CN103592403A - Detection method for simultaneous determination of residual quantity of five fresh fruit preservatives - Google Patents
Detection method for simultaneous determination of residual quantity of five fresh fruit preservatives Download PDFInfo
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Abstract
The invention relates to the field of food safety detection, and provides a detection method for simultaneous determination of residual quantity of five fresh fruit preservatives including methyl-p-hydroxybenzoate, ethyl p-hydroxybenzoate, 2,4-dichlorphenoxyacetic acid, ethyl naphthol and 4-phenyl phenol. The detection method for simultaneous determination of the residual quantity of the five fresh fruit preservatives comprises the following steps: sample extraction, concentration, purification and liquid chromatography-mass spectrography determination. The method is simple and easy to operate in pretreatment, short in analysis time, wide in linearity range, high in sensitivity and accurate in detection result; and the detection limit is lower than 1.0 mu g/kg, and qualitative and quantitative detection requirements of the preservatives can be met.
Description
Technical field
The present invention relates to food safety detection field, relate in particular to a kind of detection method of simultaneously measuring five kinds of fresh fruit antistaling agent residual quantities.
Background technology
< < food additives are used standard > > (GB2760-2011) to make clear and definite regulation to the antistaling agent kind that allows in fresh fruit to use and maximum use amount, residual quantity.Although chemical preservation antistaling agent has the effect of anti-corrosive fresh-keeping, but mostly can produce and have toxic action in various degree human body, to health, bring adverse effect, even occur the situations such as carcinogenic, teratogenesis, mutagenesis, strengthen antiseptic and fresh-keeping agent for fruits Residue Monitoring significant for this reason.Parabens (methyl esters, ethyl ester), ethyl naphthol, 4-phenylphenol, 2, and 4-dichlorphenoxyacetic acid (2,4-D) be the fruit antistaling agent of relatively commonly using, they have certain toxicity to human body.
In prior art, have high performance liquid chromatography to parabens, ethyl naphthol, 2,4-D and 4-phenylphenol residual quantity are distinguished method for measuring, but testing process is loaded down with trivial details, labor intensive material resources.Also have to adopt and utilize GC-MS to measure the report of methyl p-hydroxybenzoate, ethyl-para-hydroxybenzoate, ethyl naphthol, 4-phenylphenol and Biphenyl Ether residual quantity simultaneously, but lowest detectable limit is higher.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of detection method of simultaneously measuring five kinds of fresh fruit antistaling agent residual quantities, be intended to solve problem loaded down with trivial details to the testing process of antisepsis antistaling agent in prior art.
The invention provides a kind of detection method of simultaneously measuring five kinds of fresh fruit antistaling agent residual quantities, described five kinds of antisepsis antistaling agents are methyl p-hydroxybenzoate, ethyl-para-hydroxybenzoate, 2,4-dichlorphenoxyacetic acid, ethyl naphthol and 4-phenylphenol; The described detection method of simultaneously measuring five kinds of fresh fruit antistaling agent residual quantities comprises the following steps:
Sample extraction: testing sample is smashed to pieces, vibrated after adding the ether of 4～7 times of testing sample quality, ultrasonic, then add the sodium chloride vibration of 0.8～1.2 times of sample quality, and centrifugal, get organic phase;
Concentrated: to repeat described sample extraction step 2～3 time, be concentrated into 1/15～1/20 of its volume after merging described organic phase, obtain liquid to be clean;
Purify: pour after solid-phase extraction column described liquid to be clean into be 1:1 with volume ratio acetoneand ethyl acetate mixed liquor wash-out, eluent blows to doing with nitrogen, and methanol constant volume, to 1mL, after 0.45 μ m membrane filtration, obtains liquid to be measured;
Sample determination: liquid chromatography mass Instrument measuring, wherein, liquid phase chromatogram condition is chromatographic column: Thermo HYPERSIL ODS-2C
18post, 4.6 * 150mm * 5 μ m, eluent gradient elution requirement is in Table 1; Column temperature is 40 ℃; Sample size is 2 μ L.
Table 1
Mass spectrum condition is: electric spray ion source: ESI-, collision gas CAD:6psi, gas curtain atmospheric pressure CUR:24psi, atomization gas pressure GS1:55psi, auxiliary heater GS2:55psi, spray voltage IS:-4500V, ion source temperature TEM:600 ℃, the multiple-reaction monitoring mass spectrum parameter of five kinds of fresh fruit antistaling agents is in Table 2, and wherein, with * is quota ion.
Table 2
The detection method of simultaneously measuring five kinds of fresh fruit antistaling agent residual quantities provided by the present invention, by liquid chromatography-mass spectrometry, the residual quantity of five kinds of antisepsis antistaling agents is realized to qualitative, quantitative measurement simultaneously, this detection method is short analysis time, and the range of linearity is wide, highly sensitive, testing result is accurate, and detectability, lower than 1.0 μ g/kg, can meet the requirement of antisepsis antistaling agent qualitative and quantitative analysis.
Accompanying drawing explanation
Fig. 1 is the LC-MS/MS collection of illustrative plates of the mixed marks of five kinds of fresh fruit antistaling agents (0.4 μ g/mL), and wherein, 1 represents 2,4-D; 2 represent methyl p-hydroxybenzoate; 3 represent ethyl-para-hydroxybenzoate; 4 represent ethyl naphthol; 5 represent 4-phenylphenol.
Fig. 2 is the LC-MS/MS collection of illustrative plates of apple.
Fig. 3 is the LC-MS/MS collection of illustrative plates of apple mark-on (0.4 μ g/mL), and wherein, 1 represents 2,4-D; 2 represent methyl p-hydroxybenzoate; 3 represent ethyl-para-hydroxybenzoate; 4 represent ethyl naphthol; 5 represent 4-phenylphenol.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The invention provides a kind of detection method of simultaneously measuring five kinds of fresh fruit antistaling agent residual quantities, described five kinds of antisepsis antistaling agents are methyl p-hydroxybenzoate, ethyl-para-hydroxybenzoate, 2,4-dichlorphenoxyacetic acid, ethyl naphthol and 4-phenylphenol; The described detection method of simultaneously measuring five kinds of fresh fruit antistaling agent residual quantities comprises the following steps:
S01: sample extraction: testing sample is smashed to pieces, vibrated after adding the ether of 4～7 times of testing sample quality, ultrasonic, then add the sodium chloride vibration of 0.8～1.2 times of sample quality, and centrifugal, get organic phase;
S02: concentrated: repeat described sample extraction step 2～3 time, be concentrated into 1/15～1/20 of its volume after merging described organic phase, obtain liquid to be clean;
S03: purify: pour after solid-phase extraction column described liquid to be clean into be 1:1 by volume ratio acetoneand ethyl acetate mixed liquor wash-out, eluent dries up, and methanol constant volume, to 1mL, after 0.45 μ m membrane filtration, obtains liquid to be measured;
S04: sample determination: liquid chromatography mass Instrument measuring, wherein, liquid phase chromatogram condition is chromatographic column: Thermo HYPERSIL ODS-2C
18post, 4.6 * 150mm * 5 μ m, eluent gradient elution requirement is in Table 1; Column temperature is 40 ℃; Sample size is 2 μ L.
Table 1
Mass spectrum condition: electric spray ion source: ESI-, collision gas CAD:6psi, gas curtain atmospheric pressure CUR:24psi, atomization gas pressure GS1:55psi, auxiliary heater GS2:55psi, spray voltage IS:-4500V, ion source temperature TEM:600 ℃, the multiple-reaction monitoring mass spectrum parameter of five kinds of fresh fruit antistaling agents is in Table 2, and wherein, with * is quota ion.
Table 2
In step S01, preferably testing sample is smashed to pieces, vibrated after adding the ether of 5～6 times of testing sample quality, ultrasonic, then add the sodium chloride vibration of 1 times of sample quality, and centrifugal, get organic phase.Concrete steps can be smashed to pieces for 100g fresh fruit is put into bruiser, stand-by after stirring.Take 2.0g sample (being accurate to 0.001g) and put into 50mL centrifuge tube, add 10mL ether, ultrasonic extraction 4～8min again after vortex vibration 2min, adds 2.0g sodium chloride vortex 2min again, and the centrifugal 4～8min of 4000～5000r/min, gets organic phase.
In step S02, repeating step S01, extracts 2～3 times, preferably extracts 2 times, merges organic phase.Organic phase is concentrated into about 1mL on parallel evaporimeter (pressure 689mbar), for purified treatment.Parallel evaporimeter is for example selected Switzerland BUCHI.
In step S03, preferably adopt activated charcoal pillar (Supelclean
tMeNVI
tM-Carb SPE Tubes, 3mL, 0.25g) purify.Activated charcoal pillar is first used 2mL acetone: ethyl acetate solution (volume ratio is 1:1) activation, and liquid to be clean is poured into and used 5mL acetone after solid-phase extraction column: ethyl acetate solution (volume ratio is 1:1) wash-out.Eluent blows near dry with nitrogen, by methanol constant volume, to 1mL, supplies efficient liquid phase chromatographic analysis after 0.45 μ m membrane filtration.
In step S04, liquid chromatograph can be selected Shimadzu LC-30 series, Japanese Shimadzu company; Mass spectrometer can select API4000 to be furnished with electric spray ion source (ESI) and Analysit1.6 data handling system, Applied biosystems (ABI).The present invention has compared Thermo HYPERSIL BDS-2Column(2.1 * 100mm * 5 μ m), Thermo HYPERSIL ODS-2Column(4.6 * 150mm * 5 μ m), Agilent ZORBAX Extend Column(4.6 * 150mm * 5 μ m) three kinds of pillars, discovery with HYPERSIL ODS post to 5 kinds of antistaling agents, especially 2, the retention of 4-D, sensitivity and peak type show obvious advantage.
Adopting acetonitrile and 50% methanol aqueous solution is that mobile phase carries out gradient elution, and 5 kinds of antistaling agents are all separated good, and peak type is sharply symmetrical, just can complete the detection of 5 kinds of antistaling agents, and target peak does not have matrix interference (see figure 1) in 10min.Acetonitrile, methyl alcohol and deionized water are the standing reagent in laboratory, have saved the step of configuration mobile phase, simultaneously little to the loss of pillar, save the time of rinsing pillar simultaneously, have greatly improved work efficiency.
The present invention adopts the mixed mark solution of 0.8 μ g/mL, with peristaltic pump sample loading mode, under Negative electrospray ionization pattern, carry out parent ion full scan, find out accurately molion as parent ion, then the molion of take carries out full scan to its daughter ion as parent ion, finally choose 2 daughter ions that abundance is stronger, optimize the mass spectrum parameters such as its taper hole voltage, collision energy.Choose abundance large and respond the stable quota ion of doing.
Typical curve, the range of linearity and detection limit
Standard solution preparation: accurately take methyl p-hydroxybenzoate, ethyl-para-hydroxybenzoate, 2,4-D, ethyl naphthol and each 0.05g(of 4-phenylphenol standard items are accurate to 0.001g), with methyl alcohol, be mixed with the standard items storing solution that concentration is 1.0mg/mL, 4 ℃ of Refrigerator stores are standby.Storing solution methyl alcohol stepwise dilution, prepares serial working fluid.
Under definite chromatographic condition, to mass concentration, be 0.0,0.05,0.1,0.2, the hybrid standard product of 0.4,0.8,1.2 μ g/mL are measured respectively, with the peak area (Y) of each component, its mass concentration (X, μ g/mL) are carried out to linear regression, the results are shown in Table 3.5 kinds of standard substances are good linear relation within the scope of 0.05～0.8 μ g/mL, and related coefficient all can reach more than 0.99.The detectability that calculates 5 kinds of standard substances with signal to noise ratio (S/N ratio) S/N=3, the detection of 2,4-D is limited to 0.1 μ g/kg, and the detection of methyl p-hydroxybenzoate, ethyl-para-hydroxybenzoate is limited to 0.5 μ g/kg, and the detection of 4-phenylphenol, ethyl naphthol is limited to 1.0 μ g/kg.
Table 3
The recovery and precision analysis
In apple, pears, grape, orange, strawberry and 6 kinds of fresh fruit samples of Kiwi berry, add the mixing mark thing of 0.1,0.2,0.4,0.8 μ g/mL, after said method extraction, purified treatment, carry out HPLC-MS/MS mensuration, apple sample and sample add target using high performance liquid chromatography tandem mass spectrum figure respectively as shown in Figures 2 and 3.Result shows: can be well by 5 kinds of target substance separation under this chromatographic condition.Measured value and actual value calculate recovery rate are pressed in this research, 5 double counting coefficient of variation, and recovery of standard addition and precision the results are shown in Table 4.In 6 kinds of fruit, the background values of Biphenyl Ether, methyl p-hydroxybenzoate, ethyl-para-hydroxybenzoate, ethyl naphthol and 4-phenylphenol is 0mg/kg, the average recovery rate of 5 kinds of standard substances is 81.2%～104.5%, relative standard deviation (RSD) is 1.41%～6.76%, meets the requirement of method for detecting residue to the recovery and precision.
The test of actual sample
In order to verify the feasibility of this method, oranges and tangerines, apple, grape, pears, Kiwi berry, strawberry, peach, black cloth Lee, cherry and 10 kinds of fresh fruit samples of little tomato from fruit wholesale market, supermarket and shop, have been bought respectively.Use the HPLC-MS/MS analytical approach of setting up herein, wherein methyl p-hydroxybenzoate, ethyl-para-hydroxybenzoate, 2, the content of 4-D, ethyl naphthol and 4-phenylphenol are processed and measured to fresh fruit sample.Result shows, does not all detect this 5 kinds of fresh fruit antistaling agents in institute's test sample product.
When the embodiment of the present invention provides, measure the detection method of five kinds of fresh fruit antistaling agent residual quantities, by fresh fruit sample extracted by ether, Solid-Phase Extraction activated-charcoal column purifies, C
18chromatographic column is separated, take acetonitrile and 50% methanol-water carries out gradient elution as mobile phase, the ionization of Negative electrospray ionization (ESI-) pattern, after liquid chromatography-mass spectrography (LC-MS/MS) is measured, result shows: methyl p-hydroxybenzoate, ethyl-para-hydroxybenzoate, 2,4-D, ethyl naphthol and 4-phenylphenol standard substance present good linear relationship within the scope of 0.05～0.8 μ g/mL, and coefficient R 2 is all greater than 0.99.Within the scope of this, recovery of standard addition is 81.2%～104.5%, relative standard deviation (RSD) is 1.41%～6.76%, 2, the detection of 4-D is limited to 0.1 μ g/kg, the detection of methyl p-hydroxybenzoate and ethyl-para-hydroxybenzoate is limited to 0.5 μ g/kg, and the detection of 4-phenylphenol and ethyl naphthol is limited to 1.0 μ g/kg.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (6)
1. a detection method of simultaneously measuring five kinds of fresh fruit antistaling agent residual quantities, is characterized in that, described five kinds of antisepsis antistaling agents are methyl p-hydroxybenzoate, ethyl-para-hydroxybenzoate, 2,4-dichlorphenoxyacetic acid, ethyl naphthol and 4-phenylphenol; The described detection method of simultaneously measuring five kinds of fresh fruit antistaling agent residual quantities comprises the following steps:
Sample extraction: testing sample is smashed to pieces, vibrated after adding the ether of 4～7 times of testing sample quality, ultrasonic, then add the sodium chloride vibration of 0.8～1.2 times of sample quality, and centrifugal, get organic phase;
Concentrated: to repeat described sample extraction step 2～3 time, be concentrated into 1/15～1/20 of its volume after merging described organic phase, obtain liquid to be clean;
Purify: pour after solid-phase extraction column described liquid to be clean into be 1:1 with volume ratio acetoneand ethyl acetate mixed liquor wash-out, eluent blows to doing with nitrogen, and methanol constant volume, to 1mL, after 0.45 μ m membrane filtration, obtains liquid to be measured;
Sample determination: liquid chromatography mass Instrument measuring, wherein, liquid phase chromatogram condition is chromatographic column: Thermo HYPERSIL ODS-2C
18post, 4.6 * 150mm * 5 μ m, eluent gradient elution requirement is in Table 1; Column temperature is 40 ℃; Sample size is 2 μ L.
Table 1
Mass spectrum condition: electric spray ion source: ESI-, collision gas CAD:6psi, gas curtain atmospheric pressure CUR:24psi, atomization gas pressure GS1:55psi, auxiliary heater GS2:55psi, spray voltage IS:-4500V, ion source temperature TEM:600 ℃, the multiple-reaction monitoring mass spectrum parameter of five kinds of fresh fruit antistaling agents is in Table 2, and wherein, with * is quota ion.
Table 2
2. the detection method of simultaneously measuring five kinds of fresh fruit antistaling agent residual quantities according to claim 1, it is characterized in that, described sample extraction is for to smash testing sample to pieces, after adding the ether of 5～6 times of testing sample quality, vibrate, ultrasonic, add again the sodium chloride vibration of 1 times of sample quality, centrifugal, get organic phase.
3. the detection method of simultaneously measuring five kinds of fresh fruit antistaling agent residual quantities according to claim 1 and 2, is characterized in that, the described ultrasonic time is 4～8min, and described centrifugal speed is 4000～5000r/min, and the described centrifugal time is 4～8min.
4. the detection method of simultaneously measuring five kinds of fresh fruit antistaling agent residual quantities according to claim 1, is characterized in that, described organic phase is concentrated adopts parallel evaporimeter concentrated.
5. the detection method of simultaneously measuring five kinds of fresh fruit antistaling agent residual quantities according to claim 1, is characterized in that, described solid-phase extraction column is activated charcoal pillar Supelclean
tMeNVI
tM-Carb SPE Tubes.
6. the detection method of simultaneously measuring five kinds of fresh fruit antistaling agent residual quantities according to claim 5, is characterized in that, after the acetone ethyl acetate mixture activation that described activated charcoal pillar is first 1:1 by volume ratio, carries out scavenging solution wash-out again.
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| CN114441682A (en) * | 2022-01-28 | 2022-05-06 | 山东省食品药品检验研究院 | Method for rapidly determining p-phenylphenol in fruits and vegetables by high performance liquid chromatography |
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