters were set as: when 0min is reached, the volume fraction of the mobile phase B is 5-10%; from 0min to 5.0min, the volume fraction of the mobile phase B is increased from 5-10% to 20-25%; from 5.0min to 5.1min, the volume fraction of the mobile phase B is increased from 20-25% to 40-50%, and the volume fraction is kept for 6.0 min; and (3) reducing the volume fraction of the mobile phase B from 40-50% to 5-10% from 6.0min to 8.0min, and keeping the balance for 1 min.
The sample injection amount is 0.5-5 mu L;
the detection time is 3-8 min;
compensation liquid: methanol (containing 0.1% ammonia water) with the flow rate of 0.20-0.6 mL/min;
a flow divider: four-way (PEEK tubing of 1/16);
the detection conditions for MS were set as follows:
mass spectrometry: QTof
Ionization mode: ESI-
Capillary voltage: 1.0KV
Taper hole voltage: 30V
Source temperature: 100 deg.C
Desolventizing steam temperature: 500 deg.C
Flow rate of taper hole gas: 10L/h
Desolventizing steam flow rate: 600L/h
The collection range is as follows: 50-600m/Z
The neutral mass number and the ion mass number are shown in table 1 below:
table 1: the number of 32 free fatty acids and the corresponding retention time
And step 3: detection of a wine sample to be tested
Taking 1.0-2.0 mL of the sample to be detected obtained in the step 1, detecting according to the detection conditions in the step 2 to obtain a chromatogram of the sample to be detected, carrying out qualitative analysis on the sample to be detected according to the selected ions, and then carrying out quantitative analysis on the sample to be detected according to the standard curve of 32 free fatty acids.
For this study, five replicate injections of each health wine were collected in the MSE mode, which is unbiased Tof collection methods, where the mass spectrometer switched between low and high collision energies when alternating scans were performed.
The following sensitivity tests were performed on the method of the invention: the sensitivity test comprises the sensitivity of an instrument and the sensitivity of a method, the sensitivity of the instrument is represented by the detection limit of the instrument, and the minimum concentration of the free fatty acid mixed standard solution with the signal-to-noise ratio of more than or equal to 3 is taken as the detection limit of the instrument; the sensitivity of the method is expressed by the quantitative limit of the method, and the minimum concentration of the free fatty acid mixed standard solution with the signal-to-noise ratio of more than or equal to 9 is taken as the quantitative limit of the method. The resulting correlation data are shown in table 2 below.
The method comprises the following accuracy and reproducibility experiments, namely selecting wine samples which are pretreated to be used as blank samples and dividing the blank samples into 3 parts, adding mixed standard working solutions to perform a labeling recovery experiment respectively, calculating the recovery rate, selecting 1 wine sample to be treated by the same pretreatment method to perform experiments respectively, and judging the reproducibility of an analysis method by calculating the Relative Standard Deviation (RSD) range of the wine samples, wherein the accuracy of the method is expressed by the recovery rate, shown in a table 3, the reproducibility of the method is expressed by the Relative Standard Deviation (RSD), shown in a table 4, the recovery rate is 80-120%, and the RSD is less than 10%.
Table 3: experiment for standard recovery rate of 32 free fatty acids
Table 4: reproducibility test of 32 free fatty acids
The invention has the beneficial effects that:
1. the invention establishes methods for simultaneously and rapidly determining 32 free fatty acids in the health-care wine by using UPC2-QTof, can accurately perform qualitative and quantitative determination on the 32 free fatty acids in the health-care wine, and provides scientific basis for accurate determination and rapid detection of the free fatty acids in the wine.
2. The ultra-efficient synthetic phase chromatography tandem QTof mass spectrometry detector is simple, fast, accurate, reliable and good in repeatability.
3. The invention relates to a HSS C18SB synthetic phase special chromatographic column with the diameter of 2.1x 150mm and the diameter of 1.8 mu m and CO2And the selection of the methanol mobile phase achieves excellent separation effect on 32 free fatty acids in the wine.
4. The invention does not need derivatization, can realize simpler and faster sample preparation and avoid interference.
5. The organic solvent extract can be directly injected into the system, so that the time and cost of each analysis are saved
6. The invention can complete chromatographic separation within three minutes, and the speed is 10 times faster than that of GC/MS. And using less toxic, more economical CO2As a solvent. The higher speed can analyze the larger sample size efficiently, thereby improving the overall efficiency of the experiment.
7. The detection method is environment-friendly 'green' technology, the main mobile phase carbon dioxide adopted in analysis is from other industrially released recovered carbon dioxide, and the carbon dioxide used in the experiment can not generate new greenhouse gas any more.
8. The invention also has important characteristics, and can separate and detect lipid isomers.
9. The present invention can save costs by reducing the use of laboratory consumables.
Drawings
FIG. 1 is a chromatogram of a standard working solution of 32 free fatty acids.
Detailed Description
The invention is further illustrated in step with reference to specific examples.
This example measures 32 free fatty acids in a wine as follows:
1. pretreatment
Measuring 25mL of a wine sample to be measured in a 50mL plastic centrifuge tube, removing ethanol by using a nitrogen blowing instrument, stopping nitrogen blowing when 1-2 mL of residual liquid remains, transferring the residual liquid after removing the ethanol to a 5mL volumetric flask, fixing the volume by using dichloromethane, and filtering by using a 0.22 mu m needle type filter to obtain a sample to be measured;
2. detecting parameter settings
The detection conditions of the ultra-high efficiency phase-combination chromatograph are set as follows:
the chromatographic column is a 2.1x 150mm, 1.8 μm HSS C18SB chromatographic column;
the column temperature is 50 ℃;
the temperature of the sample chamber is 10 ℃;
mobile phase: phase A is carbon dioxide, phase B is 0.1% formic acid solution of methanol;
the flow rate is 0.23 mL/min;
the elution mode is gradient elution; the elution procedure was as follows: at 0min, the volume fraction of the mobile phase B is 5%; from 0min to 5.0min, the volume fraction of mobile phase B rose from 5% to 25%; from 5.0min to 5.1min, the volume fraction of mobile phase B increased from 25% to 50%, held to 6.0 min; and (3) reducing the volume fraction of the mobile phase B from 50% to 5% from 6.0min to 8.0min, and keeping the balance for 1 min. Specifically, the curve 6 in the apparatus used was selected for the profile of each step of the gradient elution.
The sample injection amount is 0.5 mu L;
the detection time is 8 min;
compensation liquid: methanol (containing 0.1% ammonia) at a flow rate of 0.20 mL/min;
a flow divider: four-way (PEEK tubing of 1/16);
the detection conditions for MS were set as follows:
mass spectrometry: QTof
Ionization mode: ESI-
Capillary voltage: 1.0KV
Taper hole voltage: 30V
Source temperature: 100 deg.C
Desolventizing steam temperature: 500 deg.C
Flow rate of taper hole gas: 10L/h
Desolventizing steam flow rate: 600L/h
The collection range is as follows: 50-600m/Z
The neutral mass number and the ion mass number are shown in Table 1 above.
3. Drawing of standard curve
Preparing 32 mixed standard solutions (FFA standard mixtures: various saturated FFA standards containing C8 to C24 with even numbers of carbon atoms are purchased from Sigma company; complex model mixtures of different FFA standards (GLC-85, FFA form) are purchased from Nu-Chek Prep) by chloroform to obtain 1mg/mL stock solutions, and then diluting the stock solutions by chloroform to obtain 0.1mg/mL working mixed solutions (the concentrations of 32 free fatty acids are all 0.1 mg/mL); diluting the obtained working mixed solution with chloroform to obtain mixed standard working solutions with different concentrations, detecting by using an ultra-high performance phase-combination chromatograph equipped with a QTof detector, performing linear regression on the corresponding mass concentration of the object to be detected by using the peak area of the object to be detected to obtain linear regression equations of 32 free fatty acids, wherein the curve corresponding to each linear regression equation is the standard curve of the corresponding free fatty acid;
the concentrations of the mixed standard working solution are respectively 5ng/ml, 50ng/ml, 200ng/ml, 500ng/ml and 1000 ng/ml.
The linear regression equation corresponding to the 32 free fatty acids and the correlation coefficient r2See table 2 below.
Table 2: linear regression equation, correlation coefficient, detection limit, and quantification limit of 32 kinds of free fatty acids
4. Detection of a wine sample to be tested
Taking 1.0-2.0 mL of the sample to be detected obtained in the step 1, detecting according to the detection conditions in the step 2 to obtain a chromatogram of the sample to be detected, carrying out qualitative analysis on the sample to be detected according to the selected ions, and then carrying out quantitative analysis on the sample to be detected according to the standard curve of 32 free fatty acids.
For this study, five replicate injections of each health wine were collected in the MSE mode, which is unbiased Tof collection methods, where the mass spectrometer switched between low and high collision energies when alternating scans were performed.
TABLE 5 comparison of the test data of the present method with the test data of the prior art method
As can be seen from the data in Table 5, compared with the existing method, the existing method needs 8 methods to completely detect 32 fatty acids, the detection limit is high, many trace components cannot be detected, the 32 fatty acids can be simultaneously detected by the method, the detection limit of the method is low, the content which cannot be detected by the existing method can be detected by the method, the content which is above the detection limit can be detected by two methods, the detection data by the two methods can be detected within a reasonable error range, and the detection data can fully indicate that the method is superior to the existing method, so that the 32 fatty acids in the health care wine can be accurately quantified.

Claims (3)

1, method for simultaneously and rapidly determining 32 free fatty acids in health wine by using UPC2-QTof, which is characterized by comprising the following steps:
step 1: pretreatment
Measuring 20-50 mL of a wine sample to be measured in a 50mL plastic centrifuge tube, removing ethanol by using a nitrogen blowing instrument, stopping nitrogen blowing when 1-2 mL of residual liquid remains, transferring the residual liquid after removing the ethanol into a 5mL volumetric flask, fixing the volume by using dichloromethane, and filtering by using a 0.22 mu m needle type filter to obtain a sample to be measured;
step 2: drawing of standard curve
Preparing 32 kinds of mixed standard solutions with chloroform respectively to obtain 1mg/mL stock solutions, and then diluting with chloroform to obtain 0.1mg/mL working mixed solution; diluting the obtained working mixed solution with chloroform to obtain mixed standard working solutions with different concentrations, detecting by using an ultra-high performance phase-combination chromatograph equipped with a QTof detector, performing linear regression on the corresponding mass concentration of the object to be detected by using the peak area of the object to be detected to obtain linear regression equations of 32 free fatty acids, wherein the curve corresponding to each linear regression equation is the standard curve of the corresponding free fatty acid;
and step 3: detection of a wine sample to be tested
Taking 1.0-2.0 mL of the sample to be detected obtained in the step (1), detecting according to the detection conditions of the step (2) to obtain a chromatogram of the sample to be detected, carrying out qualitative analysis on the sample to be detected according to the selected ions, and then carrying out quantitative analysis on the sample to be detected according to a standard curve of 32 free fatty acids;
in the step 2, the detection conditions of the ultra-high performance phase-matching chromatograph are set as follows:
the chromatographic column is a 2.1x 150mm, 1.8 μm HSS C18SB chromatographic column;
the column temperature is 3-50 ℃;
the temperature of the sample chamber is 10-20 DEG C
Mobile phase: phase A is carbon dioxide, phase B is 0.1% formic acid solution of methanol;
the flow rate is 0.2-0.5 mL/min;
the elution mode is gradient elution;
the sample injection amount is 0.5-5 mu L;
the detection time is 3-8 min;
compensation liquid: methanol containing 0.1% ammonia water, with a flow rate of 0.20-0.6 mL/min;
a flow divider: 1/16 PEEK four-way tube;
in step 2, the detection conditions of the MS are set as follows:
mass spectrometry: QTof
Ionization mode: ESI-
Capillary voltage: 1.0KV
Taper hole voltage: 30V
Source temperature: 100 deg.C
Desolventizing steam temperature: 500 deg.C
Flow rate of taper hole gas: 10L/h
Desolventizing steam flow rate: 600L/h
The collection range is as follows: 50-600 m/Z;
the neutral mass number and the ion mass number are as follows:
2. the method of claim 1, wherein:
in the step 2, the concentration of the mixed standard working solution is 5-1000 ng/mL, and at least 5 point values with different concentrations are obtained by dilution.
3. The method of claim 1, wherein:
gradient elution parameters were set as: when 0min is reached, the volume fraction of the mobile phase B is 5-10%; from 0min to 5.0min, the volume fraction of the mobile phase B is increased from 5-10% to 20-25%; from 5.0min to 5.1min, the volume fraction of the mobile phase B is increased from 20-25% to 40-50%, and the volume fraction is kept for 6.0 min; and (3) reducing the volume fraction of the mobile phase B from 40-50% to 5-10% from 6.0min to 8.0min, and keeping the balance for 1 min.
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