CN103197009A - Measuring method of residual quantity of preservatives - Google Patents
Measuring method of residual quantity of preservatives Download PDFInfo
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- CN103197009A CN103197009A CN2013101242516A CN201310124251A CN103197009A CN 103197009 A CN103197009 A CN 103197009A CN 2013101242516 A CN2013101242516 A CN 2013101242516A CN 201310124251 A CN201310124251 A CN 201310124251A CN 103197009 A CN103197009 A CN 103197009A
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Abstract
The invention discloses a measuring method of the residual quantity of preservatives. The measuring method of the residual quantity of the preservatives is used for simultaneously measuring five preservatives through using gas chromatography-mass spectrometry, the five preservatives comprise methyl p-hydroxybenzoate, ethyl p-hydroxybenzaote, beta-naphthol, 4-phenylphenol and diphenyl ether; and the measuring method of the residual quantity of the preservatives specifically comprises the following steps of: smashing a sample to be measured, performing ultrasonic extraction on the sample to be measured through an organic solvent, concentrating the sample to be measured through a parallel evaporator for the first time, purifying the sample to be measured through a solid phase extraction column, concentrating the purified sample to be measured for the second time, fixing the volume through methanol, filtering the treated sample, and performing gas chromatography-mass spectrometry analysis on the filtered sample. The method has the advantages of being convenient and quick for operation and good in repeatability, and the like, the adding standard recovery of the method is 80.5-104%, the relative standard deviation (RSD) is 1.21-6.41%, and the method is capable of meeting the monitoring demands of the residual quantities of the five preservatives in fresh fruits.
Description
Technical field
The present invention relates to the food safety detection field, relate in particular to a kind of assay method of antisepsis antistaling agent residual quantity, simultaneously five kinds of antisepsis antistaling agents are measured by the gaschromatographic mass spectrometry method.
Background technology
" food additives use standard " (GB2760-2011) made clear and definite regulation to antistaling agent kind that allow to use in the fresh fruit and maximum use amount, residual quantity.Though the chemical preservation antistaling agent has the effect of anti-corrosive fresh-keeping, but can produce the toxic action that has in various degree to human body mostly, bring adverse effect to health, even situations such as carcinogenic, teratogenesis, mutagenesis occur, strengthen the residual monitoring of antiseptic and fresh-keeping agent for fruits significant for this reason.Parabens (methyl esters, ethyl ester), ethyl naphthol, 4-phenylphenol, biphenyl ether are the fruit antistaling agents of relatively using always, and they have certain toxicity to human body.
In the prior art, the antisepsis antistaling agent residual quantity is measured, in the majority with chromatography.Also there is the high performance liquid chromatography of employing that parabens, ethyl naphthol and 4-phenylphenol residual quantity are distinguished method for measuring.Owing in the prior art mensuration of antisepsis antistaling agent is all carried out respectively, can't measure simultaneously, therefore, testing process is loaded down with trivial details, the labor intensive material resources.
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 assay method of antisepsis antistaling agent residual quantity, the mensuration side of antisepsis antistaling agent residual quantity provided by the present invention realizes method for measuring simultaneously by the gaschromatographic mass spectrometry method to five kinds of antisepsis antistaling agents, is intended to solve problem loaded down with trivial details to the testing process of antisepsis antistaling agent in the prior art.
Technical scheme of the present invention is as follows:
A kind of assay method of antisepsis antistaling agent residual quantity, wherein, the assay method of described antisepsis antistaling agent residual quantity is by the gaschromatographic mass spectrometry method five kinds of antisepsis antistaling agents to be realized measuring simultaneously, and wherein five kinds of antisepsis antistaling agents are to comprise methyl hydroxybenzoate, ethyl-para-hydroxybenzoate, ethyl naphthol, 4-phenylphenol and biphenyl ether; The assay method of described antisepsis antistaling agent residual quantity specifically may further comprise the steps:
Testing sample is smashed, with organic solvent testing sample is carried out ultrasonic extraction, after parallel evaporimeter concentrates for the first time, adopt the Solid-Phase Extraction column purification, methanol constant volume after concentrating is for the second time filtered the back for gas chromatography-mass spectrometry analysis.
The assay method of described antisepsis antistaling agent residual quantity, wherein, the organic solvent that adopts in the described ultrasonic leaching process is normal hexane, ethyl acetate or ether.
The assay method of described antisepsis antistaling agent residual quantity, wherein, the organic solvent that adopts in the described ultrasonic leaching process is ether.
The assay method of described antisepsis antistaling agent residual quantity, wherein, described ultrasonic leaching process is specific as follows:
Add ether in testing sample, ultrasonic extraction 5～6min again behind vortex vibration 2～3min adds sodium chloride vortex 2～3min again, the centrifugal 5～10min of 4000～5000r/min; Divide 2 times again and add ether, the centrifugal 5～10min of 4000～5000r/min behind vortex vibration 2～3min merges organic phase.
The assay method of described antisepsis antistaling agent residual quantity, wherein, the process of described employing Solid-Phase Extraction column purification adopts activated charcoal pillar or C
18Post purifies.
The assay method of described antisepsis antistaling agent residual quantity, wherein, the process of described employing Solid-Phase Extraction column purification is to adopt the activated charcoal pillar to purify, its detailed process is:
The activated charcoal pillar activates with eluent earlier, uses the eluent wash-out after pouring the concentrate of testing sample into the activated charcoal pillar again;
Described eluent is ethyl acetate and/or acetone, and consumption is 5～10 times of concentrate volume.
The assay method of described antisepsis antistaling agent residual quantity, wherein, described eluent is the equal-volume mixed liquor of ethyl acetate and acetone.
The assay method of described antisepsis antistaling agent residual quantity, wherein, described second time, concentration process was to adopt nitrogen to blow, and impelled the eluent volatilization.
The assay method of described antisepsis antistaling agent residual quantity, wherein, described filter process is to adopt 0.45 μ m filter membrane to filter.
The assay method of described antisepsis antistaling agent residual quantity, wherein, the mass spectrum condition is: chromatographic column: the HP-5 capillary chromatographic column; The temperature of injection port is 240 ℃～260 ℃; Input mode is split sampling not; Sampling volume is 0.5 μ L～1.0 μ L; The chromatographic column heating schedule is 80 ℃ of initial column temperatures, keeps 0.5min, and 30 ℃/min is warming up to 200 ℃, keeps 1.5min, and 25 ℃/min is warming up to 280 ℃, keeps 0.5min; Carrier gas is helium; GC-MS transmission line temperature is 240 ℃～270 ℃; Electron energy is 70eV; Ion source temperature is 230 ℃; Level Four bar temperature is 150 ℃; Mass scanning scope: be 50～350m/z.
Beneficial effect: the assay method of antisepsis antistaling agent residual quantity provided by the present invention, by residual quantity realization simultaneously qualitative, the quantitative measurement of gaschromatographic mass spectrometry method to five kinds of antisepsis antistaling agents, advantages such as that this method has is easy and simple to handle, quick, good reproducibility, the method recovery of standard addition is between 80.5%～104%, relative standard deviation (RSD) is 1.21%～6.41%, can satisfy above-mentioned 5 kinds of antisepsis antistaling agent residual quantities monitoring requirement in the fresh fruit.
Description of drawings
Fig. 1 is that eluting solvent (ethyl acetate) and volume thereof are to the synoptic diagram that influences of standard substance elution efficiency; Wherein, a represents biphenyl ether; B represents methyl p-hydroxybenzoate; C represents ethyl-para-hydroxybenzoate; D represents ethyl naphthol; E represents the 4-phenylphenol.
Fig. 2 is that eluting solvent (acetone) and volume thereof are to the synoptic diagram that influences of standard substance elution efficiency; Wherein, a represents biphenyl ether; B represents methyl p-hydroxybenzoate; C represents ethyl-para-hydroxybenzoate; D represents ethyl naphthol; E represents the 4-phenylphenol.
Fig. 3 is that eluting solvent (acetone and ethyl acetate equal-volume mixed liquor) and volume thereof are to the synoptic diagram that influences of standard substance elution efficiency; Wherein, a represents biphenyl ether; B represents methyl p-hydroxybenzoate; C represents ethyl-para-hydroxybenzoate; D represents ethyl naphthol; E represents the 4-phenylphenol.
The recovery total ion current figure of grape sample grape in Fig. 4 embodiment of the invention.
The recovery total ion current figure of grape mark-on sample in Fig. 5 embodiment of the invention; Wherein, 1 is biphenyl ether; 2 is methyl p-hydroxybenzoate; 3 is ethyl-para-hydroxybenzoate; 4 is ethyl naphthol; 5 is the 4-phenylphenol.
Embodiment
The invention provides a kind of assay method of antisepsis antistaling agent residual quantity, clearer, clear and definite for making purpose of the present invention, technical scheme and effect, below the present invention is described in more detail.Should be appreciated that specific embodiment described herein only in order to explaining the present invention, and be not used in restriction the present invention.
The assay method of a kind of antisepsis antistaling agent residual quantity provided by the present invention, by the gaschromatographic mass spectrometry method five kinds of antisepsis antistaling agents are realized measuring simultaneously, wherein five kinds of antisepsis antistaling agents are methyl p-hydroxybenzoate, ethyl-para-hydroxybenzoate, ethyl naphthol, 4-phenylphenol and biphenyl ether.Particularly, the assay method of described antisepsis antistaling agent residual quantity may further comprise the steps:
Testing sample is smashed, with organic solvent testing sample is carried out ultrasonic extraction, after parallel evaporimeter concentrates for the first time, adopt the Solid-Phase Extraction column purification, methanol constant volume after concentrating is for the second time filtered the back for gas chromatography-mass spectrometry analysis.
Wherein, carry out the described organic solvent that ultrasonic extraction adopts and to be organic solvents such as normal hexane, ethyl acetate and ether.Biphenyl ether recovery height may be relevant with its physical property of volatilizing easily, when carrying out recovery test, when serving as the extraction solvent with normal hexane and ethyl acetate, the recovery of biphenyl ether is relatively poor, is lower than 70%, and when ether is the extraction solvent, the recovery of biphenyl ether has raising, can reach more than 80%, therefore, the preferred ether that adopts is as extracting solvent in technical solution of the present invention.
Return the preferred operations process of described ultrasonic extraction among the present invention, testing sample with 2.0g is example, detailed process is: add 10～15mL ether (being about 3～6 times testing sample weight) in testing sample, ultrasonic extraction 5～6min again behind vortex vibration 2～3min, add 2.0～3.0g sodium chloride vortex 2～3min again, the centrifugal 5～10min of 4000～5000r/min; Divide 2 times again and add 10～15mL ether (being about 3～6 times testing sample weight), centrifugal 5～10min(revolution is the same behind vortex vibration 2～3min), merge organic phase, about 20～28mL(is about 7～10 times testing sample weight).Method of extraction is adopted in this ultrasonic extraction twice, has guaranteed the complete of extraction, to obtain the good recovery.
The process that concentrates the described first time adopts parallel evaporimeter that sample extraction liquid is concentrated, its specific operation process can for: get 10～20mL organic phase and on parallel evaporimeter (pressure 689mbar), be concentrated into about 1mL.Resulting sample concentration liquid is used for purified treatment, has guaranteed the collimation of extracting.
Because the separation of the meeting of the materials such as pigment in fruit jamming target thing has been carried out the Solid-Phase Extraction column purification to crude extract in the technical program for this reason.The process of described employing Solid-Phase Extraction column purification can adopt activated charcoal pillar and C
18Post is preferably and adopts the activated charcoal pillar to purify, and is better than C because the activated charcoal pillar is removed the effect of pigment in the sample
18Pillar, and its adsorptive power to object is also strong.Return among the present invention and adopt the activated charcoal pillar to carry out the optimal technical scheme of Solid-Phase Extraction column purification, be specially: the activated charcoal pillar activates with eluent earlier, uses the eluent wash-out after pouring the concentrate of testing sample into the activated charcoal pillar again.Because the kind of eluent and volume can be all the elution efficiency of object are impacted, in order to have guaranteed good elute effect, suitable eluent and effluent volume have been chosen among the present invention, described eluent can be ethyl acetate and/or acetone, and the consumption of described eluent is the concentrate volume of 5～10 times of employings.Because biphenyl ether and methyl p-hydroxybenzoate, ethyl ester are easier to wash-out, and acetone is better than ethyl acetate to the eluting power of ethyl naphthol and 4-phenylphenol, concentrate sample with 1mL is example, when adopting 8 times after the ethyl acetate of concentrate volume and acetone carry out wash-out to concentrate, the recovery of 5 kinds of objects all can reach more than 90%, as depicted in figs. 1 and 2.Preferably, ethyl acetate and acetone equal-volume mixing back elute effect is better, eluent consumption volume can be reduced to 5 times of concentrate volumes, as shown in Figure 3.Therefore, described eluent is preferably and adopts ethyl acetate and the isopyknic mixed liquor of acetone.And in the process that activates, can adopt the eluent of 2～3 times of concentrate volumes that the activated charcoal pillar is activated, guarantee good clean-up effect.
Described second time, concentration process was to adopt nitrogen to blow, and impelled the eluent volatilization, when the solution that obtains when purification is blown near doing by nitrogen, used methanol constant volume again.
Described filter process is to adopt 0.45 μ m filter membrane to filter, and further discharges the interference of other materials, guarantees to measure effect.
Among the present invention, take by weighing the standard items of methyl p-hydroxybenzoate, ethyl-para-hydroxybenzoate, ethyl naphthol, 4-phenylphenol and biphenyl ether, after the methyl alcohol preparation, be diluted to the standard solution of a series of concentration, air feed phase chromatograph mass spectrum analysis, external standard method is quantitative, makes typical curve.
The computing formula of five kinds of antisepsis antistaling agents is as follows in the testing sample:
Wherein, the X in the formula refers to the content of five kinds of antistaling agents in the sample, and unit is every kilogram (mg/kg) of milligram; C refers to that unit is every milliliter of microgram (μ g/mL) through looking into the concentration that typical curve calculates gained sample introduction liquid; V refers to the sample constant volume, and unit is milliliter (mL); M refers to sample weighting amount, and unit is gram (g); Result of calculation remains to 2 significant digits.
In the present invention, give the condition of utilizing gas chromatography mass spectrometer that the testing sample treating fluid is detected, have good separating effect with this understanding.Actual conditions is:
Chromatographic column: HP-5 capillary chromatographic column or suitable post, 30m * 0.25mm(internal diameter), 0.25 μ m(thickness);
Injection port: 240 ℃～260 ℃;
Input mode: do not shunt;
Sampling volume: 0.5 μ L～1.0 μ L;
Column temperature: 80 ℃ of initial column temperatures keep 0.5min; 30 ℃/min is warming up to 200 ℃, keeps 1.5min; 25 ℃/min is warming up to 280 ℃, keeps 0.5min;
Carrier gas: helium;
GC-MS transmission line temperature: 240 ℃～270 ℃;
Electron energy: 70eV;
Ion source temperature: 230 ℃;
Level Four bar temperature: 150 ℃;
Mass scanning scope: 50～350m/z.
Adopt method provided by the present invention, detecting of biphenyl ether is limited to 0.05mg/kg, detecting of methyl p-hydroxybenzoate, ethyl-para-hydroxybenzoate, ethyl naphthol and 4-phenylphenol is limited to 0.1mg/kg, recovery of standard addition is between 80.5%～104%, and relative standard deviation RSD is 1.21%～6.41%.Method provided by the present invention is easy and simple to handle, and sensitivity is higher, selectivity good, and detection limit and the recovery all can satisfy the detection requirement.This shows that method of the present invention is the detection of five kinds of antistaling agents in the fresh fruit, a kind of method of implementing reliably be convenient to is provided, can satisfy the needs of daily research, market monitoring and production testing.
Embodiment
Be that the series standard solution of 0.2,0.4,1.0,2.0 and 4.0 μ g/mL is set up working curve with mass concentration, linearly dependent coefficient sees Table 1.5 kinds of standard substances (biphenyl ether, methyl p-hydroxybenzoate, ethyl-para-hydroxybenzoate, ethyl naphthol, 4-phenylphenol) are the good linear relation in 0.2～4.0 μ g/mL scope, the facies relationship number average can reach 0.99.With the detection limit of 3 times of signal-noise ratio computation methods, detecting of biphenyl ether is limited to 0.05mg/kg, and detecting of methyl p-hydroxybenzoate, ethyl-para-hydroxybenzoate, ethyl naphthol and 4-phenylphenol is limited to 0.1mg/kg.
Working curve and the detection limit of 5 kinds of standard substances of table 1
The precision of five kinds of antistaling agent residual quantities and the recovery detect in fresh fruit, implement as follows:
In oranges and tangerines, apple, grape, pears, Kiwi berry, 6 kinds of fresh fruit samples of strawberry, add the mixing mark thing of 4 μ g/mL, after extracted by ether, activated-charcoal column purified treatment, carry out GC-MS and measure.
Described extracted by ether, activated-charcoal column decontamination process are specific as follows:
Take by weighing 2.0g sample (being accurate to 0.001g) and put into the 50mL centrifuge tube, add the 10mL ether, ultrasonic extractions 5min again behind the vortex vibration 2min, adding 2.0g sodium chloride is vortex 2min again, the centrifugal 5min of 4000r/min; Divide 2 times again and add the 10mL ether, centrifugal 5min(revolution is the same behind the vortex vibration 2min), merge organic phase.Get the 20mL organic phase and on parallel evaporimeter (pressure 689mbar), be concentrated into about 1mL, be used for purified treatment.Adopt activated charcoal pillar (Supelclean
TMENVI
TM-Carb SPE Tubes, 3mL 0.25g) purifies.The activated charcoal pillar use earlier 2mL acetone: ethyl acetate solution (volume ratio is 1:1) activates, and liquid to be clean is poured into used 5mL acetone behind the solid-phase extraction column: ethyl acetate solution (volume ratio is 1:1) wash-out.Eluent blows near with nitrogen to be done, and to 1mL, supplies gas chromatography-mass spectrometry analysis with methanol constant volume behind the 0.45 μ m membrane filtration.
The mass spectrum condition is: chromatographic column: the HP-5 capillary chromatographic column; The temperature of injection port is 250 ℃; Input mode is split sampling not; Sampling volume is 1.0 μ L; The chromatographic column heating schedule is 80 ℃ of initial column temperatures, keeps 0.5min, and 30 ℃/min is warming up to 200 ℃, keeps 1.5min, and 25 ℃/min is warming up to 280 ℃, keeps 0.5min; Carrier gas is helium; GC-MS transmission line temperature is 250 ℃; Electron energy is 70eV; Ion source temperature is 230 ℃; Level Four bar temperature is 150 ℃; The mass scanning scope is 50～350m/z.
Press measured value and actual value calculate recovery rate, 5 double counting coefficient of variation, and then calculate recovery of standard addition and precision result.Total ion current figure behind grape sample blank and the mark-on sees Fig. 4 and shown in Figure 5.Press measured value and actual value calculate recovery rate, 5 double counting coefficient of variation, recovery of standard addition and precision the results are shown in Table 2.
Recovery of standard addition and the precision analysis (n=5) of 5 kinds of standard substances of table 2 in 6 kinds of fruit
As can be seen from the above results, the background values of biphenyl ether, methyl p-hydroxybenzoate, ethyl-para-hydroxybenzoate, ethyl naphthol and 4-phenylphenol is 0mg/kg in 6 kinds of fruit, the recovery of standard addition of 5 kinds of standard substances is between 80.5%～104%, and relative standard deviation is 1.21%～6.41%.
In sum, the invention provides the method for the residual quantity of 5 kinds of antisepsis antistaling agents (comprising methyl p-hydroxybenzoate, ethyl-para-hydroxybenzoate, ethyl naphthol, 4-phenylphenol and biphenyl ether) in a kind of can be simultaneously qualitative, quantitative measurement fresh fruit, advantages such as that this method has is easy and simple to handle, quick, good reproducibility, the method recovery of standard addition is between 80.5%～104%, relative standard deviation (RSD) is 1.21%～6.41%, can satisfy above-mentioned 5 kinds of antisepsis antistaling agent residual quantities monitoring requirement in the fresh fruit.
Should be understood that application of the present invention is not limited to above-mentioned giving an example, for those of ordinary skills, can be improved according to the above description or conversion that all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (10)
1. the assay method of an antisepsis antistaling agent residual quantity, it is characterized in that, the assay method of described antisepsis antistaling agent residual quantity is by the gaschromatographic mass spectrometry method five kinds of antisepsis antistaling agents to be realized measuring simultaneously, and wherein five kinds of antisepsis antistaling agents are to comprise methyl hydroxybenzoate, ethyl-para-hydroxybenzoate, ethyl naphthol, 4-phenylphenol and biphenyl ether; The assay method of described antisepsis antistaling agent residual quantity specifically may further comprise the steps:
Testing sample is smashed, with organic solvent testing sample is carried out ultrasonic extraction, after parallel evaporimeter concentrates for the first time, adopt the Solid-Phase Extraction column purification, methanol constant volume after concentrating is for the second time filtered the back for gas chromatography-mass spectrometry analysis.
2. the assay method of antisepsis antistaling agent residual quantity according to claim 1 is characterized in that, the organic solvent that adopts in the described ultrasonic leaching process is normal hexane, ethyl acetate or ether.
3. the assay method of antisepsis antistaling agent residual quantity according to claim 1 is characterized in that, the organic solvent that adopts in the described ultrasonic leaching process is ether.
4. the assay method of antisepsis antistaling agent residual quantity according to claim 1 is characterized in that, described ultrasonic leaching process is specific as follows:
Add ether in testing sample, ultrasonic extraction 5～6min again behind vortex vibration 2～3min adds sodium chloride vortex 2～3min again, the centrifugal 5～10min of 4000～5000r/min; Divide 2 times again and add ether, the centrifugal 5～10min of 4000～5000r/min behind vortex vibration 2～3min merges organic phase.
5. the assay method of antisepsis antistaling agent residual quantity according to claim 1 is characterized in that, the process of described employing Solid-Phase Extraction column purification adopts activated charcoal pillar or C
18Post purifies.
6. the assay method of antisepsis antistaling agent residual quantity according to claim 1 is characterized in that, the process of described employing Solid-Phase Extraction column purification is to adopt the activated charcoal pillar to purify, and its detailed process is:
The activated charcoal pillar activates with eluent earlier, uses the eluent wash-out after pouring the concentrate of testing sample into the activated charcoal pillar again;
Described eluent is ethyl acetate and/or acetone.
7. the assay method of antisepsis antistaling agent residual quantity according to claim 6 is characterized in that, described eluent is the equal-volume mixed liquor of ethyl acetate and acetone.
8. the assay method of antisepsis antistaling agent residual quantity according to claim 6 is characterized in that, described second time, concentration process was to adopt nitrogen to blow, and impelled the eluent volatilization.
9. the assay method of antisepsis antistaling agent residual quantity according to claim 1 is characterized in that, described filter process is to adopt 0.45 μ m filter membrane to filter.
10. the assay method of antisepsis antistaling agent residual quantity according to claim 1 is characterized in that, the mass spectrum condition is: chromatographic column: the HP-5 capillary chromatographic column; The temperature of injection port is 240 ℃～260 ℃; Input mode is split sampling not; Sampling volume is 0.5 μ L～1.0 μ L; The chromatographic column heating schedule is 80 ℃ of initial column temperatures, keeps 0.5min, and 30 ℃/min is warming up to 200 ℃, keeps 1.5min, and 25 ℃/min is warming up to 280 ℃, keeps 0.5min; Carrier gas is helium; GC-MS transmission line temperature is 240 ℃～270 ℃; Electron energy is 70eV; Ion source temperature is 230 ℃; Level Four bar temperature is 150 ℃; The mass scanning scope is 50～350m/z.
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| CN104614466A (en) * | 2015-02-16 | 2015-05-13 | 国家烟草质量监督检验中心 | Method for measuring preservatives in tobacco juice of electronic cigarettes |
| CN105699475A (en) * | 2016-01-14 | 2016-06-22 | 中国检验检疫科学研究院 | Method for quick detection of parabens preservative forbidden in cosmetics |
| CN105911171A (en) * | 2016-04-14 | 2016-08-31 | 梧州市产品质量检验所 | Determination method for preservative in food |
| CN109557209A (en) * | 2018-12-17 | 2019-04-02 | 邵阳学院 | A method of based on methyl p-hydroxybenzoate in vortex oscillation measurement drug |
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- 2013-04-11 CN CN201310124251.6A patent/CN103197009B/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103592403A (en) * | 2013-11-15 | 2014-02-19 | 广东省惠州市质量计量监督检测所 | Detection method for simultaneous determination of residual quantity of five fresh fruit preservatives |
| CN103592403B (en) * | 2013-11-15 | 2015-02-18 | 广东省惠州市质量计量监督检测所 | Detection method for simultaneous determination of residual quantity of five fresh fruit preservatives |
| CN104614466A (en) * | 2015-02-16 | 2015-05-13 | 国家烟草质量监督检验中心 | Method for measuring preservatives in tobacco juice of electronic cigarettes |
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| CN105699475A (en) * | 2016-01-14 | 2016-06-22 | 中国检验检疫科学研究院 | Method for quick detection of parabens preservative forbidden in cosmetics |
| CN105911171A (en) * | 2016-04-14 | 2016-08-31 | 梧州市产品质量检验所 | Determination method for preservative in food |
| CN109557209A (en) * | 2018-12-17 | 2019-04-02 | 邵阳学院 | A method of based on methyl p-hydroxybenzoate in vortex oscillation measurement drug |
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| Publication number | Publication date |
|---|---|
| CN103197009B (en) | 2014-08-13 |
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