CN103344724A - Analysis method of mancozeb - Google Patents
Analysis method of mancozeb Download PDFInfo
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- CN103344724A CN103344724A CN2013103057492A CN201310305749A CN103344724A CN 103344724 A CN103344724 A CN 103344724A CN 2013103057492 A CN2013103057492 A CN 2013103057492A CN 201310305749 A CN201310305749 A CN 201310305749A CN 103344724 A CN103344724 A CN 103344724A
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Abstract
The invention discloses an analysis method of mancozeb. The method comprises the following steps of: using a high efficiency liquid chromatography, taking mixing solution of methanol and buffer solution as a mobile phase by adopting a C18 chromatographic column; carrying out detection at proper flow velocity, column temperature and detection wavelength; and analyzing the content of the mancozeb. The analysis method disclosed by the invention is simple, convenient, fast, high in accuracy, and good in precision; a reagent can be saved; and industrial pollution also can be reduced.
Description
Technical field
The present invention relates to analysis of agricultural drugs field, specifically, relate to a kind of analytical approach of high performance liquid chromatography.
Background technology
Mancozeb, chemical name are the co-ordination complex of ethylene bisdithiocarbamic manganese and zinc ion.Pure product are white powder, and industrial goods are canescence or pale yellow powder, water insoluble and most of organic solvents, but can be dissolved in the pyridine, to light, heat, moist unstable, easily decomposite carbon disulphide, when storing for 35 ℃, every month weightlessness 0.18%, high temperature is met moist and is met acid and then decompose.Rat acute per os LD5012800～14000mg/kg.
Mancozeb is used for the protection germifuge of many leaf diseases, and the downy mildew in wheat rust, the leaf blight of corn, the vegetables, anthracnose and black spot of fruit tree are had good effect.Mancozeb and other mixed pesticides, effect is better.Complex compound method, GC method and the GB GB20699-2006 method that has a large amount of reports: HPLC to measure both at home and abroad to the Mancozeb analytical approach also has the potpourri of L-cysteine hydrochloric acid and EDTA and iodomethane methylation method to survey Mancozeb at present.Yet, also there are a lot of deficiencies at present in the reported method, for example, the GB20699-2006 method is measured to be needed to use many solution, and the heavy metal liquid waste processing that contains in reaction product trouble.It is concentrated that the potpourri of L-cysteine hydrochloric acid and EDTA and iodomethane methylation method sample need extraction, merging organic phase and nitrogen to blow, complex operation step.
Summary of the invention
In order to solve the many shortcomings that exist in the prior art, the invention provides a kind of analytical approach of Mancozeb, this method good separating effect, reduce pollution factor, save cost, and accuracy and precision all can obtain such as the result that can fit like a glove etc. and to be satisfied with ratio content with the GB chemical analysis.
The analytical approach of the Mancozeb that the present invention relates to is achieved through the following technical solutions:
The present invention uses high performance liquid chromatography (HPLC) that Mancozeb content is analyzed
A kind of analytical approach of Mancozeb may further comprise the steps:
(1) preparation of standard solution: take by weighing standard items, taking by weighing afterwards, use mixed solution B dissolves, the constant volume mixing is standby, described mixed solution B is for adding the solution that sodium sulphite is mixed with in mixed solution A, described mixed solution A is the mixed aqueous solution of EDTA, dipotassium hydrogen phosphate and 4-butyl ammonium hydrogen sulfate;
(2) preparation of sample solution: take by weighing the Mancozeb sample, taking by weighing afterwards, the described mixed solution B of use dissolves, the constant volume mixing is standby;
(3) carrying out HPLC analyzes: adopt the C18 chromatographic column, flowing is mutually: methyl alcohol: buffer solution=7:3(V/V), flow velocity is 0.6-1.2ml/min, and column temperature is 27-40 ℃, and the detection wavelength is 270-290nm, and sample size is 20 μ L.The solution of getting the preparation of step (1) and step (2) respectively carries out HPLC to be analyzed, and obtains Mancozeb HPLC chromatogram, and described buffer solution is adjusted to described mixed solution A the solution of alkalescence for using KOH or NAOH;
(4) according to Mancozeb content in liquid chromatography external standard method formula (I) calculation sample:
Wherein:
A1 represents in the standard solution for peak area,
A2 represents in the sample solution for peak area,
M1 represents standard items quality (mg),
M2 represents sample quality (mg),
P represents standard items quality percentage (%),
X represents Mancozeb percentage composition in the sample.
Described mixed solution A is for containing the mixed aqueous solution of 10mM EDTA, dipotassium hydrogen phosphate and 4-butyl ammonium hydrogen sulfate respectively.
The solution that described mixed solution B is mixed with for the sodium sulphite that adds 1g/L in described mixed solution A.
The pH value of described buffer solution is 9.5.
Compared with prior art, the present invention has the following advantages:
1. the present invention is flowed and to be reached dilute sample mutually and carry out under alkali condition, avoids Mancozeb to meet acid and decomposes;
2. HPLC detection analytical approach of the present invention accuracy reaches: average recovery rate is 99.23%, and precision reaches: standard deviation is 0.12%, and the coefficient of variation is 0.13%;
3. HPLC detection analytical approach of the present invention and GB20699-2006 analytical approach comparing result deviation are all in 0.5% scope.
Description of drawings
Fig. 1-4 is respectively the HPLC figure of standard items, sample, sample, standard items among the embodiment 2;
Fig. 5 is the Mancozeb canonical plotting.
Embodiment
In order better to explain the present invention, the invention will be further described below in conjunction with specific embodiment.The instrument that uses in the following example is: liquid chromatograph band UV-detector, 7725 sampling valve data workstations (S); Chromatographic column is: (C18) 250 * 4.6(PH4-13); Injector is: 100 μ L injectors.Mancozeb standard items described in the embodiment are Mancozeb content 88.0wt%, and other material and reagent all can obtain if no special instructions from commercial channels.
In following examples, mixed solution A is for containing the mixed aqueous solution of EDTA, dipotassium hydrogen phosphate and the 4-butyl ammonium hydrogen sulfate of 10mM respectively;
Buffer solution is adjusted to 9.5 solution for using KOH or NAOH with the PH of mixed solution A;
The solution that mixed solution B is mixed with for the sodium sulphite that adds 1g/L in mixed solution A.
Preparation standard product solution: the standard items 100mg(that accurately takes by weighing content and be 88.0wt% is accurate to 0.01mg), in the 100ml volumetric flask, add an amount of mixed solution B, the excusing from death dissolving, add above-mentioned mixed solution B again and be settled to scale, get 1ml behind the mixing in the 25ml volumetric flask, use mixed solution B dilution to be settled to scale, mixing is standby.
Preparation sample solution: accurately take by weighing about Mancozeb sample 100mg (being accurate to 0.01mg) in the 100ml volumetric flask, add an amount of mixed solution B, the excusing from death dissolving, add above-mentioned mixed solution B again and be settled to scale, get 1ml behind the mixing in the 25ml volumetric flask, use mixed solution B dilution to be settled to scale, mixing is standby.
Adopt the C18 chromatographic column, flowing is methyl alcohol mutually: buffer solution=7:3(V/V), flow velocity is 0.9ml/min, and column temperature is 29 ℃, and the detection wavelength is 282nm, and sample size is 20 μ L.Enter standard solution under these conditions, repeat sample introduction till the difference of the peak area that adjacent twice sample introduction obtains is less than 1%, carrying out HPLC according to the order of standard items, sample, sample, standard items then analyzes, the results are shown in accompanying drawing 1-4, thereby obtain Mancozeb content, its content is 91.07%.
Adopt the C18 chromatographic column, flowing is methyl alcohol mutually: buffer solution=7:3(V/V), flow velocity is 0.6ml/min, and column temperature is 27 ℃, and the detection wavelength is 270nm, and sample size is 20 μ L.Enter standard solution under these conditions, repeat sample introduction till the difference of the peak area that adjacent twice sample introduction obtains is less than 1%, analyze according to the order of standard items, sample, sample, standard items then, obtain Mancozeb content, its content is 90.17%.
Adopt the C18 chromatographic column, flowing is methyl alcohol mutually: buffer solution=7:3(V/V), flow velocity is 1.2ml/min, and column temperature is 40 ℃, and the detection wavelength is 285nm, and sample size is 20 μ L.Enter standard solution under these conditions, repeat sample introduction till the difference of the peak area that adjacent twice sample introduction obtains is greater than 1%, analyze according to the order of standard items, sample, sample, standard items then, obtain Mancozeb content, its content is 89.69%.
Adopt the C18 chromatographic column, flowing is methyl alcohol mutually: buffer solution=7:3(V/V), flow velocity is 0.6ml/min, and column temperature is 27 ℃, and the detection wavelength is 270nm, and sample size is 20 μ L.Enter standard solution under these conditions, repeat sample introduction till the difference of the peak area that adjacent twice sample introduction obtains is less than 1%, carry out HPLC according to the order of standard items, sample, sample, standard items then and analyze, obtain Mancozeb content, its content is 90.29%.
Embodiment 6
Adopt the C18 chromatographic column, flowing is methyl alcohol mutually: buffer solution=7:3(V/V), flow velocity is 1.2ml/min, and column temperature is 40 ℃, and the detection wavelength is 285nm, and sample size is 20 μ L.Enter standard solution under these conditions, repeat sample introduction till the difference of the peak area that adjacent twice sample introduction obtains is greater than 1%, carry out HPLC according to the order of standard items, sample, sample, standard items then and analyze, obtain Mancozeb content, its content is 89.96%.
Adopt the C18 chromatographic column, flowing is methyl alcohol mutually: buffer solution=7:3(V/V), flow velocity is 0.9ml/min, and column temperature is 30 ℃, and the detection wavelength is 285nm, and sample size is 20 μ L.Enter standard solution under these conditions, repeat sample introduction till the difference of the peak area that adjacent twice sample introduction obtains is less than 1%, analyze according to the order of standard items, sample, sample, standard items then, obtain Mancozeb content, its content is 90.26%.
Adopt the C18 chromatographic column, flowing is methyl alcohol mutually: buffer solution=7:3(V/V), flow velocity is 1.0ml/min, and column temperature is 35 ℃, and the detection wavelength is 270nm, and sample size is 20 μ L.Enter standard solution under these conditions, repeat sample introduction till the difference of the peak area that adjacent twice sample introduction obtains is less than 1%, carry out HPLC according to the order of standard items, sample, sample, standard items then and analyze, obtain Mancozeb content, its content is 91.19%.
Adopt the C18 chromatographic column, flowing is methyl alcohol mutually: buffer solution=7:3(V/V), flow velocity is 0.9ml/min, and column temperature is 29 ℃, and the detection wavelength is 290nm, and sample size is 20 μ L.Enter standard solution under these conditions, repeat sample introduction till the difference of the peak area that adjacent twice sample introduction obtains is less than 1%, carry out HPLC according to the order of standard items, sample, sample, standard items then and analyze, obtain Mancozeb content, its content is 90.74%.
Below be the embodiment that analysis Mancozeb content method of the present invention is investigated
Take by weighing the Mancozeb standard items of different quality respectively, method according to the preparation standard product solution among the embodiment 1 is made the Mancozeb standard solution that concentration is respectively 40.096mg/L, 42.092mg/L, 44.096mg/L, 46.144mg/L and 48.060mg/L, and according to the chromatographic condition sample introduction among the embodiment 2, measure peak area, measurement result sees Table 1.
The table 1 Mancozeb quantitative test range of linearity is measured
Be horizontal ordinate with the weighing sample, peak area is ordinate, the drawing standard curve, and obtaining regression equation is Y=45310X+871789, coefficient R
2=0.991, typical curve is seen Fig. 5.
The test of embodiment 11 precision
Take by weighing respectively different quality the Mancozeb sample (batch: 201301015-2) according to the method for preparing sample solution among the embodiment 1 and the chromatographic condition identical with embodiment 2, preparation Mancozeb sample solution, sample introduction also detects, measure peak area, and going out the content of Mancozeb in each Mancozeb sample according to the typical curve regression equation calculation of embodiment 10, it the results are shown in Table 2.
Table 2 Mancozeb quantitative test precision measurement result
Table 2 result shows that the standard deviation of the Mancozeb content of acquisition is 0.12%, and the coefficient of variation is 0.13%.
Add the different Mancozeb standard items of measuring respectively in the former medicine of Mancozeb, be made into the sample of known content, sample introduction also detects, and measures peak area, and it the results are shown in Table 3 to measure its recovery of calculating according to embodiment 1.
Table 3 Mancozeb quantitative test accuracy determination result
Table 3 result shows that the average recovery rate of Mancozeb standard items is 99.23%, shows the accuracy height that uses efficient liquid phase chromatographic analysis Mancozeb content.
Use HPLC of the present invention to detect analytical approach (according to the chromatographic condition of embodiment 2) respectively and with the GB20699-2006 analytical approach Mancozeb content in the Mancozeb sample is analyzed, analysis result sees Table 4.
The Mancozeb content that the different analytical approachs of table 4 obtain
Table 4 result shows, HPLC of the present invention detect analytical approach and GB20699-2006 analytical approach to the deviation of Mancozeb content in 0.5% scope.
Though illustrate and described exemplary embodiments more of the present invention, but those skilled in the art should know, without departing from the principles and spirit of the present invention, can make change to these exemplary embodiments, scope of the present invention is limited by claim and equivalent thereof.
Claims (4)
1. the analytical approach of a Mancozeb said method comprising the steps of:
(1) preparation of standard solution: take by weighing standard items, use mixed solution B dissolving, constant volume mixing standby after taking by weighing respectively, described mixed solution B is for adding the solution that sodium sulphite is mixed with in mixed solution A, described mixed solution A is the mixed aqueous solution of EDTA, dipotassium hydrogen phosphate and 4-butyl ammonium hydrogen sulfate;
(2) preparation of sample solution: take by weighing the Mancozeb sample, use described mixed solution B dissolving, constant volume mixing standby respectively;
(3) carrying out HPLC analyzes: adopt the C18 chromatographic column, flowing is mutually: methyl alcohol: buffer solution=7:3(V/V), flow velocity is 0.6-1.2ml/min, and column temperature is 27-40 ℃, and the detection wavelength is 270-290nm, and sample size is 20 μ L,
The solution of getting the preparation of step (1) and step (2) respectively carries out HPLC to be analyzed, and obtains Mancozeb HPLC chromatogram, and described buffer solution is adjusted to described mixed solution A the solution of alkalescence for using KOH or NAOH;
(4) according to Mancozeb content in liquid chromatography external standard method formula (I) calculation sample:
Wherein:
A1 represents in the standard solution for peak area
A2 represents in the sample solution for peak area,
M1 represents standard items quality (mg),
M2 represents sample quality (mg),
P represents standard items quality percentage (%),
X represents Mancozeb percentage composition in the sample.
2. the analytical approach of Mancozeb according to claim 1, described mixed solution A is for containing the mixed aqueous solution of 10mM EDTA, dipotassium hydrogen phosphate and 4-butyl ammonium hydrogen sulfate respectively.
3. the analytical approach of Mancozeb according to claim 1, the solution that described mixed solution B is mixed with for the sodium sulphite that adds 1g/L in described mixed solution A.
4. the analytical approach of Mancozeb according to claim 1, the pH value of described buffer solution is 9.5.
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| CN104535672A (en) * | 2014-12-04 | 2015-04-22 | 苏州国环环境检测有限公司 | Method for detecting residues of mancozeb in cucumber |
| CN107315056A (en) * | 2017-07-08 | 2017-11-03 | 万舒（北京）医药科技有限公司 | The method for determining the DTPA Ca in rat plasma biological sample |
| CN107340343A (en) * | 2017-07-08 | 2017-11-10 | 万舒（北京）医药科技有限公司 | The method for determining the DTPA Zn in human plasma biological sample |
| CN109738566A (en) * | 2019-02-27 | 2019-05-10 | 贵州健安德科技有限公司 | A method of utilizing copper 8-hydroxyquinolinate in UPLC-MS/MS method detection water |
| CN109738563A (en) * | 2018-12-29 | 2019-05-10 | 华南农业大学 | A kind of non-derived detection method of ethylene bisdithiocarbamic salt pesticide |
| CN110596276A (en) * | 2019-10-14 | 2019-12-20 | 普洱市质量技术监督综合检测中心 | Method for measuring dithiocarbamate residues in tea leaves by headspace-gas chromatography-mass spectrometry |
| CN112014504A (en) * | 2020-08-31 | 2020-12-01 | 河北双吉化工有限公司 | Analysis method of Dyson series |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104535672A (en) * | 2014-12-04 | 2015-04-22 | 苏州国环环境检测有限公司 | Method for detecting residues of mancozeb in cucumber |
| CN107315056A (en) * | 2017-07-08 | 2017-11-03 | 万舒（北京）医药科技有限公司 | The method for determining the DTPA Ca in rat plasma biological sample |
| CN107340343A (en) * | 2017-07-08 | 2017-11-10 | 万舒（北京）医药科技有限公司 | The method for determining the DTPA Zn in human plasma biological sample |
| CN107315056B (en) * | 2017-07-08 | 2019-09-24 | 万舒（北京）医药科技有限公司 | The method for measuring the DTPA-Ca in rat plasma biological sample |
| CN109738563A (en) * | 2018-12-29 | 2019-05-10 | 华南农业大学 | A kind of non-derived detection method of ethylene bisdithiocarbamic salt pesticide |
| CN109738566A (en) * | 2019-02-27 | 2019-05-10 | 贵州健安德科技有限公司 | A method of utilizing copper 8-hydroxyquinolinate in UPLC-MS/MS method detection water |
| CN109738566B (en) * | 2019-02-27 | 2021-04-02 | 贵州健安德科技有限公司 | Method for detecting oxine-copper in water by using UPLC-MS/MS method |
| CN110596276A (en) * | 2019-10-14 | 2019-12-20 | 普洱市质量技术监督综合检测中心 | Method for measuring dithiocarbamate residues in tea leaves by headspace-gas chromatography-mass spectrometry |
| CN112014504A (en) * | 2020-08-31 | 2020-12-01 | 河北双吉化工有限公司 | Analysis method of Dyson series |
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Effective date of registration: 20200120 Address after: 221400 Xinyi Economic Development Zone, Jiangsu, Xuzhou Patentee after: Limin Chemical Co., Ltd. Address before: 221400 Xinyi Economic Development Zone, Jiangsu, Xuzhou Patentee before: Limin Chemical Co., Ltd. |