CN113049694A - Method for detecting furan and alkyl furan compounds in infant food - Google Patents
Method for detecting furan and alkyl furan compounds in infant food Download PDFInfo
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Abstract
The invention provides a method for detecting furan and alkyl furan compounds in infant food, and belongs to the technical field of substance detection. The method adopts a headspace sampling method, does not use an organic solvent, is environment-friendly, and has simple and easy-to-operate sample pretreatment; in addition, when the gas phase detection is carried out, the DB-624 column is taken as a chromatographic column, so that the separation of 2-ethylfuran and 2, 5-dimethylfuran can be realized; meanwhile, D4-furan, D6-2-methylfuran, D3-3-methylfuran, D5-2-ethylfuran, D3-2, 5-dimethylfuran and D11-2-pentylfuran are respectively used as internal standard substances, so that accurate quantification and detection of furan, 2-methylfuran, 3-methylfuran, 2-ethylfuran, 2, 5-dimethylfuran and 2-pentylfuran can be realized simultaneously, and the detection sensitivity is high.
Description
Technical Field
The invention relates to the technical field of substance detection, in particular to a method for detecting furan and alkyl furan compounds in infant food.
Background
Furan is a five-membered heterocyclic compound containing one oxygen heteroatom, and is used as an intermediate for synthesizing furan drugs. Furan, because of its high volatility and lipophilicity, is readily absorbed by the lungs or intestines through biological membranes, and can cause tumors or canceration in the human body. The results of the study indicated that furan is a significant carcinogen in mice and classified furan as a group 2B that is likely to be carcinogenic in humans.
With the discovery of scientific progress, furan has been found to be ubiquitous in a wide variety of thermally processed foods and is believed to be a by-product of heat treatment and high energy irradiation of foods. Modern people's life focuses more on convenience, so convenience food is popular, and although convenience food is simpler in later-stage treatment and only needs to be flushed by water, heat treatment is required in the food processing process to cure the food, so that many convenience foods need to be subjected to heat treatment or irradiation treatment. This also leads to the inevitable presence of furan in the food product. Although furan is unavoidable, it is still a hot topic of concern for food safety in recent years due to its great harm to the human body.
The detection of furan and alkyl furan compounds in infant food is of great importance due to poor resistance of infants. In the prior art, although a detection method and a detection result of furan in food are reported, a method for simultaneously detecting furan and alkyl furan compounds is rare; meanwhile, 2-ethylfuran and 2, 5-dimethylfuran are isomers which are difficult to detect simultaneously.
Disclosure of Invention
In view of the above, the present invention provides a method for detecting furan and alkyl furan compounds in infant food. The detection method provided by the invention can separate 2-ethylfuran from 2, 5-dimethylfuran; meanwhile, the method can realize accurate quantification and detection of furan, 2-methylfuran, 3-methylfuran, 2-ethylfuran, 2, 5-dimethylfuran and 2-pentylfuran, and has high detection sensitivity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for detecting furan and alkyl furan compounds in infant food, which comprises the following steps:
mixing a sample to be detected, a sodium chloride solution and an internal standard substance, and performing gas chromatography-mass spectrometry detection on the obtained mixed solution in a headspace sample injection manner to obtain the peak area ratio of the sample to be detected to the internal standard substance; the analyte comprises furan and alkyl furan compounds, wherein the alkyl furan compounds comprise 2-methylfuran, 3-methylfuran, 2-ethylfuran, 2, 5-dimethylfuran and 2-pentylfuran; the internal standard substance comprises D4Furan, D6-2-methylfuran, D3-3-methylfuran, D5-2-ethylfuran, D3-2, 5-dimethylfuran and D11-2-pentylfuran;
obtaining the content of furan and alkyl furan compounds in the sample to be detected based on a furan concentration-peak area ratio standard curve, a 2-methylfuran concentration-peak area ratio standard curve, a 3-methylfuran concentration-peak area ratio standard curve, a 2-ethylfuran concentration-peak area ratio standard curve, a 2, 5-dimethylfuran concentration-peak area ratio standard curve and a 2-pentylfuran concentration-peak area ratio standard curve;
the gas mass spectrometry detection parameters comprise gas chromatography conditions and mass spectrometry detection conditions;
the gas chromatography conditions include:
a chromatographic column: DB-624 capillary chromatography column, 30m × 0.25mm × 1.4 μm;
sample inlet temperature: 250 ℃;
column temperature: the initial temperature is 40 ℃, the temperature is kept for 2min, the temperature is increased to 70 ℃ at the speed of 5 ℃/min, the temperature is increased to 210 ℃ at the speed of 20 ℃/min, and the operation is carried out for 10min after the temperature is 250 ℃;
carrier gas: helium with purity more than or equal to 99.999%;
flow rate: 1.0 mL/min;
the split ratio is as follows: 10: 1;
the mass spectrometry detection conditions include:
ionization mode: electron bombardment source with energy of 70eV, automatic tuning;
temperature of the quadrupole rods: 150 ℃;
ion source temperature: 230 ℃;
transmission line temperature: 250 ℃;
solvent retardation: 2 min;
the monitoring mode is as follows: and selecting an ion monitoring mode.
Preferably, the mass concentration of the sodium chloride solution is 10-30%.
Preferably, the sample to be detected comprises a solid sample to be detected or a liquid sample to be detected; the particle size of the solid sample to be detected is 20-80 meshes.
Preferably, when the sample to be detected is a solid sample to be detected, the usage ratio of the solid sample to be detected to the sodium chloride solution is 0.2-1.0 g: 10 mL;
when the sample to be detected is a liquid sample to be detected, the volume ratio of the liquid sample to be detected to the sodium chloride solution is 0.2-2 mL: 10 mL.
Preferably, the concentration of the internal standard substance in the mixed solution is 5-20 ng/mL.
Preferably, the concentration of the internal standard substance in the mixed solution is 10 ng/mL.
Preferably, the parameters of the headspace sampling comprise: the heating time is 30min, the equilibrium temperature is 60 ℃, the temperature of a sample injection needle is 70 ℃, the sample injection volume is 1mL, the sample injection speed is 30mL/min, the GC cycle time is 35min, and the vibration frequency of the sample bottle is 150 r/min.
The invention provides a method for detecting furan and alkyl furan compounds in infant food, which comprises the following steps: mixing a sample to be detected, a sodium chloride solution and an internal standard substance, and performing gas chromatography-mass spectrometry detection on the obtained mixed solution in a headspace sample injection manner to obtain the peak area ratio of the sample to be detected to the internal standard substance; the analyte comprises furan and alkyl furan compounds, wherein the alkyl furan compounds comprise 2-methylfuran, 3-methylfuran, 2-ethylfuran, 2, 5-dimethylfuran and 2-pentylfuran; the internal standard substance comprises D4Furan, D6-2-methylfuran, D3-3-methylfuran, D5-2-ethylfuran, D3-2, 5-dimethylfuran and D11-2-pentylfuran; obtaining the content of furan and alkyl furan compounds in the sample to be detected based on a furan concentration-peak area ratio standard curve, a 2-methylfuran concentration-peak area ratio standard curve, a 3-methylfuran concentration-peak area ratio standard curve, a 2-ethylfuran concentration-peak area ratio standard curve, a 2, 5-dimethylfuran concentration-peak area ratio standard curve and a 2-pentylfuran concentration-peak area ratio standard curve; the gas mass spectrometry detection parameters comprise gas chromatography conditions and mass spectrometry detection conditions; the gas chromatography conditions include: a chromatographic column: DB-624 capillary chromatography column, 30m × 0.25mm × 1.4 μm; sample inlet temperature: 250 ℃; column temperature: the initial temperature is 40 ℃, the temperature is kept for 2min, the temperature is increased to 70 ℃ at the speed of 5 ℃/min, the temperature is increased to 210 ℃ at the speed of 20 ℃/min, and the operation is carried out for 10min after the temperature is 250 ℃; carrier gas: helium with purity more than or equal to 99.999%; flow rate: 1.0 mL/min; the split ratio is as follows: 10: 1; the mass spectrometry detection conditions include: ionization mode: electron bombardment source with energy of 70eV, automatic tuning; temperature of the quadrupole rods: 150 ℃; ion source temperature: 230 ℃; transmission line temperature: 250 ℃; solvent retardation: 2 min; the monitoring mode is as follows: and selecting an ion monitoring mode.
The method adopts a headspace sampling method, does not use an organic solvent, is environment-friendly, and has simple and easy-to-operate sample pretreatment; in addition, when the gas phase detection is carried out, the DB-624 column is taken as a chromatographic column, so that the separation of 2-ethylfuran and 2, 5-dimethylfuran can be realized; at the same time, respectively with D4Furan, D6-2-methylfuran, D3-3-methylfuran, D5-2-ethylfuran, D3-2, 5-dimethylfuran and D11The-2-pentylfuran is used as an internal standard substance, can simultaneously realize accurate quantification and detection of furan, 2-methylfuran, 3-methylfuran, 2-ethylfuran, 2, 5-dimethylfuran and 2-pentylfuran, and has high detection sensitivity.
Drawings
FIG. 1 is a total ion flow diagram of a sodium chloride solution having a mass concentration of 20%;
FIG. 2 is a total ion flow graph of an internal standard mixed application solution with a concentration of 10 ng/mL;
FIG. 3 is a total ion flow graph of an internal standard mixed application solution at a concentration of 10ng/mL and a standard mixed solution at a concentration of 10 ng/mL;
FIGS. 4 to 6 are partially enlarged views of FIG. 3;
FIG. 7 is a total ion flow graph of infant rice flour;
FIG. 8 is a total ion flow graph of infant milk powder;
FIG. 9 is a total ion flow graph of baby canned puree;
FIG. 10 is a total ion flow graph of baby canned puree;
FIG. 11 is a total ion flow PLOT for HP-PLOT detection on a chromatographic column;
FIG. 12 is a partial enlarged view of the 2-ethylfuran and 2, 5-dimethylfuran moieties of FIG. 11.
Detailed Description
The invention provides a method for detecting furan and alkyl furan compounds in infant food, which comprises the following steps:
mixing a sample to be detected, a sodium chloride solution and an internal standard substance, and performing gas chromatography-mass spectrometry detection on the obtained mixed solution in a headspace sample injection manner to obtain the peak area ratio of the sample to be detected to the internal standard substance; the analyte comprises furan and alkyl furan compounds, wherein the alkyl furan compounds comprise 2-methylfuran, 3-methylfuran, 2-ethylfuran, 2, 5-dimethylfuran and 2-pentylfuran; the internal standard substance comprises D4Furan, D6-2-methylfuran, D3-3-methylfuran, D5-2-ethylfuran, D3-2, 5-dimethylfuran and D11-2-pentylfuran;
and obtaining the content of furan and alkyl furan compounds in the sample to be detected based on a furan concentration-peak area ratio standard curve, a 2-methylfuran concentration-peak area ratio standard curve, a 3-methylfuran concentration-peak area ratio standard curve, a 2-ethylfuran concentration-peak area ratio standard curve, a 2, 5-dimethylfuran concentration-peak area ratio standard curve and a 2-pentylfuran concentration-peak area ratio standard curve.
In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
According to the invention, a sample to be detected, a sodium chloride solution and an internal standard substance are mixed, and the obtained mixed solution is subjected to gas chromatography-mass spectrometry detection in a headspace sample injection manner, so as to obtain the peak area ratio of the object to be detected in the sample to be detected relative to the internal standard substance.
In the present invention, the sample to be tested is preferably stored at 4 ℃ or-18 ℃ before being mixed with the sodium chloride solution and the internal standard substance, so as to avoid volatilization loss of the furan compound in the sample to be tested; the internal standard is preferably stored at-18 ℃ protected from light.
In the present invention, the concentration of the sodium chloride solution is preferably 10 to 30%, and more preferably 20%.
In the present invention, the sample to be tested preferably includes a solid sample to be tested or a liquid sample to be tested; the solid sample to be detected preferably comprises infant milk powder, infant rice powder, canned fruit and vegetable paste, canned meat paste, auxiliary cereal food, wheat breakfast or oat breakfast; the liquid sample to be tested preferably includes, but is not limited to, apple juice or orange juice beverage. In the invention, when the sample to be detected is a solid sample to be detected, the particle size of the solid sample to be detected is preferably 20-80 meshes; the preferable dosage ratio of the solid sample to be detected to the sodium chloride solution is 0.2-1.0 g: 10mL, more preferably 0.5 g: 10 mL. In the invention, when the sample to be detected is preferably a liquid sample to be detected, the volume ratio of the liquid sample to be detected to the sodium chloride solution is preferably 0.2-2 mL: 10mL, more preferably 0.5: 10 mL.
In the present invention, the internal standard substance comprises D4Furan, D6-2-methylfuran, D3-3-methylfuran, D5-2-ethylfuran solution, D3-2, 5-dimethylfuran and D11-2-pentylfuran; the concentration of the internal standard substance in the mixed solution is preferably 5-20 ng/mL independently, and more preferably 10 ng/mL.
In the present invention, the sample to be tested, the sodium chloride solution and the internal standard substance are preferably mixed in a headspace bottle, and the mixing specifically preferably includes the following steps:
quantitatively putting a sample to be detected into a headspace bottle, adding a sodium chloride solution, adding an internal standard substance, immediately covering a cover of the headspace bottle, and uniformly mixing.
After the mixed solution is obtained, the gas chromatography-mass spectrometry detection is carried out on the obtained mixed solution in a headspace sampling mode, and the peak area ratio of the object to be detected in the sample to be detected relative to the internal standard substance is obtained.
In the present invention, the parameters of the headspace sampling preferably include: the parameters of headspace sampling comprise: the heating time is 30min, the equilibrium temperature is 60 ℃, the temperature of a sample injection needle is 70 ℃, the sample injection volume is 1mL, the sample injection speed is 30mL/min, the GC cycle time is 35min, and the vibration frequency of the sample bottle is 150 r/min.
In the invention, the gas mass spectrometry detection parameters comprise gas chromatography conditions and mass spectrometry detection conditions;
the gas chromatography conditions include:
a chromatographic column: DB-624 capillary chromatography column, 30m × 0.25mm × 1.4 μm;
sample inlet temperature: 250 ℃;
column temperature: the initial temperature is 40 ℃, the temperature is kept for 2min, the temperature is increased to 70 ℃ at the speed of 5 ℃/min, the temperature is increased to 210 ℃ at the speed of 20 ℃/min, and the operation is carried out for 10min after the temperature is 250 ℃;
carrier gas: helium with purity more than or equal to 99.999%;
flow rate: 1.0 mL/min;
the split ratio is as follows: 10: 1;
the mass spectrometry detection conditions include:
ionization mode: electron bombardment source with energy of 70eV, automatic tuning;
temperature of the quadrupole rods: 150 ℃;
ion source temperature: 230 ℃;
transmission line temperature: 250 ℃;
solvent retardation: 2 min;
the monitoring mode is as follows: and selecting an ion monitoring mode.
In the present invention, the ion information for mass spectrometry is shown in table 1.
TABLE 1 summary of mass spectrometric monitoring ion information
Note: the bands "+" are the quantitative ions.
In the invention, the peak area ratios of the to-be-detected substance to the internal standard substance in the to-be-detected sample respectively comprise furan relative D4Peak area ratio of furan, 2-methylfuran relative to D6Peak area ratio of 2-methylfuran, 3-methylfuran relative to D3Peak area ratio of 3-methylfuran, 2-ethylfuran relative to D5Peak area ratio of 2-ethylfuran, 2, 5-dimethylfuran relative to D3Peak area ratio of 2, 5-dimethylfuran, 2-pentylfuran relative to D11-peak area ratio of 2-pentylfuran.
After the peak area ratio of the object to be detected in the sample to be detected relative to the internal standard substance is reached, the content of furan and alkyl furan compounds in the sample to be detected is obtained based on a furan concentration-peak area ratio standard curve, a 2-methylfuran concentration-peak area ratio standard curve, a 3-methylfuran concentration-peak area ratio standard curve, a 2-ethylfuran concentration-peak area ratio standard curve, a 2, 5-dimethylfuran concentration-peak area ratio standard curve and a 2-pentylfuran concentration-peak area ratio standard curve, so that the content of furan and alkyl furan compounds in the sample to be detected is obtained.
The method for acquiring the furan concentration-peak area ratio standard curve, the 2-methylfuran concentration-peak area ratio standard curve, the 3-methylfuran concentration-peak area ratio standard curve, the 2-ethylfuran concentration-peak area ratio standard curve, the 2, 5-dimethylfuran concentration-peak area ratio standard curve and the 2-pentylfuran concentration-peak area ratio standard curve is not particularly limited, and the method for acquiring the standard curve of the numerical value of a person skilled in the art can be adopted without introducing too much.
The content of the furan compound in the sample to be detected is calculated according to the formula (1):
in the formula:
Xi-the content of the ith furan compound in the sample to be tested is microgram per kilogram (mug/Kg);
Cithe peak area ratio of the ith furan compound chromatographic peak to the internal standard chromatographic peak in the sample to be detected corresponds to the concentration of the ith furan compound in the standard curve, and the unit is nanogram/milliliter (ng/mL);
Ci0the peak area ratio of the ith furan compound chromatographic peak to the internal standard chromatographic peak in the blank process corresponds to the concentration of the ith furan compound in the standard curve, and the unit is nanogram/milliliter (ng/mL);
v-volume of solution in milliliters (mL);
m is the sample size in grams (g);
the calculation results are expressed as the arithmetic mean of two independent measurements obtained under repetitive conditions, leaving the decimal point 1 position.
The following examples are provided to describe in detail the method for detecting furan and alkylfuran compounds in infant food according to the present invention, but they should not be construed as limiting the scope of the present invention.
The parameters of the headspace injection used in the following examples are preferably: the parameters of headspace sampling comprise: the heating time is 30min, the equilibrium temperature is 60 ℃, the temperature of a sample injection needle is 70 ℃, the sample injection volume is 1mL, the sample injection speed is 30mL/min, the GC cycle time is 35min, and the vibration frequency of the sample bottle is 150 r/min;
the following examples used both chromatographic and mass spectral parameters:
the gas chromatography conditions include:
a chromatographic column: DB-624 capillary chromatography column, 30m × 0.25mm × 1.4 μm;
sample inlet temperature: 250 ℃;
column temperature: the initial temperature is 40 ℃, the temperature is kept for 2min, the temperature is increased to 70 ℃ at the speed of 5 ℃/min, the temperature is increased to 210 ℃ at the speed of 20 ℃/min, and the operation is carried out for 10min after the temperature is 250 ℃;
carrier gas: helium with purity more than or equal to 99.999%;
flow rate: 1.0 mL/min;
the split ratio is as follows: 10: 1;
the mass spectrometry detection conditions include:
ionization mode: electron bombardment source with energy of 70eV, automatic tuning;
temperature of the quadrupole rods: 150 ℃;
ion source temperature: 230 ℃;
transmission line temperature: 250 ℃;
solvent retardation: 2 min;
the monitoring mode is as follows: and selecting an ion monitoring mode.
Example 1
(1.1) 5 standard mixed stock solutions of 2-methylfuran, 3-methylfuran, 2-ethylfuran, 2, 5-dimethylfuran, 2-pentylfuran (2.0 mg/mL): respectively weighing 50.0mg of 2-methylfuran, 3-methylfuran, 2-ethylfuran, 2, 5-dimethylfuran and 2-pentylfuran in a 25mL volumetric flask, dissolving with methanol to a constant volume, transferring into a brown liquid storage bottle, storing at-18 ℃ in a dark place, and keeping for 1 year in validity period.
(1.2) 5 Standard Mixed intermediate solutions (100. mu.g/mL) of 2-methylfuran, 3-methylfuran, 2-ethylfuran, 2, 5-dimethylfuran, 2-pentylfuran: taking 0.5mL of 5 standard mixed stock solutions of 2.0mg/mL into a 10mL volumetric flask, fixing the volume with methanol, transferring into a brown stock solution bottle, storing at-18 ℃ in a dark place, and keeping the effective period for 3 months.
(1.3) Standard Mixed application solution (1.0. mu.g/mL): and (3) respectively sucking a furan standard methanol solution (100 mu g/mL) and 0.25mL of the standard solution prepared in the step (1.2) into a 25mL volumetric flask, metering the volume with methanol, storing at-18 ℃ in a dark place, and keeping the effective period for 1 month.
(1.4) Standard Mixed solution (0.10. mu.g/mL): 1.0mL of the 1.3 standard solution was pipetted into a 10mL volumetric flask, and the volumetric capacity was determined with methanol, and the solution was stored at-18 ℃ in the dark for 1 week.
(1.5)D4Intermediate furan internal standard (2.0. mu.g/mL): 0.5mL of 100. mu.g/mL of suction D4-in furanThe standard solution was made up to 25mL with methanol and stored at-18 ℃ in the dark.
(1.6)D6-2-methylfuran solution (0.5 mg/mL): take 5.0mg of D6Dissolving 2-methylfuran with methanol to 10mL, and storing at 18 ℃ in dark.
(1.7)D3-3-methylfuran solution (0.5 mg/mL): take 5.0mg of D3Dissolving 3-methylfuran with methanol to 10mL, and storing at 18 ℃ in dark.
(1.8)D5-2-ethylfuran solution (0.5 mg/mL): take 5.0mg of D5Dissolving 2-ethyl furan with methanol to a constant volume of 10mL, and storing at 18 ℃ in a dark place.
(1.9)D3-2, 5-dimethylfuran solution (0.1 mg/mL): take 1.0mg of D3Dissolving 2, 5-dimethylfuran with methanol to 10mL, and storing at-18 ℃ in dark.
(1.10)D11-2-pentylfuran solution (0.1 mg/mL): take 1.0mg of D11Dissolving 2-amyl furan with methanol to a constant volume of 10mL, and storing at 18 ℃ in a dark place.
(1.11)D6-2-methylfuran, D3-3-methylfuran, D5-2-ethylfuran solution, D3-2, 5-dimethylfuran, D11-2-pentylfuran 5 internal standard mixed solutions (10.0 μ g/mL): each 0.2mL0.5mg/mL of D6-2-methylfuran solution, 0.5mg/mL D3-3-methylfuran solution, 0.5mg/mL D5-2-ethylfuran solution, and 0.1mg/mL D3-2, 5-dimethylfuran solution, 0.1mg/mL D111.0mL of-2-pentylfuran solution respectively, diluting the solution to 10mL with methanol, storing the solution at the temperature of-18 ℃ in a dark place, and keeping the solution for 1 year in validity period.
(1.12)6 internal standards mix application solutions (1.0. mu.g/mL): sucking 1.0mL of 10.0. mu.g/mL of 5 internal standard mixed solutions, 5mL of 2.0. mu.g/mL of D4Intermediate liquid of furan internal standard is prepared to 10mL by methanol, and is stored in dark at 18 ℃ with the effective period of 1 year.
Taking 8 20mL headspace sample bottles, adding 10mL sodium chloride solution with the mass concentration of 20% and 100 μ L of 1.0 μ g/mL 6 internal standards respectively, mixing the application liquid in the headspace bottles, respectively adding 0, 20 mu L, 50 mu L and 100 mu L of 0.1 mu g/mL 6 furan mixed standard use solutions, 20 mu L, 50 mu L, 100 mu L and 200 mu L of 1.0 mu g/mL 6 furan mixed standard use solutions, covering a headspace bottle cap, uniformly mixing to prepare mixed standard solutions with the concentrations of 0ng/mL, 0.2ng/mL, 0.5ng/mL, 1.0ng/mL, 2.0ng/mL, 5.0ng/mL, 10.0ng/mL and 20.0ng/mL, adding an internal standard substance when in use, wherein the concentration of the internal standard substance is 10.0ng/mL, drawing a standard curve after gas phase mass spectrometry detection, and obtaining the results shown in Table 2.
TABLE 2 Standard Linear Range and correlation coefficients
As can be seen from table 2: the correlation coefficients of the 6 compounds are all above 0.999, which shows that the linear correlation of the instrument is better and the quantification is accurate when the headspace gas chromatography product is used for detecting the 6 compounds in the concentration range by adopting an internal standard method.
Example 2
And (3) adding 10mL of sodium chloride solution with the mass concentration of 20% into a 20mL headspace sample injection bottle, and performing gas mass spectrometry to obtain a spectrogram shown in figure 1.
Adding 10mL of sodium chloride solution with mass concentration of 20% into a 20mL headspace sample injection bottle, adding 6 internal standard substances with concentration of 10ng/mL respectively, tightly covering a bottle cap, and placing into an automatic headspace sample injection device for gas mass spectrometry, wherein the obtained spectrogram is shown in FIG. 2.
As can be seen from fig. 1 and 2: under the experimental condition, the blank value of the sodium chloride solution is well controlled, and no interferents exist. The addition of sodium chloride can promote the volatilization of the compound to be detected, improve the sensitivity and simultaneously play a role in preventing microorganisms.
Adding 10mL of sodium chloride solution with the mass concentration of 20% into a 20mL headspace sample injection bottle, adding 6 internal standard substances with the concentration of 10ng/mL and standard substances with the concentration of 10ng/mL respectively, tightly covering a bottle cap, and putting into an automatic headspace sample injection device for gas mass spectrometry, wherein the obtained total ion flow graph is shown in FIG. 3; fig. 4 to 6 are partially enlarged views of the total ion flow diagram obtained in fig. 3.
As can be seen from FIGS. 3-6: all compounds are completely separated, and the method is accurate in qualitative and quantitative determination; and can separate the isomers of 2-ethyl furan and 2, 5-dimethyl furan well.
Example 3
Taking 0.5g (accurate to 0.001g) of infant milk powder, rice flour, fruit and vegetable paste and meat paste to 20mL of headspace sample injection bottles, adding 10mL of sodium chloride solution with the mass concentration of 20%, adding 6 internal standard substances with the concentration of 10ng/mL respectively, covering the bottle caps tightly, and putting the bottles into an automatic headspace sample injection device for gas mass spectrometry; the limit of quantitation (LOQ) of the substance was determined according to the 10-fold signal-to-noise ratio of the detected substance, and the results are shown in Table 3; the limit of detection (LOD) of the substance was determined according to the 3-fold signal-to-noise ratio of the substance to be detected, and the results are shown in Table 3.
TABLE 3 limits of quantitation and detection of various compounds (. mu.g/kg)
Example 4
Recovery rate of added standard
Weighing 0.50g (accurate to 0.001g) of sample with known substance content into a 20mL headspace sample bottle, adding 10mL of sodium chloride solution with the mass concentration of 20%, adding 6 internal standard substances with the concentration of 10ng/mL respectively, adding mixed standard substances with the concentrations of 0.25ng/mL and 2.5ng/mL respectively, tightly covering a bottle cap, and putting into an automatic headspace sample injection device for gas mass spectrometry, wherein the gas mass spectrometry is equivalent to the sample adding standard of 5.0 mug/kg and 50.0 mug/kg. The average recovery obtained is shown in table 4.
TABLE 4 infant food normalized average recovery
As can be seen from table 4: the recovery rate of the 6 furan compounds is 85.2-107.7%, and the RSD is less than 10%.
Example 5
Commercially available infant rice flour was collected and frozen in a-18 ℃ freezer for 2 hours, and sampled for analysis as soon as possible.
Weighing 0.5g (accurate to 0.001g) of infant rice flour, putting the infant rice flour into a 20mL headspace bottle, adding 10mL of sodium chloride solution with the mass concentration of 20%, adding 100 μ L of 6 internal standard mixed application liquids (the concentration of internal standard substances in the mixed liquid is independently 10ng/mL), immediately covering a headspace bottle cover, uniformly mixing, putting the headspace bottle on a headspace sampling device, and automatically performing gas mass spectrometry, wherein the obtained total ion flow diagram is shown in FIG. 7.
Based on the standard curve and calculation method of example 1, we obtained: in the commercially available infant rice flour, the content of furan is 26.8 mu g/kg, and the content of 2-methylfuran is 4.7 mu g/kg; the content of 3-methylfuran is 2.0 mu g/kg; the content of 2-ethyl furan is 3.0 mu g/kg; the content of 2, 5-dimethylfuran is <2.0 mug/kg; the content of 2-pentylfuran was 50.9. mu.g/kg.
The commercial infant milk powder is tested according to the scheme, and the obtained total ion flow graph is shown in fig. 8.
Based on the standard curve and calculation method of example 1, we obtained: in the commercially available infant milk powder, the content of furan is 4.5 mu g/kg, and the content of 2-methylfuran is 3.0 mu g/kg; the content of 3-methylfuran is 2.5 mug/kg; the content of 2-ethyl furan is 8.0 mu g/kg; the content of 2, 5-dimethylfuran is <2.0 mug/kg; the content of 2-pentylfuran was 9.9. mu.g/kg.
The commercially available fruit and vegetable puree for baby canning is detected according to the scheme, and the obtained total ion flow diagram is shown in fig. 9.
Based on the standard curve and calculation method of example 1, we obtained: in the canned fruit and vegetable puree for the commercially available infants, the content of furan is 6.4 mu g/kg, and the content of 2-methylfuran is 3.4 mu g/kg; the content of 3-methylfuran is 2.8 mug/kg; 2-ethylfuran <2.0 μ g/kg; 2, 5-dimethylfuran <2.0 μ g/kg; 2-pentylfuran < 2.0. mu.g/kg.
The commercially available canned mashed meat for infants is detected according to the scheme, and the obtained total ion flow diagram is shown in fig. 10.
Based on the standard curve and calculation method of example 1, we obtained: in the canned meat paste for the commercial infants, the content of furan is 18.9 mug/kg, and the content of 2-methylfuran is 8.7 mug/kg; the content of 3-methylfuran is 3.4 mug/kg; the content of 2-ethyl furan is 11.4 mu g/kg; 2, 5-dimethylfuran <2.0 μ g/kg; the content of 2-pentylfuran was 42.2. mu.g/kg.
Comparative example 1
The column in the gas chromatography conditions was replaced with an HP-PLOT column.
The standard mixture containing the internal standard substance and the standard substance in example 2 was tested under the above-mentioned chromatographic conditions, and the resultant total ion flow chart is shown in FIG. 11, and FIG. 12 is a partial enlarged view of the 2-ethylfuran and 2, 5-dimethylfuran moieties in FIG. 11. As can be seen by comparing FIG. 12 with FIG. 5, the 2-ethylfuran and 2, 5-dimethylfuran cannot be separated by the HP-PLOT column; and DB-624 capillary chromatography column can separate them.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A method for detecting furan and alkyl furan compounds in infant food is characterized by comprising the following steps:
mixing a sample to be detected, a sodium chloride solution and an internal standard substance, and performing gas chromatography-mass spectrometry detection on the obtained mixed solution in a headspace sample injection manner to obtain the peak area ratio of the sample to be detected to the internal standard substance; the analyte comprises furan and alkyl furan compounds, wherein the alkyl furan compounds comprise 2-methylfuran, 3-methylfuran, 2-ethylfuran, 2, 5-dimethylfuran and 2-pentylfuran; the internal standard substance comprises D4Furan, D6-2-methylfuran, D3-3-methylfuran, D5-2-ethylfuran, D3-2, 5-dimethylfuran and D11-2-pentylfuran;
obtaining the content of furan and alkyl furan compounds in the sample to be detected based on a furan concentration-peak area ratio standard curve, a 2-methylfuran concentration-peak area ratio standard curve, a 3-methylfuran concentration-peak area ratio standard curve, a 2-ethylfuran concentration-peak area ratio standard curve, a 2, 5-dimethylfuran concentration-peak area ratio standard curve and a 2-pentylfuran concentration-peak area ratio standard curve;
the gas mass spectrometry detection parameters comprise gas chromatography conditions and mass spectrometry detection conditions;
the gas chromatography conditions include:
a chromatographic column: DB-624 capillary chromatography column, 30m × 0.25mm × 1.4 μm;
sample inlet temperature: 250 ℃;
column temperature: the initial temperature is 40 ℃, the temperature is kept for 2min, the temperature is increased to 70 ℃ at the speed of 5 ℃/min, the temperature is increased to 210 ℃ at the speed of 20 ℃/min, and the operation is carried out for 10min after the temperature is 250 ℃;
carrier gas: helium with purity more than or equal to 99.999%;
flow rate: 1.0 mL/min;
the split ratio is as follows: 10: 1;
the mass spectrometry detection conditions include:
ionization mode: electron bombardment source with energy of 70eV, automatic tuning;
temperature of the quadrupole rods: 150 ℃;
ion source temperature: 230 ℃;
transmission line temperature: 250 ℃;
solvent retardation: 2 min;
the monitoring mode is as follows: and selecting an ion monitoring mode.
2. The detection method according to claim 1, wherein the sodium chloride solution has a mass concentration of 10 to 30%.
3. The detection method according to claim 1, wherein the sample to be detected comprises a solid sample to be detected or a liquid sample to be detected; the particle size of the solid sample to be detected is 20-80 meshes.
4. The detection method according to claim 3, wherein when the sample to be detected is a solid sample to be detected, the ratio of the amount of the solid sample to be detected to the amount of the sodium chloride solution is 0.2-1.0 g: 10 mL;
when the sample to be detected is a liquid sample to be detected, the volume ratio of the liquid sample to be detected to the sodium chloride solution is 0.2-2 mL: 10 mL.
5. The detection method according to claim 1, wherein the concentration of the internal standard substance in the mixed solution is 5 to 20 ng/mL.
6. The detection method according to claim 5, wherein the concentration of the internal standard substance in the mixed solution is 10 ng/mL.
7. The detection method according to claim 1, wherein the parameters of the headspace sampling comprise: the heating time is 30min, the equilibrium temperature is 60 ℃, the temperature of a sample injection needle is 70 ℃, the sample injection volume is 1mL, the sample injection speed is 30mL/min, the GC cycle time is 35min, and the vibration frequency of the sample bottle is 150 r/min.
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