CN103344724B - Analysis method of mancozeb - Google Patents

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

A kind of analytical approach of Mancozeb

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 is the co-ordination complex of ethylene bisdithiocarbamic manganese and zinc ion.Sterling is white powder, and industrial goods are canescence or pale yellow powder, water insoluble and most of organic solvents, but can be dissolved in pyridine, to light, heat, moist unstable, easily decomposite carbon disulphide, in the time storing for 35 DEG C, monthly weightlessness 0.18%, high temperature wet wets and meets acid and decompose.Rat acute LD50 of passing through mouth 12800～14000mg/kg.

Mancozeb, for the protection germifuge of many leaf diseases, has good effect to the downy mildew in wheat rust, the leaf blight of corn, vegetables, anthracnose and black spot of fruit tree.Mancozeb and other mixed pesticides, effect is better.The complex compound method, GC method and the GB GB20699-2006 method that have a large amount of reports: HPLC to measure both at home and abroad to Mancozeb analytical approach at present, also have the potpourri of L-cysteine hydrochloric acid and EDTA and iodomethane methylation method to survey Mancozeb.But, in the method for report, also there are at present a lot of deficiencies, for example, GB20699-2006 method is measured to be needed to use much solution, and the heavy metal liquid waste processing containing 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 shortcomings existing in prior art, the invention provides a kind of analytical approach of Mancozeb, the method good separating effect, reduce pollution factor, cost-saving, and veracity and precision all can obtain such as fitting like a glove and wait the result being satisfied with GB chemical analysis contrast content.

The analytical approach of the Mancozeb the present invention relates to, is achieved through the following technical solutions:

The present invention uses high performance liquid chromatography (HPLC) to analyze Mancozeb content

An analytical approach for Mancozeb, comprises the following steps:

(1) preparation of standard solution: take standard items, take that rear use mixed solution B dissolves, constant volume mixes for subsequent use, described mixed solution B is the solution that adds sodium sulphite to be mixed with in mixed solution A, and 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 Mancozeb sample, take that the described mixed solution B of rear use dissolves, constant volume mixes for subsequent use;

(3) carry out HPLC analysis: adopt C18 chromatographic column, mobile phase is: methyl alcohol: buffer solution=7:3 (V/V), flow velocity is 0.6-1.2ml/min, and column temperature is 27-40 DEG C, and detection wavelength is 270-290nm, and sample size is 20 μ L.Get respectively solution prepared by step (1) and step (2) and carry out HPLC analysis, obtain Mancozeb HPLC chromatogram, described buffer solution is to use KOH or NAOH that described mixed solution A is adjusted to alkaline solution;

(4) according to Mancozeb content in liquid chromatography external standard method formula (I) calculation sample:

$X\%=\frac{A_2\·m_1\·P}{A_1\·m_2}\·100\%$

(I)

Wherein:

A ₁represent in standard solution for peak area,

A ₂represent in sample solution for peak area,

M1 represents standard items quality, and unit is mg,

M2 represents sample quality, and unit is mg,

P represents standard items quality percentage, and unit is %,

X represents Mancozeb percentage composition in sample.

Described mixed solution A is the mixed aqueous solution that contains respectively 10mM EDTA, dipotassium hydrogen phosphate and 4-butyl ammonium hydrogen sulfate.

Described mixed solution B is the solution that adds the sodium sulphite of 1g/L to be mixed with 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. mobile phase of the present invention and dilute sample all carry out under alkali condition, avoid Mancozeb acid decomposition;

2. HPLC determination method 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 determination method of the present invention and GB20699-2006 analytical approach comparing result deviation are all in 0.5% scope.

Brief description of the drawings

Fig. 1-4 are respectively the HPLC figure of embodiment 2 Plays product, sample, sample, standard items;

Fig. 5 is Mancozeb canonical plotting.

Embodiment

In order better to explain the present invention, below in conjunction with specific embodiment, the invention will be further described.The instrument using 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 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 the mixed aqueous solution of the EDTA, dipotassium hydrogen phosphate and the 4-butyl ammonium hydrogen sulfate that contain respectively 10mM;

Buffer solution is to use KOH or NAOH the PH of mixed solution A to be adjusted to 9.5 solution;

Mixed solution B is the solution that adds the sodium sulphite of 1g/L to be mixed with in mixed solution A.

Embodiment 1

Preparation standard product solution: accurately taking content is the standard items 100mg (being accurate to 0.01mg) of 88.0wt%, in 100ml volumetric flask, add appropriate mixed solution B, ultrasonic dissolution, add again above-mentioned mixed solution B to be settled to scale, after mixing, get 1ml in 25ml volumetric flask, use mixed solution B dilution to be settled to scale, mix for subsequent use.

Prepare sample solution: accurately take Mancozeb sample 100mg left and right (being accurate to 0.01mg) in 100ml volumetric flask, add appropriate mixed solution B, ultrasonic dissolution, add again above-mentioned mixed solution B to be settled to scale, after mixing, get 1ml in 25ml volumetric flask, use mixed solution B dilution to be settled to scale, mix for subsequent use.

Embodiment 2

Adopt C18 chromatographic column, mobile phase is methyl alcohol: buffer solution=7:3 (V/V), and flow velocity is 0.9ml/min, and column temperature is 29 DEG C, and detection wavelength is 282nm, and sample size is 20 μ L.Engage of standard product solution under these conditions, repeat sample introduction until the difference of the peak area that adjacent twice sample introduction obtains is less than 1%, then carry out HPLC analysis according to the order of standard items, sample, sample, standard items, the results are shown in accompanying drawing 1-4, thereby obtain Mancozeb content, its content is 91.07%.

Embodiment 3

Adopt C18 chromatographic column, mobile phase is methyl alcohol: buffer solution=7:3 (V/V), and flow velocity is 0.6ml/min, and column temperature is 27 DEG C, and detection wavelength is 270nm, and sample size is 20 μ L.Engage of standard product solution under these conditions, repeat sample introduction until the difference of the peak area that adjacent twice sample introduction obtains is less than 1%, then analyze according to the order of standard items, sample, sample, standard items, obtain Mancozeb content, its content is 90.17%.

Embodiment 4

Adopt C18 chromatographic column, mobile phase is methyl alcohol: buffer solution=7:3 (V/V), and flow velocity is 1.2ml/min, and column temperature is 40 DEG C, and detection wavelength is 285nm, and sample size is 20 μ L.Engage of standard product solution under these conditions, repeat sample introduction until the difference of the peak area that adjacent twice sample introduction obtains is greater than 1%, then analyze according to the order of standard items, sample, sample, standard items, obtain Mancozeb content, its content is 89.69%.

Embodiment 5

Adopt C18 chromatographic column, mobile phase is methyl alcohol: buffer solution=7:3 (V/V), and flow velocity is 0.6ml/min, and column temperature is 27 DEG C, and detection wavelength is 270nm, and sample size is 20 μ L.Engage of standard product solution under these conditions, repeat sample introduction until the difference of the peak area that adjacent twice sample introduction obtains is less than 1%, then carry out HPLC analysis according to the order of standard items, sample, sample, standard items, obtain Mancozeb content, its content is 90.29%.

Embodiment 6

Adopt C18 chromatographic column, mobile phase is methyl alcohol: buffer solution=7:3 (V/V), and flow velocity is 1.2ml/min, and column temperature is 40 DEG C, and detection wavelength is 285nm, and sample size is 20 μ L.Engage of standard product solution under these conditions, repeat sample introduction until the difference of the peak area that adjacent twice sample introduction obtains is greater than 1%, then carry out HPLC analysis according to the order of standard items, sample, sample, standard items, obtain Mancozeb content, its content is 89.96%.

Embodiment 7

Adopt C18 chromatographic column, mobile phase is methyl alcohol: buffer solution=7:3 (V/V), and flow velocity is 0.9ml/min, and column temperature is 30 DEG C, and detection wavelength is 285nm, and sample size is 20 μ L.Engage of standard product solution under these conditions, repeat sample introduction until the difference of the peak area that adjacent twice sample introduction obtains is less than 1%, then analyze according to the order of standard items, sample, sample, standard items, obtain Mancozeb content, its content is 90.26%.

Embodiment 8

Adopt C18 chromatographic column, mobile phase is methyl alcohol: buffer solution=7:3 (V/V), and flow velocity is 1.0ml/min, and column temperature is 35 DEG C, and detection wavelength is 270nm, and sample size is 20 μ L.Engage of standard product solution under these conditions, repeat sample introduction until the difference of the peak area that adjacent twice sample introduction obtains is less than 1%, then carry out HPLC analysis according to the order of standard items, sample, sample, standard items, obtain Mancozeb content, its content is 91.19%.

Embodiment 9

Adopt C18 chromatographic column, mobile phase is methyl alcohol: buffer solution=7:3 (V/V), and flow velocity is 0.9ml/min, and column temperature is 29 DEG C, and detection wavelength is 290nm, and sample size is 20 μ L.Engage of standard product solution under these conditions, repeat sample introduction until the difference of the peak area that adjacent twice sample introduction obtains is less than 1%, then carry out HPLC analysis according to the order of standard items, sample, sample, standard items, obtain Mancozeb content, its content is 90.74%.

Below the embodiment that analysis Mancozeb content method of the present invention is investigated

Embodiment 10 formulates typical curve

Take respectively the Mancozeb standard items of different quality, make concentration and be respectively the Mancozeb standard solution of 40.096mg/L, 42.092mg/L, 44.096mg/L, 46.144mg/L and 48.060mg/L according to the method for the preparation standard product solution in embodiment 1, and according to the chromatographic condition sample introduction in embodiment 2, measure peak area, measurement result is in table 1.

The table 1 Mancozeb quantitative test range of linearity is measured

To weigh sample as horizontal ordinate, peak area is ordinate, drawing standard curve, and obtaining regression equation is Y=45310X+871789, coefficient R 2=0.991, typical curve is shown in Fig. 5.

Embodiment 11 precision tests

Take respectively different quality Mancozeb sample (batch: 201301015-2) according to the method for preparing sample solution in embodiment 1 and the chromatographic condition identical with embodiment 2, prepare 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

The demonstration of table 2 result, the standard deviation of the Mancozeb content of acquisition is 0.12%, the coefficient of variation is 0.13%.

Embodiment 12 accuracy experiments

In the former medicine of Mancozeb, add respectively the Mancozeb standard items of different amounts, be made into the sample of known content, sample introduction also detects, and measure peak area, and it the results are shown in Table 3 to carry out its recovery of measure and calculation according to embodiment 1.

Table 3 Mancozeb quantitative test accuracy determination result

The demonstration of table 3 result, the average recovery rate of Mancozeb standard items is 99.23%, shows to use the accuracy of efficient liquid phase chromatographic analysis Mancozeb content high.

Embodiment 13

Use respectively HPLC determination method of the present invention (according to the chromatographic condition of embodiment 2) and GB20699-2006 analytical approach to analyze Mancozeb content in Mancozeb sample, analysis result is in table 4.

The Mancozeb content that the different analytical approachs of table 4 obtain

Table 4 result show, HPLC determination method of the present invention and GB20699-2006 analytical approach to the deviation of Mancozeb content in 0.5% scope.

Although 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 (2)

1. an analytical approach for Mancozeb, said method comprising the steps of:

(1) preparation of standard solution: take standard items, taking rear mixed solution B dissolving, the constant volume of using respectively mixes for subsequent use, described mixed solution B is the solution that adds the sodium sulphite of 1g/L to be mixed with in mixed solution A, and described mixed solution A is the mixed aqueous solution that contains respectively 10mM EDTA, dipotassium hydrogen phosphate and 4-butyl ammonium hydrogen sulfate;

(2) preparation of sample solution: take Mancozeb sample, use respectively described mixed solution B dissolving, constant volume to mix for subsequent use;

(3) carry out HPLC analysis: adopt C18 chromatographic column, mobile phase is: the volume ratio of methyl alcohol and buffer solution is 7:3, and flow velocity is 0.6-1.2ml/min, and column temperature is 27-40 DEG C, and detection wavelength is 270-290nm, and sample size is 20 μ L,

Get respectively solution prepared by step (1) and step (2) and carry out HPLC analysis, obtain Mancozeb HPLC chromatogram, described buffer solution is to use KOH or NAOH that described mixed solution A is adjusted to alkaline solution;

(4) according to Mancozeb content in liquid chromatography external standard method formula (I) calculation sample:

(I)

Wherein:

A ₁represent in standard solution for peak area

A ₂represent in sample solution for peak area,

M1 represents standard items quality, and unit is mg,

M2 represents sample quality, and unit is mg,

P represents standard items quality percentage, and unit is %,

X represents Mancozeb percentage composition in sample.

2. the analytical approach of Mancozeb according to claim 1, the pH value of described buffer solution is 9.5.