CN103235052B - Determination method for 2,4-dinitrophenol in dry food packaging paper - Google Patents
Determination method for 2,4-dinitrophenol in dry food packaging paper Download PDFInfo
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Abstract
The present invention discloses a determination method for 2,4-dinitrophenol in dry food packaging paper. The determination method comprises: standard working solution preparation, sample solution preparation, high-performance liquid chromatography analysis, standard curve drawing and result calculation. According to the determination method, extraction is performed on dry food packaging paper to obtain 2,4-dinitrophenol, a DAD detector is adopted to carry out qualitative confirmation and quantitative detection on the 2,4-dinitrophenol, operation is simple and accurate, the target object and other impurity chromatographic peaks brought by the sample matrix can be well separated with the used chromatographic conditions, good linear correlation is provided, a detection limit is 0.44 mg/kg, an average relative standard deviation is 1.6%, a standard addition recovery rate is 93.20-116.62%, and characteristics of rapidness, accuracy, high sensitivity, good repeatability, high recovery rate and the like are provided. The determination method is especially suitable for determination of 2,4-dinitrophenol content in dry food packaging paper.
Description
Technical field
The invention belongs to wrappage physical and chemical index detection technique field, be specifically related to the assay method of 2,4-DNP in a kind of dry food wrapping paper (mainly comprising fast food wrapping paper, candy paper using, wheaten food paper using etc.).
Background technology
2,4-DNP (2,4-dinitrophenol is called for short DNP), is slightly soluble in water, is dissolved in the organic solvents such as ethanol, ether, benzene and chloroform.2,4-DNP belongs to protoplasmic poison, and toxicity is very large, people's per os minimum lethal dose LDLo is 36mg/kg, and rat oral median lethal dose (LD50) is 30mg/kg, and its mechanism of poisoning is mainly to directly act on energetic supersession, stimulate oxidizing process, suppress phosphorylation process.Be mainly used in the industry such as dyestuff, developer, medicine, indicator, pesticide and wood preservation.
Dry food wrapping paper is important component part indispensable in packaging for foodstuff, and its security is the very important aspect of food overall security, and the source of packaging material for food security control is raw materials for production at all.Very likely can serve as raw materials for production in view of 2,4-DNP, in the production run of paper, use.Therefore exploring one 2,4-DNP detection method fast and accurately, the 2,4-DNP in dry food wrapping paper is control effectively, ensure the safety in utilization of dry food wrapping paper, is very urgent and necessary.
At present, the detection method of trace 2,4-DNP is had multiple, have respectively liquid phase chromatography, spectrophotometric method, vapor-phase chromatography, full spectral technique analysis, gas chromatography/mass spectrometry method, Differential Pulse Voltammetry, electrochemical assay etc.Wherein, liquid phase chromatography is highly sensitive, reproducible, is easy to apply; Color resin spectrophotometric method is the method for innovation, but complex pretreatment is not easy to automation mechanized operation; Full spectral technique is suitable for the discrimination analysis containing various structures analog in sample, and shortcoming is that instrument is more expensive, is difficult to apply; In view of the polarity of 2,4-DNP is stronger, in the analytic process of GC, can cause peak shape seriously to trail, and post effect is seriously reduced, therefore, 2,4-DNP be not suitable for directly using vapor-phase chromatography or gas chromatography/mass spectrometry method to analyze; Differential Pulse Voltammetry, electrochemical assay selectivity is high, sensitivity good, but is not easy to apply.
In sum, liquid phase chromatography is one of important means of measuring 2,4-DNP content.But existing bibliographical information concentrates on the report of the aspect such as waste water, environmental sample mostly, 2,4-DNP residual in paper is not studied.
Summary of the invention
Goal of the invention: for the deficiencies in the prior art, the object of this invention is to provide in a kind of dry food wrapping paper 2, the assay method of 2, 4-dinitrophenol, the method adopts liquid phase chromatography (use diode array detector) to measure in dry food wrapping paper 2,2, 4-dinitrophenol, can fast, accurately detect the content of 2,4-DNP in dry food wrapping paper, there is the features such as result is accurate, interference is few.
Technical scheme: in order to realize foregoing invention object, the technical solution used in the present invention is as follows:
An assay method for 2,4-DNP in dry food wrapping paper, comprises the following steps:
(1) preparation of standard operation solution: taking 2,4-DNP as standard items, make solvent with methyl alcohol, be configured to standard operation solution through stepwise dilution;
(2) preparation of sample solution: take dry food wrapping paper sample, pulverize, use solvent mechanical shaking extraction, extract is crossed to organic filter membrane, obtain sample solution;
(3) efficient liquid phase chromatographic analysis: use with diode array detector high performance liquid chromatograph (HPLC) standard operation solution and sample solution are detected to analysis;
(4) Specification Curve of Increasing and result are calculated.
In step (1), specifically comprise the following steps:
(1) standard reserving solution: accurately take 0.1～0.3g reference material 2,4-DNP, disperse, dissolve with ethanol, then be settled in the volumetric flask of 100mL as solvent with methyl alcohol, obtain the standard reserving solution that concentration is 1000～3000mg/L;
(2) standard operation solution: accurately pipette respectively 5 μ L, 25 μ L, 100 μ L, 250 μ L, 500 μ L and 1000 μ L standard reserving solutions, be settled in the volumetric flask of 100mL as solvent with methyl alcohol.
In step (2), the preparation of sample solution specifically comprises the following steps: take 0.5g sample (being accurate to 0.1mg), be cut into the fragment below 5mm × 5mm, being placed in 50mL tool plug triangular flask, accurately pipetting 10mL extraction solvent methyl alcohol, is oscillation extraction 20min under the condition of 120 revs/min at rotating speed, get appropriate extract centrifugal 5min in centrifuge tube, get supernatant liquor, after 0.45 μ m organic system membrane filtration, obtain sample solution.
In step (3), chromatographiccondition is: chromatographic column is C18 chromatographic column, and specification is 150 mm(length) × 4.6 mm(internal diameters) × 5.0 μ m(filler granularities); Column temperature is 30 DEG C; Flow velocity is 1.0 mL/min; Sample size is 10 μ L; Mobile phase A is methyl alcohol, and the acetum that Mobile phase B is 1% adopts isocratic elution (wherein volume ratio V/V is 35%/65%～65%/35%); The detection wavelength of DAD detecting device is 258nm; Be about 10 min analysis time.
In step (4), described Specification Curve of Increasing and result are calculated as follows: taking the concentration of 2,4-DNP in working solution as horizontal ordinate, taking the peak area of 2,4-DNP in chromatogram as ordinate, carry out regretional analysis, obtain typical curve; By the chromatographic peak area of 2,4-DNP in the sample solution recording under the same terms, substitution working curve, tries to achieve the content of 2,4-DNP in sample.
Beneficial effect: compared with prior art, in dry food wrapping paper of the present invention 2, the assay method of 2, 4-dinitrophenol, from dry food wrapping paper, extraction obtains 2,2, 4-dinitrophenol, utilizes DAD detecting device that it is carried out qualitative confirmation and is quantitatively detected, and has the features such as quick, accurate, sensitivity is high, be particularly suitable for measuring the content of 2,4-DNP in dry food wrapping paper.
Brief description of the drawings
Fig. 1 is the chromatogram of standard operation solution;
Fig. 2 is the chromatogram of mark-on sample;
Fig. 3 is the spectrogram of 2,4-DNP.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described.
Embodiment 1
An assay method for 2,4-DNP in dry food wrapping paper, detailed process is as follows:
(1) preparation of standard operation solution
Take 0.2g reference material 2,4-DNP, first disperse, dissolve with 10 mL ethanol, then be settled in the volumetric flask of 100mL as solvent with methyl alcohol, obtain the standard reserving solution that concentration is 2000mg/L.Accurately pipette respectively again 5 μ L, 25 μ L, 100 μ L, 250 μ L, 500 μ L and 1000 μ L standard reserving solutions, be settled to methanol solvate in the volumetric flask of 100mL.This series standard working solution concentration is respectively 0.1mg/L, 0.5mg/L, 2.0mg/L, 5.0mg/L, 10mg/L and 20mg/L.Standard operation solution needs matching while using.
(2) preparation of sample solution
Take 0.5g outturn (being accurate to 0.1 mg), be cut into the fragment below 5mm × 5mm, be placed in 50mL tool plug triangular flask, accurately pipette 10mL extraction solvent methyl alcohol, be oscillation extraction 20min under the condition of 120 revs/min at rotating speed, get appropriate extract centrifugal 5min in centrifuge tube, get supernatant liquor, after 0.45 μ m organic system membrane filtration, obtain sample solution.
(3) efficient liquid phase chromatographic analysis
The working stamndard solution of extracting sample solution, mark-on sample solution, 6 variable concentrations carries out respectively liquid-phase chromatographic analysis, its chromatographiccondition is: chromatographic column is C18 chromatographic column, and specification is 150mm(length) × 4.6mm(internal diameter) × 5.0 μ m(filler granularities); Column temperature is 30 DEG C; Flow velocity is 1.0mL/min; Sample size is 10 μ L; Mobile phase A is methyl alcohol, and the acetum that Mobile phase B is 1% adopts isocratic elution (wherein volume ratio V/V is 45%/55%); The detection wavelength of DAD detecting device is 258nm; Be about 10 min analysis time.As shown in Figure 1, the chromatogram of mark-on sample as shown in Figure 2 for the chromatogram of standard operation solution.
(4) Specification Curve of Increasing and result are calculated
First with in standard operation solution 2, the concentration of 2, 4-dinitrophenol is horizontal ordinate, with in chromatogram 2, the peak area of 2, 4-dinitrophenol is ordinate, carries out regretional analysis, obtains typical curve, get the standard operation solution of least concentration, do 10 Parallel testing analyses, calculate its standard deviation, taking concentration corresponding to the standard deviations of 3 times as detection limit.The data result such as regression equation, related coefficient corresponding with standard working curve is as follows:
The regression equation of 2,4-DNP: Y=34.20X+1.223, related coefficient is 0.99994, the range of linearity 0.1～20 mg/L, detectability 0.438 mg/kg.
Then by the chromatographic peak area of 2,4-DNP in the sample solution recording under the same terms, substitution working curve, tries to achieve the content of 2,4-DNP in sample, and computing formula is as follows:
In formula: X is the content of 2,4-DNP in sample, mg/kg; C is the concentration by 2,4-DNP in the sample solution reading on standard working curve, mg/L; C
0for the concentration of 2,4-DNP in the blank solution by reading on standard working curve, mg/L; V is the volume of extraction system, mL; M is the quality of sample, g.
(5) sample determination
As stated above, get 20 dry food wrapping paper samples (comprising fast food wrapping paper, candy paper using, wheaten food paper using etc.) and detect, all do not detect 2,4-DNP.In addition, taking a candy paper using as determination object (measured value is not for detecting), adding concentration to it is the standard specimen of 80.0 mg/kg, and fructufy measured value is 81.53mg/kg, and relative deviation is 0.95%, and the accuracy of visible measurement result is better.
The qualitative confirmation of embodiment 2 object 2,4-DNPs
Must meet following two conditions to the qualitative confirmation method of object 2,4-DNP: 1. contrast the permissible error that the retention time of sample chromatogram figure is ± 2.5% with the retention time of standard model chromatogram; 2. contrast (Fig. 3 is its spectrogram, as can be seen from the figure, has stronger uv absorption at wavelength 258nm place, Gu Analysis about Selection wavelength is 258nm) with the spectrogram of standard model, the spectrogram of sample must be consistent.
Embodiment 3 mobile phase ratio optimizations
The present embodiment is optimized mobile phase ratio used of the present invention, and concrete operation step is with reference to embodiment 1:
Composition and the ratio of flow phase of the present invention are optimized, and concrete outcome is in table 1.For different dryness food wrappers, its matrix variation differs greatly, and object goes out the impurity peaks too early easily being brought by sample substrate at peak to be disturbed, and for this reason, the appearance time of object should extend as far as possible.For this reason, integration objective thing appearance time (retention time), and the response condition of peak area and peak height, mobile phase adopts methyl alcohol/1% acetic acid (volume ratio V/V is 45/55) for testing conditions preferably.
The composition of table 1 mobile phase and ratio optimization test findings
| Sequence number | Mobile phase composition (V/V) | Retention time (min) | Peak area | Peak height |
| 1 | Acetonitrile/1% acetic acid (50/50) | 2.974 | 337.01 | 52.2 |
| 2 | Methyl alcohol/1% acetic acid (35/65) | 9.571 | 362.68 | 17.8 |
| 3 | Methyl alcohol/1% acetic acid (45/55) | 5.505 | 347.72 | 26.2 |
| 4 | Methyl alcohol/1% acetic acid (50/50) | 4.319 | 342.68 | 32.6 |
| 5 | Methyl alcohol/1% acetic acid (55/45) | 3.504 | 339.45 | 41.5 |
| 6 | Methyl alcohol/1% acetic acid (65/35) | 2.477 | 337.87 | 49.2 |
The detection method of embodiment 4 precision and recovery of standard addition
The detection of precision: taking a candy paper using as object (measured value is not for detecting), in its mark-on sample of 6 replicate determinations (mark-on level is 7 mg/kg) 2, the content of 2, 4-dinitrophenol, calculate relative standard deviation, the precision of investigation method, result is as shown in table 2, and the reproducible of this method has been described.
The precision (n=6) of table 2 method
| Sequence number | Measured value (mg/kg) |
| 1 | 6.61 |
| 2 | 6.95 |
| 3 | 7.05 |
| 4 | 6.33 |
| 5 | 6.47 |
| 6 | 6.11 |
| Relative standard deviation (%) | 5.49 |
The detection of the recovery: choose 2 kinds of representational samples (fast food wrapping paper and candy paper using) as mark-on sample substrate, make respectively the mark-on sample of basic, normal, high 3 concentration levels, the recovery of investigation method, result is as shown in table 3, the recovery of fast food wrapping paper is 93.00～116.62%, the recovery of candy paper using is 93.20～109.61%, has illustrated that the recovery of this method is better.
Table 3 2,4-DNP recovery of standard addition
Above embodiment interior mark liquid used and standard solution only describe as an example of one of them concentration example, typical curve and regression equation that the interior mark liquid that other concentration value configures and standard solution obtain through liquid-phase chromatographic analysis are same as the previously described embodiments, are not enumerating at this.Just method for a better understanding of the present invention of illustrated embodiment, does not have any restriction, and said method or the method that is equal to above-mentioned situation are all included in the protection domain of technical scheme of the present invention.
Claims (4)
1. an assay method for 2,4-DNP in dry food wrapping paper, is characterized in that, comprises the following steps:
(1) taking 2,4-DNP as standard items, make solvent with methyl alcohol, be configured to standard operation solution through stepwise dilution;
(2) take dry food wrapping paper sample, pulverize, use solvent mechanical shaking extraction, extract is crossed to organic filter membrane, obtain sample solution;
(3) use with diode array detector high performance liquid chromatograph standard operation solution and sample solution are detected to analysis;
(4) Specification Curve of Increasing and result are calculated;
In step (3), chromatographiccondition is: chromatographic column is C18 chromatographic column, and specification is 150mm × 4.6mm × 5.0 μ m; Column temperature is 30 DEG C; Flow velocity is 1.0mL/min; Sample size is 10 μ L; Mobile phase A is methyl alcohol, the acetum that Mobile phase B is 1%, and the volume ratio of A and B is 35%/65%～65%/35%, adopts isocratic elution; The detection wavelength of DAD detecting device is 258nm.
2. the assay method of 2,4-DNP in dry food wrapping paper according to claim 1, is characterized in that, in step (1), concrete operations are as follows:
(1) standard reserving solution: accurately take 0.1～0.3g reference material 2,4-DNP, disperse, dissolve with ethanol, then be settled in the volumetric flask of 100mL as solvent with methyl alcohol, obtain the standard reserving solution that concentration is 1000～3000mg/L;
(2) standard operation solution: accurately pipette respectively 5 μ L, 25 μ L, 100 μ L, 250 μ L, 500 μ L and 1000 μ L standard reserving solutions, be settled in the volumetric flask of 100mL as solvent with methyl alcohol.
3. in dry food wrapping paper according to claim 12, the assay method of 2, 4-dinitrophenol, it is characterized in that, in step (2), concrete operations are as follows: take 0.5g sample, be cut into the fragment below 5mm × 5mm, be placed in 50mL tool plug triangular flask, accurately pipette 10mL extraction solvent methyl alcohol, be oscillation extraction 20min under the condition of 120 revs/min at rotating speed, get extract centrifugal 5min in centrifuge tube, get supernatant liquor, after 0.45 μ m organic system membrane filtration, obtain sample solution.
4. in dry food wrapping paper according to claim 12, the assay method of 2, 4-dinitrophenol, it is characterized in that, in step (4), described Specification Curve of Increasing and result are calculated as follows: taking the concentration of 2,4-DNP in working solution as horizontal ordinate, with in chromatogram 2, the peak area of 2, 4-dinitrophenol is ordinate, carries out regretional analysis, obtains typical curve; By the chromatographic peak area of 2,4-DNP in the sample solution recording under the same terms, substitution working curve, tries to achieve the content of 2,4-DNP in sample.
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| CN105866267B (en) * | 2016-03-29 | 2018-08-31 | 福建中烟工业有限责任公司 | The extraction of residual solvent, detection method and kit and purposes in packaging material |
| RU2757540C1 (en) * | 2020-12-21 | 2021-10-18 | федеральное государственное бюджетное образовательное учреждение высшего образования "Кемеровский государственный университет" (КемГУ) | Method for voltammetric determination of 2,4-dinitrophenol in water and water bodies |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63246659A (en) * | 1986-12-09 | 1988-10-13 | Snow Brand Milk Prod Co Ltd | Determination of carbonyl group-containing organic component by fast liquid chromatograph |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS63246659A (en) * | 1986-12-09 | 1988-10-13 | Snow Brand Milk Prod Co Ltd | Determination of carbonyl group-containing organic component by fast liquid chromatograph |
Non-Patent Citations (4)
| Title |
|---|
| Determination of 11 priority pollutant phenols in wastewater using dispersive liquid—liquid microextraction followed by high-performance liquid chromatography-diode-array detection;Mohammad Saraji et al;《Anal Bioanal Chem》;20100213;第396卷(第7期);2685-2693页 * |
| HPLC法同时测定工作场所空气中的苯酚、对硝基苯酚、2,4-二硝基苯酚、2,4,6-三硝基苯酚和间苯二酚;王若燕等;《中国卫生检验杂志》;20100610;第20卷(第6期);1362-1363页 * |
| Mohammad Saraji et al.Determination of 11 priority pollutant phenols in wastewater using dispersive liquid—liquid microextraction followed by high-performance liquid chromatography-diode-array detection.《Anal Bioanal Chem》.2010,第396卷(第7期), |
| 王若燕等.HPLC法同时测定工作场所空气中的苯酚、对硝基苯酚、2,4-二硝基苯酚、2,4,6-三硝基苯酚和间苯二酚.《中国卫生检验杂志》.2010,第20卷(第6期), |
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