CN103592403B - 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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- CN103592403B CN103592403B CN201310571385.2A CN201310571385A CN103592403B CN 103592403 B CN103592403 B CN 103592403B CN 201310571385 A CN201310571385 A CN 201310571385A CN 103592403 B CN103592403 B CN 103592403B
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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 field of detection of food safety, particularly relate to the detection method of a kind of Simultaneously test five kinds of fresh fruit antistaling agent residual quantities.
Background technology
" food additives use standard " (GB2760-2011) has made clear and definite regulation to the antistaling agent kind allowing 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 to human body the toxic action had in various degree, bring adverse effect to health, 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, 2,4-dichlorphenoxyacetic acids (2,4-D) are the fruit antistaling agents relatively commonly used, and they have certain toxicity to human body.
Have in prior art high performance liquid chromatography to parabens, ethyl naphthol, 2,4-D and 4-phenylphenol residual quantity carry out difference method for measuring, but testing process is loaded down with trivial details, labor intensive material resources.Also have the report adopting and utilize GC-MS Simultaneously test methyl p-hydroxybenzoate, ethyl-para-hydroxybenzoate, ethyl naphthol, 4-phenylphenol and Biphenyl Ether residual quantity, 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 the detection method of a kind of Simultaneously test 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 the detection method of a kind of Simultaneously test 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 acids, ethyl naphthol and 4-phenylphenol; The detection method of described Simultaneously test five kinds of fresh fruit antistaling agent residual quantities comprises the following steps:
Sample extraction: smashed to pieces by testing sample, vibrates after adding the ether of testing sample quality 4 ~ 7 times, ultrasonic, then adds the sodium chloride vibration of sample quality 0.8 ~ 1.2 times, centrifugal, gets organic phase;
Concentrated: to repeat described sample extraction step 2 ~ 3 time, after merging described organic phase, be concentrated into 1/15 ~ 1/20 of its volume, obtain liquid to be clean;
Purification: the acetoneand ethyl acetate mixed liquor wash-out after pouring described liquid to be clean into solid-phase extraction column by volume ratio being 1:1, eluent nitrogen blows to dry, and methanol constant volume, to 1mL, after 0.45 μm of membrane filtration, obtains liquid to be measured;
Sample determination: liquid chromatography mass Instrument measuring, wherein, liquid phase chromatogram condition is chromatographic column: ThermoHYPERSIL ODS-2C
18post, 4.6 × 150mm × 5 μm, eluent gradient elution requirement is in table 1; Column temperature is 40 DEG C; Sample size is 2 μ L.
Table 1
Mass Spectrometry Conditions 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 DEG C, the multiple-reaction monitoring mass spectrometry parameters of five kinds of fresh fruit antistaling agents is in table 2, and wherein, band *'s is quota ion.
Table 2
The detection method of Simultaneously test provided by the present invention five kinds of fresh fruit antistaling agent residual quantities, by liquid chromatography-mass spectrometry, qualitative, quantitative measurement is simultaneously realized to the residual quantity of five kinds of antisepsis antistaling agents, this detection method is short for 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 mark (0.4 μ g/mL) of five kinds of fresh fruit antistaling agents, 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 clearly understand, 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, be not intended to limit the present invention.
The invention provides the detection method of a kind of Simultaneously test 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 acids, ethyl naphthol and 4-phenylphenol; The detection method of described Simultaneously test five kinds of fresh fruit antistaling agent residual quantities comprises the following steps:
S01: sample extraction: smashed to pieces by testing sample, vibrates after adding the ether of testing sample quality 4 ~ 7 times, ultrasonic, then adds the sodium chloride vibration of sample quality 0.8 ~ 1.2 times, centrifugal, gets organic phase;
S02: 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;
S03: purification: the acetoneand ethyl acetate mixed liquor wash-out after pouring described liquid to be clean into solid-phase extraction column by volume ratio being 1:1, eluent dries up, and methanol constant volume, to 1mL, after 0.45 μm of 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 μm, eluent gradient elution requirement is in table 1; Column temperature is 40 DEG C; Sample size is 2 μ L.
Table 1
Mass Spectrometry Conditions: 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 DEG C, the multiple-reaction monitoring mass spectrometry parameters of five kinds of fresh fruit antistaling agents is in table 2, and wherein, band *'s is quota ion.
Table 2
In step S01, preferably testing sample is smashed to pieces, vibrate after adding the ether of testing sample quality 5 ~ 6 times, ultrasonic, then add the sodium chloride vibration of sample quality 1 times, 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 oscillation 2min, adds the 2.0g sodium chloride centrifugal 4 ~ 8min of vortex 2min, 4000 ~ 5000r/min again, gets organic phase.
In step S02, repeat step S01, extract 2 ~ 3 times, preferably extract 2 times, merge organic phase.Organic phase is concentrated into about 1mL, for purified treatment in Parallel evaporator (pressure 689mbar).Parallel evaporator such as selects Switzerland BUCHI.
In step S03, preferably adopt activated charcoal pillar (Supelclean
tMeNVI
tM-Carb SPE Tubes, 3mL, 0.25g) purification.Activated charcoal pillar first uses 2mL acetone: ethyl acetate solution (volume ratio is 1:1) activates, and uses 5mL acetone: ethyl acetate solution (volume ratio is 1:1) wash-out after pouring liquid to be clean into solid-phase extraction column.Eluent nitrogen blows near dry, by methanol constant volume to 1mL, for efficient liquid phase chromatographic analysis after 0.45 μm of membrane filtration.
In step S04, liquid chromatograph can select Shimadzu LC-30 series, Japanese Shimadzu Corporation; 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 compares Thermo HYPERSIL BDS-2Column(2.1 × 100mm × 5 μm), Thermo HYPERSIL ODS-2Column(4.6 × 150mm × 5 μm), Agilent ZORBAX Extend Column(4.6 × 150mm × 5 μm) three kinds of pillars, find with HYPERSIL ODS post 5 kinds of antistaling agents, especially retention, sensitivity and the peak type of 2,4-D show obvious advantage.
Adopt acetonitrile and 50% methanol aqueous solution to be that mobile phase carries out gradient elution, 5 kinds of antistaling agents are all separated well, and peak type is sharply symmetrical, just can complete the detection of 5 kinds of antistaling agents, and target peak do not have matrix interference (see figure 1) in 10min.Acetonitrile, methyl alcohol and deionized water are the standing reagent in laboratory, eliminate the step of configuration mobile phase, simultaneously little to the loss of pillar, save the time of rinsing pillar simultaneously, substantially increase work efficiency.
The present invention adopts the mixed mark solution of 0.8 μ g/mL, under Negative electrospray ionization pattern, parent ion full scan is carried out with peristaltic pump sample loading mode, find out accurately molion as parent ion, then be that parent ion carries out full scan to its daughter ion with molion, finally choose 2 daughter ions that abundance is stronger, optimize the mass spectrometry parameters such as its taper hole voltage, collision energy.Choose abundance comparatively large and respond and stable do quota ion.
Typical curve, the range of linearity and detection limit
Standard solution is prepared: 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), be mixed with methyl alcohol the standard items storing solution that concentration is 1.0mg/mL, 4 DEG C of Refrigerator stores are for subsequent use.Storing solution methyl alcohol stepwise dilution, preparation series of working liquids.
Be 0.0,0.05 to mass concentration under the chromatographic condition determined, 0.1,0.2,0.4,0.8, the hybrid standard product of 1.2 μ g/mL measure respectively, carry out linear regression, the results are shown in Table 3 with the peak area of each component (Y) to its mass concentration (X, μ g/mL).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.Calculate the detectability of 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 Analyze
The mixing mark thing of 0.1,0.2,0.4,0.8 μ g/mL is added in apple, pears, grape, orange, strawberry and Kiwi berry 6 kinds of fresh fruit samples, 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 separated by 5 kinds of target substances under this chromatographic condition.Measured value is pressed in this research and actual value calculates the recovery, and 5 double counting coefficient of variation, 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, from fruit wholesale market, supermarket and shop, have purchased oranges and tangerines, apple, grape, pears, Kiwi berry, strawberry, peach, black cloth Lee, cherry and little tomato 10 kinds of fresh fruit samples respectively.Use the HPLC-MS/MS analytical approach set up herein, fresh fruit sample is processed and measure wherein methyl p-hydroxybenzoate, ethyl-para-hydroxybenzoate, 2,4-D, the content of ethyl naphthol and 4-phenylphenol.Result shows, does not all detect this 5 kinds of fresh fruit antistaling agents in institute's test sample product.
The detection method of the Simultaneously test that the embodiment of the present invention provides 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, with acetonitrile and 50% methanol-water for mobile phase carries out gradient elution, Negative electrospray ionization (ESI-) pattern ionizes, after liquid chromatography-mass spectrography (LC-MS/MS) measures, 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 amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. a detection method for Simultaneously test 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 acids, ethyl naphthol and 4-phenylphenol; The detection method of described Simultaneously test five kinds of fresh fruit antistaling agent residual quantities comprises the following steps:
Sample extraction: smashed to pieces by testing sample, vibrates after adding the ether of testing sample quality 4 ~ 7 times, ultrasonic, then adds the sodium chloride vibration of sample quality 0.8 ~ 1.2 times, centrifugal, gets organic phase;
Concentrated: to repeat described sample extraction step 2 ~ 3 time, after merging described organic phase, be concentrated into 1/15 ~ 1/20 of its volume, obtain liquid to be clean;
Purification: the acetoneand ethyl acetate mixed liquor wash-out after pouring described liquid to be clean into solid-phase extraction column by volume ratio being 1:1, eluent nitrogen blows to dry, and methanol constant volume, to 1mL, after 0.45 μm of 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 μm, eluent gradient elution requirement is in table 1; Column temperature is 40 DEG C; Sample size is 2 μ L;
Table 1
Mass Spectrometry Conditions: 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 DEG C, the multiple-reaction monitoring mass spectrometry parameters of five kinds of fresh fruit antistaling agents is in table 2, and wherein, band *'s is quota ion;
Table 2
2. the detection method of Simultaneously test according to claim 1 five kinds of fresh fruit antistaling agent residual quantities, it is characterized in that, described sample extraction is for smash to pieces testing sample, vibrate after adding the ether of testing sample quality 5 ~ 6 times, ultrasonic, add the sodium chloride vibration of sample quality 1 times again, centrifugal, get organic phase.
3. the detection method of Simultaneously test according to claim 1 and 2 five kinds of fresh fruit antistaling agent residual quantities, 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 test according to claim 1 five kinds of fresh fruit antistaling agent residual quantities, is characterized in that, the concentrated Parallel evaporator that adopts of described organic phase concentrates.
5. the detection method of Simultaneously test according to claim 1 five kinds of fresh fruit antistaling agent residual quantities, is characterized in that, described solid-phase extraction column is activated charcoal pillar Supelclean
tMeNVI
tM-CarbSPE Tubes.
6. the detection method of Simultaneously test according to claim 5 five kinds of fresh fruit antistaling agent residual quantities, is characterized in that, described activated charcoal pillar is first carry out scavenging solution wash-out again after the acetone ethyl acetate mixture activation of 1:1 by volume ratio.
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| CN114441682B (en) * | 2022-01-28 | 2023-03-17 | 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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| US6537823B1 (en) * | 2000-04-24 | 2003-03-25 | Sciteck Diagnostics, Inc. | Method for detection of bromine in urine using liquid chemistry dry chemistry test pads and lateral flow |
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| WO2004056444A1 (en) * | 2002-12-19 | 2004-07-08 | Council Of Scientific And Industrial Research | A process for extraction of antioxidant principles from pomegranate fruit waste |
| CN103063764A (en) * | 2012-12-21 | 2013-04-24 | 林维宣 | Detection method for residual quantity of multiple preservatives in cosmetics |
| CN103197009A (en) * | 2013-04-11 | 2013-07-10 | 广东省惠州市质量计量监督检测所 | Measuring method of residual quantity of preservatives |
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