CN109738566B - Method for detecting oxine-copper in water by using UPLC-MS/MS method - Google Patents
Method for detecting oxine-copper in water by using UPLC-MS/MS method Download PDFInfo
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Abstract
The invention relates to a method for detecting oxine-copper in water by using a UPLC-MS/MS method, belonging to the technical field of pesticide environment detection. The method comprises the steps of treating a sample with a sulfuric acid aqueous solution, converting oxine-copper into 8-hydroxyquinoline, detecting by using an ultrahigh pressure high performance liquid chromatography-tandem mass spectrum (UPLC-MS/MS), and quantifying by using an Agilent Hilic Plus RRHD (2.1 × 50mm, 1.8 μm) hydrophilic chromatographic column, an MSD detector and an external standard method. The method has the advantages of relative standard deviation of 0.96%, reference substance linear correlation coefficient of 0.9997, average recovery rate of 95.77%, LOD of 0.050 mu g/L and LOQ of 0.165 mu g/L, simple operation, rapid analysis, accurate result, good separation effect and high sensitivity.
Description
Technical Field
The invention relates to the technical field of environmental detection, in particular to a method for detecting oxine-copper in water by using a UPLC-MS/MS method.
Background
Oxine copper (oxine copper) is a quinoline protective low-toxicity bactericide, belongs to an organic copper chelate, has broad spectrum, high efficiency, low residue, safe use, good prevention and control effects on fungal and bacterial diseases, particularly good prevention and control effects on germs with drug resistance, forms a tight protective medicine film on the surface of a plant after being sprayed, has strong affinity with the plant, and is resistant to rain wash; the medicine film slowly releases bactericidal copper ions, effectively inhibits the germination and invasion of germs, thereby achieving the purpose of preventing and treating diseases.
The detection and analysis methods of the oxine-copper are reported at present by a chemical titration method, a high performance liquid chromatography method and a gas chromatography-mass spectrometry combined method, the high performance liquid chromatography method and the gas chromatography-mass spectrometry combined method in the methods can effectively detect the oxine-copper, but the methods are not high in sensitivity and cannot completely meet the requirements for trace or ultra-trace detection. However, no method for detecting trace amount of oxine-copper in water by LC-MS/MS is reported at home and abroad, so that a detection method with higher sensitivity, more effectiveness and lower detection limit is required to be explored for the analysis and detection of oxine-copper.
CN 103592404B-a method for detecting the residual quantity of organic copper pesticides in fruits and vegetables, discloses a method for detecting the residual quantity of organic copper pesticides in fruits and vegetables, adopts dispersive solid phase extraction-ultra high performance liquid chromatography-tandem mass spectrometry to detect, and specifically comprises the following steps: (1) preparing a standard solution; (2) adding a complex breaking agent into a sample to break the complex, then adding methanol, performing vortex oscillation and ultrasonic extraction; (3) purifying; (4) detecting by an instrument: injecting sample by using the series concentration standard working solution in the step (1), detecting by using UPLC-MS/MS, and carrying out UPLC-MS/MS detection on the purified sample collected in the step (3); (5) establishing a standard curve; (6) and analyzing the result, and calculating the content of the organic copper pesticide in the sample. The complex breaking agent comprises sodium sulfide (Na)2S), ferrous sulfate (FeSO)4) Sodium hypochlorite (NaClO), Fenton's reagent, some of which are inherently toxic or may react with other reagentsToxicity is generated, and the direct addition of a solid reagent has poor effect of breaking the complexes. The minimum detectable amount was 1.2X 10-11g, the lowest detection concentration is 0.01mg/kg and is higher than the detection limit of the invention by 0.050 mu g/L; the process of extracting and purifying the test sample is time-consuming.
A determination method of the residual amount of CN 105699528A-oxine-copper discloses a determination method of the residual amount of oxine-copper, which comprises the following steps: (1) preparing a standard solution; (2) extracting; (3) detecting by an instrument; (4) establishing a standard curve; (5) and analyzing results, and calculating the content of the oxine-copper in the sample. The method is suitable for detecting the residual quantity of the oxine-copper in substrates such as apples, pears, cucumbers, persimmons and the like. The method has the advantages that the quinoline copper complex is not subjected to complex breaking treatment before sample injection, the response value is low, the selected mass concentration range is high, and the working curve concentration of the quinoline copper standard solution is as follows: 0mg/L, 0.01mg/L, 0.02mg/L, 0.05mg/L, 0.1mg/L, 0.2mg/L, 0.5mg/L, 1.0mg/L, 2.0 mg/L.
CN 106198508B-a method for high-sensitivity rapid detection of pesticides containing heavy metals, which discloses contacting a sensor with pesticides, enabling an indicator on the sensor to generate a color reaction through the chelation between the indicator and heavy metals in the pesticides containing heavy metals, enriching quantitative pesticides through the sensor to improve the color change intensity of the indicator, then collecting images before and after the indicator reaction by using imaging equipment, and extracting color change values of three channels of red, green and blue (RGB); and then calculating by using a formula to obtain a color change value ED before and after the sensor reacts with the pesticide, wherein the method is a supplement method of the existing pesticide residue quick detection method, the detection limit is in the mg/kg level aiming at the detection of the residual quantity of the oxine-copper, and the detection purpose cannot be achieved when the residual quantity concentration of the oxine-copper in water is lower.
Disclosure of Invention
The invention aims to overcome the defects of high detection limit and complex operation in the prior art and provides a method for detecting oxine-copper in water by using a UPLC-MS/MS method.
The method comprises the following steps: (1) preparation of a test solution: weighing 0.0396g of 36% Chunlei quinoline copper suspending agent sample in a 100mL volumetric flask, adding aerated water to dilute the sample to a scale, putting 10.0mL in a 2000mL beaker, diluting the sample to 2000mL with aerated water to obtain a quinoline copper aqueous solution with the concentration of 653.40 mu g/L, namely the quinoline copper aqueous solution to be detected, treating the quinoline copper aqueous solution to be detected with 0.1-0.5% sulfuric acid aqueous solution to obtain a derivative quinoline copper aqueous solution, and detecting by UPLC-MS/MS; (2) preparation of control solutions: weighing 0.0114g of standard oxine-copper sample, placing the standard oxine-copper sample in a 100.00mL volumetric flask, treating the standard oxine-copper sample with 0.1-0.5% of sulfuric acid aqueous solution to obtain standard sample stock solution with the concentration of 113.32mg/L after derivatization, sucking the appropriate stock solution, diluting the standard sample stock solution with 0.1-0.5% of sulfuric acid aqueous solution to prepare series of standard working solutions with the gradient concentrations of 4.53 mu g/L, 9.07 mu g/L, 22.66 mu g/L, 45.33 mu g/L, 113.32 mu g/L, 226.63 mu g/L and 566.58 mu g/L, and waiting for UPLC-MS/MS measurement; (3) measurement and calculation of results: setting instrument parameters, performing UPLC-MS/MS determination on the reference solution and the test solution after the instrument is stabilized, recording a chromatogram, and calculating according to an external standard method by taking the content of 8-hydroxyquinoline as the content of oxine-copper.
Preferably, the method comprises the steps of: (1) preparation of a test solution: weighing 0.0396g of a 36% Chunlei quinoline copper suspending agent sample in a 100mL volumetric flask, adding aerated water to dilute the sample to a scale, putting 10.0mL in a 2000mL beaker, diluting the sample to the 2000mL scale with the aerated water to obtain a quinoline copper aqueous solution with the theoretical concentration of 653.40 mu g/L, namely the quinoline copper aqueous solution to be detected, treating the quinoline copper aqueous solution to be detected with 0.2-0.4% sulfuric acid aqueous solution to obtain a derivative quinoline copper aqueous solution, and detecting the derivative quinoline copper aqueous solution by UPLC-MS/MS; (2) preparation of control solutions: weighing 0.0114g of standard oxine-copper sample, placing the standard oxine-copper sample in a 100.00mL volumetric flask, treating the standard oxine-copper sample with 0.2-0.4% of sulfuric acid aqueous solution to obtain standard sample stock solution with the concentration of 113.32mg/L after derivatization, sucking the appropriate stock solution, diluting the standard sample stock solution with 0.2-0.4% of sulfuric acid aqueous solution to prepare series of standard working solutions with the gradient concentrations of 4.53 mu g/L, 9.07 mu g/L, 22.66 mu g/L, 45.33 mu g/L, 113.32 mu g/L, 226.63 mu g/L and 566.58 mu g/L, and waiting for UPLC-MS/MS measurement; (3) measurement and calculation of results: setting instrument parameters, performing UPLC-MS/MS determination on the reference solution and the test solution after the instrument is stabilized, recording a chromatogram, and calculating according to an external standard method by taking the content of 8-hydroxyquinoline as the content of oxine-copper.
Further preferably, the method comprises the steps of: (1) preparation of a test solution: weighing 0.0396g of 36% Chunlei quinoline copper suspending agent sample in a 100mL volumetric flask, adding aerated water to dilute the sample to a scale, putting 10.0mL in a 2000mL beaker, diluting the sample to the 2000mL scale with the aerated water to obtain a quinoline copper aqueous solution with the theoretical concentration of 653.40 mu g/L, namely the quinoline copper aqueous solution to be detected, treating the quinoline copper aqueous solution to be detected with 0.3% sulfuric acid aqueous solution to obtain the derivative quinoline copper aqueous solution, and detecting by UPLC-MS/MS; (2) preparation of control solutions: weighing 0.0114g of standard oxine-copper sample, placing the standard oxine-copper sample in a 100.00mL volumetric flask, treating the standard oxine-copper sample with 0.3% of sulfuric acid aqueous solution to obtain standard sample stock solution with the concentration of 113.32mg/L after derivatization, sucking proper stock solution, diluting the standard sample stock solution with 0.3% of sulfuric acid aqueous solution to prepare series standard working solution, and preparing the standard working solution with the gradient concentration of 4.53 mu g/L, 9.07 mu g/L, 22.66 mu g/L, 45.33 mu g/L, 113.32 mu g/L, 226.63 mu g/L and 566.58 mu g/L to be subjected to UPLC-MS/MS measurement; (3) measurement and calculation of results: setting instrument parameters, performing UPLC-MS/MS determination on the reference solution and the test solution after the instrument is stabilized, recording a chromatogram, and calculating according to an external standard method by taking the content of 8-hydroxyquinoline as the content of oxine-copper.
The steps of treating the sample solution and the standard sample solution by the sulfuric acid aqueous solution are as follows: (1) the step of treating the sample solution with the sulfuric acid aqueous solution comprises the following steps: and (3) mixing the copper quinoline solution to be tested of the test sample with the following components in a volume ratio of 1: 1-1: 3 adding 0.1-0.5% sulfuric acid aqueous solution, mixing for 5-20 min in a vortex manner, carrying out ultrasonic treatment for 5-20 min after full reaction, and filtering with a 0.45um filter membrane to obtain the product. (2) The step of treating the standard sample solution by the sulfuric acid aqueous solution comprises the following steps: treating the weighed oxine-copper standard sample with 0.1-0.5% sulfuric acid aqueous solution, carrying out vortex mixing for 5-20 min, carrying out ultrasonic treatment for 5-20 min after full reaction, and filtering with a 0.45um filter membrane to obtain the oxine-copper standard sample; the conversion of copper quinolinate in aqueous sulfuric acid takes place as follows:
preferably, the step of treating the sample solution and the standard sample solution with the sulfuric acid aqueous solution comprises the following steps: (1) the step of treating the sample solution with the sulfuric acid aqueous solution comprises the following steps: adding 0.2-0.4% of sulfuric acid aqueous solution into the aqueous solution of the copper quinolate to be tested of the sample according to the volume ratio of 1:2, mixing for 5-10 min in a vortex manner, carrying out ultrasonic treatment for 5-10 min after full reaction, and filtering with a 0.45um filter membrane to obtain the copper quinolate. (2) The step of treating the standard sample solution by the sulfuric acid aqueous solution comprises the following steps: treating the weighed oxine-copper standard sample with 0.2% -0.4% sulfuric acid aqueous solution, carrying out vortex mixing for 5-10 min, carrying out ultrasonic treatment for 5-10 min after full reaction, and filtering with a 0.45um filter membrane to obtain the oxine-copper standard sample; the conversion of copper quinolinate in aqueous sulfuric acid takes place as follows:
further preferably, the step of treating the sample solution and the standard sample solution with the aqueous sulfuric acid solution is: (1) the step of treating the sample solution with the sulfuric acid aqueous solution comprises the following steps: adding 0.3% aqueous solution of sulfuric acid into the aqueous solution of the copper quinoline to be tested according to the volume ratio of 1:1, mixing for 5min in a vortex manner, carrying out ultrasonic treatment for 5min after full reaction, and filtering with a 0.45um filter membrane to obtain the copper quinoline. (2) The step of treating the standard sample solution by the sulfuric acid aqueous solution comprises the following steps: treating the weighed oxine-copper standard sample with 0.3% sulfuric acid aqueous solution, carrying out vortex mixing for 5min, carrying out ultrasonic treatment for 5min after full reaction, and filtering with a 0.45um filter membrane to obtain the oxine-copper standard sample; the conversion of copper quinolinate in aqueous sulfuric acid takes place as follows:
the UPLC-MS/MS determination method has the HPLC operation conditions as follows:
1) sample introduction amount: 2.0. mu.L
2) Column temperature: 40 deg.C
3) Flow rate: 0.3 mL/min;
4) a chromatographic column: agilent Hilic Plus RRHD, Specification: 2.1X 50mm, 1.8 μm;
5) elution gradient: eluting solvent: mobile phase A, methanol, mobile phase B: 0.1% formic acid water, elution program:
| time (minutes) | Mobile phase A (%) | Mobile phase B (%) |
| 0～1.5min | 10％～90％ | 90％～10％ |
| 1.5～2.0min | 90％～10％ | 10％～90％ |
| 2.0～3.5min | 10％ | 90％ |
The UPLC-MS/MS measurement and the MSD operation conditions of the detection method are as follows:
1) and (3) monitoring mode: MRM;
2) detection mode: a negative ion mode;
3) ion source parameters: drying gas: n is a radical of2(ii) a Temperature of the drying gas: 300 ℃; flow rate of drying gas: 5L/min; sheath gas: n is a radical of2(ii) a Temperature of sheath gas: 350 deg.C(ii) a Flow rate of sheath gas: 11L/min; atomizer pressure Nebulizer: 45 psi; nozzle voltage: 500V; capillary voltage Capillary: 3500V, EMV gain: 0V;
the MRM ion acquisition parameters are as follows:
is a quantitative ion
And (3) qualitative identification: for the parent ion and the ion pair of the pesticide, if the ion chromatographic retention time is consistent with that of the standard sample working solution (the variation range is within +/-2.5 percent); and when the ion abundance Ratio (Ratio) of the target compound in the sample is not more than 20%, judging that the detected mass spectrum signal is the pesticide, and if the two conditions cannot be met simultaneously, judging that the pesticide is not contained.
The method has the detection limit LOD of 0.050 mu g/L and the quantification limit LOQ of 0.165 mu g/L for the oxine-copper.
The invention has the following advantages:
1. the detection methodology of the invention verifies that the sample concentration of the oxine-copper is in good linear relation in the range of 4.53 mu g/L-566.58 mu g/L, the linear equation is that y is 2447.66x-3454.87, and R2 is 0.9997; the average recovery rate is 95.77%, the repeatability RSD% value is 0.96%, and the method has the advantages of simplicity, convenience, rapidness, accuracy, good separation effect, high accuracy and precision and the like.
2. The method for detecting the oxine-copper in the water provided by the invention adopts the sulfuric acid aqueous solution to break complexation, and aeration stirring can achieve a good effect of breaking complexation.
3. The method uses an ultrahigh-pressure high performance liquid chromatography-mass spectrometer for detection, overcomes the high detection limit of the conventional methods such as gas chromatography, high performance liquid chromatography and the like, has the detection limit of 0.050 mu g/L and the quantification limit of 0.165 mu g/L, has high sensitivity, can well detect the content of oxine-copper in water, provides a reference basis for water quality evaluation and environmental protection, and has important significance for aquatic animal protection and water resource protection.
Description of the drawings:
FIG. 1: qualitative and quantitative ion and ion abundance ratio diagram of oxine-copper
FIG. 2: standard curve diagram of oxine-copper
FIG. 3: diagram of quinoline copper standard substance
FIG. 4: diagram of copper quinolinate sample
The specific implementation mode is as follows:
the invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Unless otherwise specified, all the raw materials and equipment used in this example were those conventionally available in the art.
Instruments and reagents involved in the following examples include, but are not limited to: instruments and reagents used in the examples:
the instrument comprises the following steps: an ultrahigh-pressure high-performance liquid chromatography-mass spectrometer (Agilent 1290-.
A chromatographic column: agilent Hilic Plus RRHD (2.1X 50mm, 1.8 μm)
Reagent:
methanol: chromatographically pure, Merck corporation, (ii) C
Reag.Ph Eur，Lot：I0930107803)；
Formic acid: chromatographic purity, Shanghai' an spectral science instruments, Inc. (CNW Technologies, Lot: K3560090);
sulfuric acid: the known mass fraction is: 95-98%, Shanghai test (written full name), Lot: 20150930;
quinoline copper standard sample: the known mass fraction is: ω 99.4%, a Chemtek Inc;
36% chunlei quinoline copper suspension concentrate: wherein the mass fraction of the copper quinoline is 33 percent; the mass fraction of kasugamycin is 3 percent.
Ultrapure water: resistivity, 18.2M Ω cm;
aeration water: the material is prepared in a laboratory and is obtained by carrying out aeration treatment on ultrapure water.
Example 1
Preparation of a test solution: weighing 0.0396g of 36% Chunlei-Quinolin copper suspending agent sample in a 100mL volumetric flask, adding aerated water to dilute to a scale, taking 10.0mL in a 2000mL beaker, diluting with aerated water to 2000mL to obtain a Quinolin copper aqueous solution with the concentration of 653.40 mug/L, namely the Quinolin copper aqueous solution to be detected, adding 0.1% sulfuric acid aqueous solution according to the volume ratio of 1:3, carrying out vortex mixing for 5min, carrying out ultrasonic treatment for 5min after full reaction, and filtering with a 0.45um filter membrane to obtain the Quinolin copper suspending agent for UPLC-MS/MS detection;
preparation of control solutions: weighing 0.0114g of oxine-copper standard sample, placing the weighed sample in a 100.00mL volumetric flask, treating the sample with 0.1% sulfuric acid aqueous solution, carrying out vortex mixing for 5min, carrying out ultrasonic treatment for 5min after full reaction, filtering the sample with a 0.45um filter membrane to obtain a standard sample stock solution with the concentration of the derived oxine-copper of 113.32mg/L, sucking a proper stock solution, diluting the standard sample stock solution with 0.1% sulfuric acid aqueous solution to prepare a series of standard working solutions with the gradient concentrations of 4.53 mu g/L, 9.07 mu g/L, 22.66 mu g/L, 45.33 mu g/L, 113.32 mu g/L, 226.63 mu g/L and 566.58 mu g/L, and determining the standard working solutions by UPLC-MS/MS;
measurement and calculation of results: setting instrument parameters, performing UPLC-MS/MS determination on a reference solution and a test solution after the instrument is stabilized, recording a chromatogram, drawing a standard curve by taking the concentration of the oxine-copper derivative 8-hydroxyquinoline as a horizontal coordinate and the peak area of the 8-hydroxyquinoline as a vertical coordinate, substituting the peak area of the oxine-copper derivative 8-hydroxyquinoline measured in the sample into the standard curve to obtain the content of the 8-hydroxyquinoline in the sample solution, and calculating by taking the content of the 8-hydroxyquinoline as the content of the oxine-copper;
wherein the HPLC operating conditions are as follows:
sample introduction volume: 2.0 mu L;
flow rate: 0.3 mL/min;
column temperature: 40 ℃;
mobile phase: methanol + 0.1% formic acid water;
the elution procedure was: mobile phase A, methanol, mobile phase B: 0.1% formic acid water;
| time (minutes) | Mobile phase A (%) | Mobile phase B (%) |
| 0～1.5min | 10％～90％ | 90％～10％ |
| 1.5～2.0min | 90％～10％ | 10％～90％ |
| 2.0～3.5min | 10％ | 90％ |
The MSD operating conditions were:
1) and (3) monitoring mode: MRM;
2) detection mode: a negative ion mode;
ion source parameters: drying gas: n is a radical of2(ii) a Temperature of the drying gas: 300 ℃; flow rate of drying gas: 5L/min; sheath gas: n is a radical of2(ii) a Temperature of sheath gas: 350 ℃; flow rate of sheath gas: 11L/min; atomizer pressure (Nebulizer): 45 psi; nozzle voltage: 500V; capillary voltage (Capillary): 3500V, EMV gain: 0V;
the MRM ion acquisition parameters are as follows:
is quantitative ion
And (3) qualitative identification: for the parent ion and the ion pair of the pesticide, if the ion chromatographic retention time is consistent with that of the standard sample working solution (the variation range is within +/-2.5 percent); and when the ion abundance Ratio (Ratio) of the target compound in the sample is not more than 20%, judging that the measured mass spectrum signal is the pesticide oxine-copper, and if the two conditions cannot be met simultaneously, judging that the pesticide oxine-copper is not contained.
Example 2
Preparation of a test solution: weighing 0.0396g of 36% Chunlei-Quinolin copper suspending agent sample in a 100mL volumetric flask, adding aerated water to dilute to a scale, taking 10.0mL in a 2000mL beaker, diluting with aerated water to 2000mL to obtain a Quinolin copper aqueous solution with the concentration of 653.40 mug/L, namely the Quinolin copper aqueous solution to be detected, adding 0.2% sulfuric acid aqueous solution according to the volume ratio of 1:2, carrying out vortex mixing for 10min, carrying out ultrasonic treatment for 10min after full reaction, and filtering with a 0.45um filter membrane to obtain the Quinolin copper suspending agent for UPLC-MS/MS detection;
preparation of control solutions: weighing 0.0114g of oxine-copper standard sample, placing the weighed sample in a 100.00mL volumetric flask, treating the sample with 0.2% sulfuric acid aqueous solution, carrying out vortex mixing for 10min, carrying out ultrasonic treatment for 10min after full reaction, filtering the sample with a 0.45um filter membrane to obtain a standard sample stock solution with the concentration of the derived oxine-copper of 113.32mg/L, sucking a proper stock solution, diluting the stock solution with 0.2% sulfuric acid aqueous solution to prepare a series of standard working solutions, wherein the gradient concentration of the standard working solutions is 4.53 mu g/L, 9.07 mu g/L, 22.66 mu g/L, 45.33 mu g/L, 113.32 mu g/L, 226.63 mu g/L and 566.58 mu g/L, and carrying out UPLC-MS/MS determination;
measurement and calculation of results: setting instrument parameters, performing UPLC-MS/MS determination on a reference solution and a test solution after the instrument is stabilized, recording a chromatogram, drawing a standard curve by taking the concentration of the oxine-copper derivative 8-hydroxyquinoline as a horizontal coordinate and the peak area of the 8-hydroxyquinoline as a vertical coordinate, substituting the peak area of the oxine-copper derivative 8-hydroxyquinoline measured in the sample into the standard curve to obtain the content of the 8-hydroxyquinoline in the sample solution, and calculating by taking the content of the 8-hydroxyquinoline as the content of the oxine-copper;
wherein the HPLC operating conditions are as follows:
sample introduction volume: 2.0 mu L;
flow rate: 0.3 mL/min;
column temperature: 40 ℃;
mobile phase: methanol + 0.1% formic acid water;
the elution procedure was: mobile phase A, methanol, mobile phase B: 0.1% formic acid water;
| time (minutes) | Mobile phase A (%) | Mobile phase B (%) |
| 0～1.5min | 10％～90％ | 90％～10％ |
| 1.5～2.0min | 90％～10％ | 10％～90％ |
| 2.0～3.5min | 10％ | 90％ |
The MSD operating conditions were:
1) and (3) monitoring mode: MRM;
2) detection mode: a negative ion mode;
ion source parameters: drying gas: n is a radical of2(ii) a Temperature of the drying gas: 300 ℃; flow rate of drying gas: 5L/min; sheath gas: n is a radical of2(ii) a Temperature of sheath gas: 350 ℃; flow rate of sheath gas: 11L/min; atomizer pressure (Nebulizer): 45 psi; nozzle voltage: 500V; capillary voltage (Capillary): 3500V, EMV gain: 0V;
the MRM ion acquisition parameters are as follows:
is quantitative ion
And (3) qualitative identification: for the parent ion and the ion pair of the pesticide, if the ion chromatographic retention time is consistent with that of the standard sample working solution (the variation range is within +/-2.5 percent); and when the ion abundance Ratio (Ratio) of the target compound in the sample is not more than 20%, judging that the measured mass spectrum signal is the pesticide oxine-copper, and if the two conditions cannot be met simultaneously, judging that the pesticide oxine-copper is not contained.
Example 3
Preparation of a test solution: weighing 0.0396g of 36% Chunlei-Quinolin copper suspending agent sample in a 100mL volumetric flask, adding aerated water to dilute to a scale, taking 10.0mL in a 2000mL beaker, diluting with aerated water to 2000mL to obtain a Quinolin copper aqueous solution with the concentration of 653.40 mug/L, namely the Quinolin copper aqueous solution to be detected, adding 0.3% sulfuric acid aqueous solution according to the volume ratio of 1:2, carrying out vortex mixing for 10min, carrying out ultrasonic treatment for 10min after full reaction, and filtering with a 0.45um filter membrane to obtain the Quinolin copper suspending agent for UPLC-MS/MS detection;
preparation of control solutions: weighing 0.0114g of oxine-copper standard sample, placing the weighed sample in a 100.00mL volumetric flask, treating the sample with 0.3% sulfuric acid aqueous solution, carrying out vortex mixing for 10min, carrying out ultrasonic treatment for 10min after full reaction, filtering the sample with a 0.45um filter membrane to obtain a standard sample stock solution with the concentration of the derived oxine-copper of 113.32mg/L, sucking a proper stock solution, diluting the standard sample stock solution with 0.3% sulfuric acid aqueous solution to prepare a series of standard working solutions with the gradient concentrations of 4.53 mu g/L, 9.07 mu g/L, 22.66 mu g/L, 45.33 mu g/L, 113.32 mu g/L, 226.6 mu g/L and 566.58 mu g/L, and determining the standard working solutions by UPLC-MS/MS;
measurement and calculation of results: setting instrument parameters, performing UPLC-MS/MS determination on a reference solution and a test solution after the instrument is stabilized, recording a chromatogram, drawing a standard curve by taking the concentration of the oxine-copper derivative 8-hydroxyquinoline as a horizontal coordinate and the peak area of the 8-hydroxyquinoline as a vertical coordinate, substituting the peak area of the oxine-copper derivative 8-hydroxyquinoline measured in the sample into the standard curve to obtain the content of the 8-hydroxyquinoline in the sample solution, and calculating by taking the content of the 8-hydroxyquinoline as the content of the oxine-copper;
wherein the HPLC operating conditions are as follows:
sample introduction volume: 2.0 mu L;
flow rate: 0.3 mL/min;
column temperature: 40 ℃;
mobile phase: methanol + 0.1% formic acid water;
the elution procedure was: mobile phase A, methanol, mobile phase B: 0.1% formic acid water;
| time (minutes) | Mobile phase A (%) | Mobile phase B (%) |
| 0～1.5min | 10％～90％ | 90％～10％ |
| 1.5～2.0min | 90％～10％ | 10％～90％ |
| 2.0～3.5min | 10％ | 90％ |
The MSD operating conditions were:
1) and (3) monitoring mode: MRM;
2) detection mode: a negative ion mode;
ion source parameters: drying gas: n is a radical of2(ii) a Temperature of the drying gas: 300 ℃; flow rate of drying gas: 5L/min; sheath gas: n is a radical of2(ii) a Temperature of sheath gas: 350 ℃; flow rate of sheath gas: 11L/min; atomizer pressure (Nebulizer): 45 psi; nozzle voltage: 500V; capillary voltage (Capillary): 3500V, EMV gain: 0V;
the MRM ion acquisition parameters are as follows:
is quantitative ion
And (3) qualitative identification: for the parent ion and the ion pair of the pesticide, if the ion chromatographic retention time is consistent with that of the standard sample working solution (the variation range is within +/-2.5 percent); and when the ion abundance Ratio (Ratio) of the target compound in the sample is not more than 20%, judging that the measured mass spectrum signal is the pesticide oxine-copper, and if the two conditions cannot be met simultaneously, judging that the pesticide oxine-copper is not contained.
Example 4
Preparation of a test solution: weighing 0.0396g of 36% Chunlei-Quinolin copper suspending agent sample in a 100mL volumetric flask, adding aerated water to dilute to a scale, taking 10.0mL in a 2000mL beaker, diluting with aerated water to 2000mL to obtain a Quinolin copper aqueous solution with the concentration of 653.40 mug/L, namely the Quinolin copper aqueous solution to be detected, adding 0.4% sulfuric acid aqueous solution according to the volume ratio of 1:1, carrying out vortex mixing for 15min, carrying out ultrasonic treatment for 15min after full reaction, and filtering with a 0.45um filter membrane to obtain the Quinolin copper suspending agent for UPLC-MS/MS detection;
preparation of control solutions: weighing 0.0114g of oxine-copper standard sample, placing the weighed sample in a 100.00mL volumetric flask, treating the sample with 0.4% sulfuric acid aqueous solution, carrying out vortex mixing for 15min, carrying out ultrasonic treatment for 15min after full reaction, filtering the sample with a 0.45um filter membrane to obtain a standard sample stock solution with the concentration of the derived oxine-copper of 113.32mg/L, sucking a proper stock solution, diluting the standard sample stock solution with 0.4% sulfuric acid aqueous solution to prepare a series of standard working solutions with the gradient concentrations of 4.53 mu g/L, 9.07 mu g/L, 22.66 mu g/L, 45.33 mu g/L, 113.32 mu g/L, 226.63 mu g/L and 566.58 mu g/L, and determining the standard working solutions by UPLC-MS/MS;
measurement and calculation of results: setting instrument parameters, performing UPLC-MS/MS determination on a reference solution and a test solution after the instrument is stabilized, recording a chromatogram, drawing a standard curve by taking the concentration of the oxine-copper derivative 8-hydroxyquinoline as a horizontal coordinate and the peak area of the 8-hydroxyquinoline as a vertical coordinate, substituting the peak area of the oxine-copper derivative 8-hydroxyquinoline measured in the sample into the standard curve to obtain the content of the 8-hydroxyquinoline in the sample solution, and calculating by taking the content of the 8-hydroxyquinoline as the content of the oxine-copper;
wherein the HPLC operating conditions are as follows:
sample introduction volume: 2.0 mu L;
flow rate: 0.3 mL/min;
column temperature: 40 ℃;
mobile phase: methanol + 0.1% formic acid water;
the elution procedure was: mobile phase A, methanol, mobile phase B: 0.1% formic acid water;
the MSD operating conditions were:
1) and (3) monitoring mode: MRM;
2) detection mode: a negative ion mode;
ion source parameters: drying gas: n is a radical of2(ii) a Temperature of the drying gas: 300 ℃; flow rate of drying gas: 5L/min; sheath gas: n is a radical of2(ii) a Temperature of sheath gas: 350 ℃; flow rate of sheath gas: 11L/min; atomizer pressure (Nebulizer): 45 psi; nozzle voltage: 500V; capillary voltage (Capillary): 3500V, EMV gain: 0V;
the MRM ion acquisition parameters are as follows:
is quantitative ion
And (3) qualitative identification: for the parent ion and the ion pair of the pesticide, if the ion chromatographic retention time is consistent with that of the standard sample working solution (the variation range is within +/-2.5 percent); and when the ion abundance Ratio (Ratio) of the target compound in the sample is not more than 20%, judging that the measured mass spectrum signal is the pesticide oxine-copper, and if the two conditions cannot be met simultaneously, judging that the pesticide oxine-copper is not contained.
Example 5
Preparation of a test solution: weighing 0.0396g of 36% Chunlei-Quinolin copper suspending agent sample in a 100mL volumetric flask, adding aerated water to dilute to a scale, taking 10.0mL in a 2000mL beaker, diluting with aerated water to 2000mL to obtain a Quinolin copper aqueous solution with the concentration of 653.40 mug/L, namely the Quinolin copper aqueous solution to be detected, adding 0.5% sulfuric acid aqueous solution according to the volume ratio of 1:1, carrying out vortex mixing for 15min, carrying out ultrasonic treatment for 15min after full reaction, and filtering with a 0.45um filter membrane to obtain the Quinolin copper suspending agent for UPLC-MS/MS detection;
preparation of control solutions: weighing 0.0114g of oxine-copper standard sample, placing the standard sample in a 100.00mL volumetric flask, treating the standard sample with 0.5% sulfuric acid aqueous solution, carrying out vortex mixing for 15min, carrying out ultrasonic treatment for 15min after full reaction, filtering the mixture with a 0.45um filter membrane to obtain a standard sample stock solution with the concentration of the derived oxine-copper of 113.32mg/L, sucking a proper stock solution, diluting the standard sample stock solution with the 0.5% sulfuric acid aqueous solution to prepare a series of standard working solutions with the gradient concentrations of 4.53 mu g/L, 9.07 mu g/L, 22.66 mu g/L, 45.33 mu g/L, 113.32 mu g/L, 226.63 mu g/L and 566.58 mu g/L, and determining the standard working solutions by UPLC-MS/MS;
measurement and calculation of results: setting instrument parameters, performing UPLC-MS/MS determination on a reference solution and a test solution after the instrument is stabilized, recording a chromatogram, drawing a standard curve by taking the concentration of the oxine-copper derivative 8-hydroxyquinoline as a horizontal coordinate and the peak area of the 8-hydroxyquinoline as a vertical coordinate, substituting the peak area of the oxine-copper derivative 8-hydroxyquinoline measured in the sample into the standard curve to obtain the content of the 8-hydroxyquinoline in the sample solution, and calculating by taking the content of the 8-hydroxyquinoline as the content of the oxine-copper;
wherein the HPLC operating conditions are as follows:
sample introduction volume: 2.0 mu L;
flow rate: 0.3 mL/min;
column temperature: 40 ℃;
mobile phase: methanol + 0.1% formic acid water;
the elution procedure was: mobile phase A, methanol, mobile phase B: 0.1% formic acid water;
| time (minutes) | Mobile phase A (%) | Mobile phase B (%) |
| 0～1.5min | 10％～90％ | 90％～10％ |
| 1.5～2.0min | 90％～10％ | 10％～90％ |
| 2.0～3.5min | 10％ | 90％ |
The MSD operating conditions were:
1) and (3) monitoring mode: MRM;
2) detection mode: a negative ion mode;
ion source parameters: drying gas: n is a radical of2(ii) a Temperature of the drying gas: 300 ℃; flow rate of drying gas: 5L/min; sheath gas: n is a radical of2(ii) a Temperature of sheath gas: 350 ℃; flow rate of sheath gas: 11L/min; atomizer pressure (Nebulizer): 45 psi; nozzle voltage: 500V; capillary voltage (Capillary): 3500V, EMV gain: 0V;
the MRM ion acquisition parameters are as follows:
is quantitative ion
And (3) qualitative identification: for the parent ion and the ion pair of the pesticide, if the ion chromatographic retention time is consistent with that of the standard sample working solution (the variation range is within +/-2.5 percent); and when the ion abundance Ratio (Ratio) of the target compound in the sample is not more than 20%, judging that the measured mass spectrum signal is the pesticide oxine-copper, and if the two conditions cannot be met simultaneously, judging that the pesticide oxine-copper is not contained.
Example 6
Preparation of a test solution: weighing 0.0396g of 36% Chunlei-Quinolin copper suspending agent sample in a 100mL volumetric flask, adding aerated water to dilute to a scale, taking 10.0mL in a 2000mL beaker, diluting with aerated water to 2000mL to obtain a Quinolin copper aqueous solution with the concentration of 653.40 mug/L, namely the Quinolin copper aqueous solution to be detected, adding 0.3% sulfuric acid aqueous solution according to the volume ratio of 1:1, carrying out vortex mixing for 20min, carrying out ultrasonic treatment for 20min after full reaction, and filtering with a 0.45um filter membrane to obtain the Quinolin copper suspending agent for UPLC-MS/MS detection;
preparation of control solutions: weighing 0.0114g of oxine-copper standard sample, placing the weighed sample in a 100.00mL volumetric flask, treating the sample with 0.3% sulfuric acid aqueous solution, vortex mixing for 20min, carrying out ultrasonic treatment for 20min after full reaction, filtering the sample with a 0.45um filter membrane to obtain a standard sample stock solution with the concentration of the derived oxine-copper of 113.32mg/L, sucking a proper stock solution, diluting the standard sample stock solution with 0.3% sulfuric acid aqueous solution to prepare a series of standard working solutions with the gradient concentrations of 4.53 mu g/L, 9.07 mu g/L, 22.66 mu g/L, 45.33 mu g/L, 113.32 mu g/L, 226.63 mu g/L and 566.58 mu g/L, and determining the standard working solutions by UPLC-MS/MS;
measurement and calculation of results: setting instrument parameters, performing UPLC-MS/MS determination on a reference solution and a test solution after the instrument is stabilized, recording a chromatogram, drawing a standard curve by taking the concentration of the oxine-copper derivative 8-hydroxyquinoline as a horizontal coordinate and the peak area of the 8-hydroxyquinoline as a vertical coordinate, substituting the peak area of the oxine-copper derivative 8-hydroxyquinoline measured in the sample into the standard curve to obtain the content of the 8-hydroxyquinoline in the sample solution, and calculating by taking the content of the 8-hydroxyquinoline as the content of the oxine-copper;
wherein the HPLC operating conditions are as follows:
sample introduction volume: 2.0 mu L;
flow rate: 0.3 mL/min;
column temperature: 40 ℃;
mobile phase: methanol + 0.1% formic acid water;
the elution procedure was: mobile phase A, methanol, mobile phase B: 0.1% formic acid water;
| time (minutes) | Mobile phase A (%) | Mobile phase B (%) |
| 0～1.5min | 10％～90％ | 90％～10％ |
| 1.5～2.0min | 90％～10％ | 10％～90％ |
| 2.0～3.5min | 10％ | 90％ |
The MSD operating conditions were:
1) and (3) monitoring mode: MRM;
2) detection mode: a negative ion mode;
ion source parameters: drying gas: n is a radical of2(ii) a Temperature of the drying gas: 300 ℃; flow rate of drying gas: 5L/min; sheath gas: n is a radical of2(ii) a Temperature of sheath gas: 350 ℃; flow rate of sheath gas: 11L/min; atomizer pressure (Nebulizer): 45 psi; nozzle voltage: 500V; capillary voltage (Capillary): 3500V, EMV gain: 0V;
the MRM ion acquisition parameters are as follows:
is quantitative ion
And (3) qualitative identification: for the parent ion and the ion pair of the pesticide, if the ion chromatographic retention time is consistent with that of the standard sample working solution (the variation range is within +/-2.5 percent); and when the ion abundance Ratio (Ratio) of the target compound in the sample is not more than 20%, judging that the measured mass spectrum signal is the pesticide oxine-copper, and if the two conditions cannot be met simultaneously, judging that the pesticide oxine-copper is not contained.
Example 7
Preparation of a test solution: weighing 0.0396g of 36% Chunlei-Quinolin copper suspending agent sample in a 100mL volumetric flask, adding aerated water to dilute to a scale, taking 10.0mL in a 2000mL beaker, diluting with aerated water to 2000mL to obtain a Quinolin copper aqueous solution with the concentration of 653.40 mug/L, namely the Quinolin copper aqueous solution to be detected, adding 0.3% sulfuric acid aqueous solution according to the volume ratio of 1:1, carrying out vortex mixing for 5min, carrying out ultrasonic treatment for 5min after full reaction, and filtering with a 0.45um filter membrane to obtain the Quinolin copper suspending agent for UPLC-MS/MS detection;
preparation of control solutions: weighing 0.0114g of oxine-copper standard sample, placing the weighed sample in a 100.00mL volumetric flask, treating the sample with 0.3% sulfuric acid aqueous solution, carrying out vortex mixing for 5min, carrying out ultrasonic treatment for 5min after full reaction, filtering the sample with a 0.45um filter membrane to obtain a standard sample stock solution with the concentration of the derived oxine-copper of 113.32mg/L, sucking a proper stock solution, diluting the standard sample stock solution with 0.3% sulfuric acid aqueous solution to prepare a series of standard working solutions with the gradient concentrations of 4.53 mu g/L, 9.07 mu g/L, 22.66 mu g/L, 45.33 mu g/L, 113.32 mu g/L, 226.63 mu g/L and 566.58 mu g/L, and determining the standard working solutions by UPLC-MS/MS;
measurement and calculation of results: setting instrument parameters, performing UPLC-MS/MS determination on a reference solution and a test solution after the instrument is stabilized, recording a chromatogram, drawing a standard curve by taking the concentration of the oxine-copper derivative 8-hydroxyquinoline as a horizontal coordinate and the peak area of the 8-hydroxyquinoline as a vertical coordinate, substituting the peak area of the oxine-copper derivative 8-hydroxyquinoline measured in the sample into the standard curve to obtain the content of the 8-hydroxyquinoline in the sample solution, and calculating by taking the content of the 8-hydroxyquinoline as the content of the oxine-copper;
wherein the HPLC operating conditions are as follows:
sample introduction volume: 2.0 mu L;
flow rate: 0.3 mL/min;
column temperature: 40 ℃;
mobile phase: methanol + 0.1% formic acid water;
the elution procedure was: mobile phase A, methanol, mobile phase B: 0.1% formic acid water;
| time (minutes) | Mobile phase A (%) | Mobile phase B (%) |
| 0～1.5min | 10％～90％ | 90％～10％ |
| 1.5～2.0min | 90％～10％ | 10％～90％ |
| 2.0～3.5min | 10％ | 90％ |
The MSD operating conditions were:
1) and (3) monitoring mode: MRM;
2) detection mode: a negative ion mode;
ion source parameters: drying gas: n is a radical of2(ii) a Temperature of the drying gas: 300 ℃; flow rate of drying gas: 5L/min; sheath gas: n is a radical of2(ii) a Temperature of sheath gas: 350 ℃; flow rate of sheath gas: 11L/min; atomizer pressure(Nebulizer): 45 psi; nozzle voltage: 500V; capillary voltage (Capillary): 3500V, EMV gain: 0V;
the MRM ion acquisition parameters are as follows:
is quantitative ion
And (3) qualitative identification: for the parent ion and the ion pair of the pesticide, if the ion chromatographic retention time is consistent with that of the standard sample working solution (the variation range is within +/-2.5 percent); and when the ion abundance Ratio (Ratio) of the target compound in the sample is not more than 20%, judging that the measured mass spectrum signal is the pesticide oxine-copper, and if the two conditions cannot be met simultaneously, judging that the pesticide oxine-copper is not contained.
Experimental example: to prove the scientificity and rationality of the invention, the following experimental studies of methodology were carried out:
1. the method comprises the following steps:
the method comprises the following steps: the method in the comparison file is adopted: the method for measuring the residual quantity of the CN 105699528A-oxine-copper is characterized in that an LC-MS/MS method is adopted for detection, and the method is formulated by combining the practical situation of an environmental research laboratory of our unit.
The instrument comprises the following steps: an ultrahigh-pressure high-performance liquid chromatography-mass spectrometer (Agilent 1290-.
A chromatographic column: c18, inner diameter 150mm multiplied by 2.1mm, 3.5 μm;
reagent:
methanol: chromatographically pure, Merck corporation, (ii) C
Reag.Ph Eur，Lot：I0930107803)；
Acetonitrile: the American world is filled with original imported chromatographic grade reagent at 4L;
formic acid: the known mass fraction is: 95-98%, Shanghai test;
quinoline copper standard sample: known mass fraction, ω 99.4%, a Chemtek Inc;
36% chunlei quinoline copper suspension concentrate: wherein the mass fraction of the copper quinoline is 33 percent; the mass fraction of kasugamycin is 3 percent.
Ultrapure water: resistivity, 18.2M Ω cm;
chromatographic and mass spectrometric conditions:
chromatographic conditions are as follows: after the instrument state is stable, injecting sample by using the series concentration standard working solution in the step (1), detecting by LC-MS/MS, and on the basis, carrying out LC-MS/MS detection on the sample collected in the step (2), wherein,
liquid phase conditions:
column temperature: 40 ℃;
mobile phase: 0.1% formic acid acetonitrile solution-0.1% formic acid solution (volume ratio 6: 4);
flow rate: 0.2 mL/min;
sample introduction amount: 5L;
mass spectrum conditions:
an ion source: electrospray ion source ESI;
the scanning mode is as follows: scanning positive ions;
the detection mode is as follows: a multiple reaction monitoring mode;
electrospray voltage: 1000 v;
sheath gas pressure: 50 Arb;
auxiliary gas pressure: 10 Arb;
and (3) purging gas: 1 Arb;
ion source temperature: 425 ℃;
transfer tube temperature: at 300 ℃.
(1) Preparation of a standard solution: weighing a proper amount of the oxine-copper standard substance in a 100mL volumetric flask, dissolving the oxine-copper standard substance with methanol, and fixing the volume to a scale to prepare a standard stock solution with the concentration of 0.1 mg/mL. Diluting the standard stock solution step by step to prepare standard working solution with the concentration of 0mg/L, 0.01mg/L, 0.02mg/L, 0.05mg/L, 0.1mg/L, 0.2mg/L, 0.5mg/L, 1.0mg/L and 2.0 mg/L;
(2) extraction: weighing 36% kasugamycin-quinoline copper suspending agent 40mg in a centrifuge tube, adding formic acid acetonitrile solution, homogenizing, performing ultrasonic treatment and centrifugation, collecting extract, and fixing the volume by using the formic acid acetonitrile solution;
(3) detecting by an instrument: and (3) after the state of the instrument is stable, injecting sample by using the series concentration standard working solution in the step (1), detecting by using LC-MS/MS, and carrying out LC-MS/MS detection on the sample collected in the step (2) on the basis. Scanning to obtain quantitative ion and qualitative ion parameters of each pesticide by adopting an SCAN mode, and analyzing and optimizing the parameters
(4) Establishment of a standard curve: adopting peak area quantification, taking the sample injection concentration as a horizontal coordinate and taking the peak area as a vertical coordinate, and drawing a standard curve;
and (4) conclusion: the method is used for measuring the content of the oxine-copper in water, and the result data is as follows: the regression equation of the obtained standard curve is: y 8.532 x 103x+0.431×106Coefficient of correlation R 21. The detection limit (calculated by the signal-to-noise ratio S/N being more than or equal to 10) is 0.089mg/L, compared with the experimental result of the invention, the response value is low, the detection limit is high, the processing process of the test sample is complicated, and the research of the method is not carried out.
2. Method two
The method comprises the following steps: the method in the comparison file is adopted: CN 103592404B-a method for detecting the residual quantity of organic copper pesticides in fruits and vegetables, the method adopts an LC-MS/MS method to detect the residual quantity of organic copper pesticides in fruits and vegetables, and the method is formulated by combining the actual conditions of the environmental research laboratory of our unit.
The instrument comprises the following steps: an ultrahigh-pressure high-performance liquid chromatography-mass spectrometer (Agilent 1290-.
A chromatographic column: c18, inner diameter 150mm multiplied by 2.1mm, 3.5 μm;
reagent:
methanol: chromatographically pure, Merck corporation, (ii) C
Reag.Ph Eur，Lot：I0930107803)；
Acetonitrile: the American world is filled with original imported chromatographic grade reagent at 4L;
formic acid: the known mass fraction is: 95-98%, Shanghai test;
quinoline copper standard sample: known mass fraction, ω 99.4%, a Chemtek Inc;
36% chunlei quinoline copper suspension concentrate: wherein the mass fraction of the copper quinoline is 33 percent; the mass fraction of kasugamycin is 3 percent.
Ultrapure water: resistivity, 18.2M Ω cm;
(1) preparing a test solution: weighing 36% kasugamycin-oxine-copper suspension 40mg in a centrifuge tube, adding 1gNa2S, fully performing vortex oscillation on a vortex oscillation instrument for 2min, then adding 15mL of methanol, performing vortex oscillation for 2min, performing ultrasonic extraction for 1h (shaking once every 20min during ultrasonic treatment), and centrifuging at 4000rpm on a centrifuge for 10 min. The extraction was repeated once by adding 5mL of methanol. And combining the two extracted supernatants, fixing the volume in a 25mL volumetric flask, and mixing uniformly. Taking 1mL of the extract, placing in a 2mL centrifuge tube, adding 50mg of PSA and 50mgC18 adsorbent, and centrifuging for 10min in an 13000rpm ultra-high speed centrifuge. Taking the supernatant, filtering with 0.45 μm filter membrane, and testing.
(2) UPLC-MS/MS detection
The detection conditions of the UPLC are as follows:
column temperature: 25 ℃;
mobile phase: phase A is acetonitrile and phase B is 0.1% formic acid solution in water. Gradient elution condition is 0-2 min, and 40% A is kept; for 2-4.5 min, 80-20% of A; keeping 80% A for 4.5-10 min; 10-12 min, 80% -40% A; keeping 40% A for 12-15 min;
flow rate: 0.20 mL/min;
sample introduction amount: 10 mu L of the solution;
the MS/MS conditions are as follows:
an ion source: electrospray ion source ESI;
the scanning mode is as follows: a negative ion source;
spraying voltage: 2800V;
capillary temperature: 350 ℃;
sheath gas pressure: 45 Arb;
auxiliary gas pressure: 15 Arb;
(3) establishment of a Standard Curve
Weighing a proper amount of the oxine-copper standard substance into a 100mL volumetric flask, dissolving with methanol to a constant volume, and preparing 100mg/L stock solution. Diluting the standard stock solution of oxine-copper step by step to prepare standard working solutions of 0.001, 0.005, 0.01, 0.05, 0.1, 0.5 and 1.0 mg/L. And drawing a standard curve by taking the sample injection concentration as a horizontal coordinate and the peak area as a vertical coordinate.
The process of treating the test sample for the method is suitable for detecting the solid objects of vegetables and fruits, the operation for detecting the residual oxine-copper in water in the natural environment is complicated, the direct addition of the solid reagent is poor in collateral breaking effect, the response value is low, and the research on the method is not carried out.
3. Method III
The following are experimental studies of the methodology of the present invention:
preparation of a test solution: weighing 0.0396g of 36% Chunlei and quinoline copper suspending agent sample (wherein the mass fraction of quinoline copper is 33%, and the mass fraction of kasugamycin is 3%) in a 100mL volumetric flask, adding aerated water to dilute the sample to a scale, putting 10.0mL in a 2000mL beaker, diluting the sample to 2000mL scale with aerated water to obtain a quinoline copper aqueous solution with the concentration of 653.40 mug/L, namely the quinoline copper aqueous solution to be detected, adding a 0.3% sulfuric acid aqueous solution according to the volume ratio of 1:1, carrying out vortex mixing for 5min, carrying out ultrasonic treatment for 5min after full reaction, and filtering with a 0.45um filter membrane to obtain the sample to be detected by UPLC-MS/MS;
preparation of control solutions: weighing 0.0114g of standard oxine-copper sample (omega is 99.4 percent), placing the standard oxine-copper sample into a 100.00mL volumetric flask, treating the standard oxine-copper sample with 0.3 percent of sulfuric acid aqueous solution, carrying out vortex mixing for 5min, carrying out ultrasonic treatment for 5min after full reaction, filtering the mixture with a 0.45um filter membrane to obtain standard sample stock solution with the concentration of the derived oxine-copper being 113.32mg/L, sucking proper stock solution, diluting the stock solution with 0.3 percent of sulfuric acid aqueous solution to prepare a series of standard working solutions with the gradient concentrations of 4.53 mu g/L, 9.07 mu g/L, 22.66 mu g/L, 45.33 mu g/L, 113.32 mu g/L, 226.63 mu g/L and 566.58 mu g/L, and determining the standard working solutions by UPLC-MS/MS;
measurement and calculation of results: setting instrument parameters, performing UPLC-MS/MS determination on a reference solution and a test solution after the instrument is stabilized, recording a chromatogram, drawing a standard curve by taking the concentration of the oxine-copper derivative 8-hydroxyquinoline as a horizontal coordinate and the peak area of the 8-hydroxyquinoline as a vertical coordinate, substituting the peak area of the oxine-copper derivative 8-hydroxyquinoline measured in the sample into the standard curve to obtain the content of the 8-hydroxyquinoline in the sample solution, and calculating by taking the content of the 8-hydroxyquinoline as the content of the oxine-copper;
wherein the HPLC operating conditions are as follows:
sample introduction volume: 2.0 mu L;
flow rate: 0.3 mL/min;
column temperature: 40 ℃;
mobile phase: methanol + 0.1% formic acid water;
the elution procedure was: mobile phase A, methanol, mobile phase B: 0.1% formic acid water;
| time (minutes) | Mobile phase A (%) | Mobile phase B (%) |
| 0～1.5min | 10％～90％ | 90％～10％ |
| 1.5～2.0min | 90％～10％ | 10％～90％ |
| 2.0～3.5min | 10％ | 90％ |
The MSD operating conditions were:
1) and (3) monitoring mode: MRM;
2) detection mode: a negative ion mode;
ion source parameters: drying gas: n is a radical of2(ii) a Temperature of the drying gas: 300 ℃; flow rate of drying gas: 5L/min; sheath gas: n is a radical of2(ii) a Temperature of sheath gas: 350 ℃; flow rate of sheath gas: 11L/min; atomizer pressure (Nebulizer): 45 psi; nozzle voltage: 500V; capillary voltage (Capillary): 3500V, EMV gain: 0V;
the MRM ion acquisition parameters are as follows:
is quantitative ion
And (3) qualitative identification: for the parent ion and the ion pair of the pesticide, if the ion chromatographic retention time is consistent with that of the standard sample working solution (the variation range is within +/-2.5 percent); and when the ion abundance Ratio (Ratio) of the target compound in the sample is not more than 20%, judging that the measured mass spectrum signal is the pesticide oxine-copper, and if the two conditions cannot be met simultaneously, judging that the pesticide oxine-copper is not contained.
1.1. Method investigation test
1.1.1 Linear test
Precisely sucking 4.53 mu g/L, 9.07 mu g/L, 22.66 mu g/L, 45.33 mu g/L, 113.32 mu g/L, 226.63 mu g/L and 566.58 mu g/L of the oxine-copper control solution, performing regression analysis on the corresponding concentrations of the oxine-copper control solution according to the chromatographic peak area of the standard working solution to obtain a linear equation of y-2447.66 x-3454.87, wherein R is2Results are shown in table 1 and figure 2, 0.9997.
The quinoline copper injection concentration is shown to be in good linear relation in the range of 4.53 mu g/L-566.58 mu g/L. The results are shown in Table 2.
TABLE 1 Quinoliness test results for copper quinolines
1.1.2 instrumental precision test
The 45.33 mug/L reference substance solution prepared by the preparation method of the reference substance solution is taken, sample injection is repeated for 6 times under the chromatographic conditions, the precision of the relative standard deviation verification method is calculated, the RSD (quinolinic copper) value is calculated to be 0.3645%, the precision of the instrument is good, and the measurement result is shown in Table 2.
TABLE 2 Instrument precision test results
1.1.3 recovery rate by adding standard:
5mL of a oxine-copper sample solution (the concentration of 8-hydroxyquinoline is 295.32. mu.g/L) prepared with aerated water was added to a quinolinone copper standard sample solution (the concentration of 8-hydroxyquinoline is 128.69. mu.g/L), and the quinolinone copper sample solution and the standard sample solution were mixed and shaken well and paralleled for 5 times. The recovery rate of the added standard is calculated according to the formula (1) by the measured value according to the operation conditions of the instrument, and the result is shown in Table 3
Normalized recovery (%) as (detected amount/normalized amount) × 100% … … … … … … formula (1)
TABLE 3 Quinoline copper aerated water recovery test results
3.2.5 stability test
Preparing a test solution by using aerated water for stability test, placing at room temperature, injecting samples for 0 hour, 24 hours and 48 hours respectively under a proposed chromatographic condition, measuring peak areas, and calculating the concentration of the oxine-copper, wherein the result shows that the oxine-copper can be maintained at more than 80% of the concentration of the oxine-copper within 0 hour within 48 hours, and the stability test result is shown in table 4.
TABLE 4 stability test results
1.1.4 detection and quantitation limits
The control solution prepared by the preparation method of the control solution is diluted into standard use solution with the concentration of 0.45 mu g/L, the measurement is repeated for 6 times, LOD and LOQ values are calculated according to S/N values, and the test result shows that the LOD of the established method for the oxine-copper is 0.050 mu g/L, and the LOQ is 0.165 mu g/L. The detailed results are shown in Table 5.
TABLE 5 analytical methods detection limit and quantitation limit test results
1.2 method one, method two and method three experimental results are summarized and compared.
1.2.1 comparison of regression equations of Standard curves
And (4) conclusion: using the comparison file, method one, in the higher concentration range of 0.01 mg/L-2.0 mg/L, the linear equation Y is 8.532 × 103X + 0.431X 106, correlation coefficient R2Method II obtains linear equation Y of 3.465 x 10 in the concentration range of 0.001mg/L to 1.0mg/L2X+16.29×104，Coefficient of correlation R20.9987, method three is the preferred method of the invention, in the lower concentration range of 4.53 ug/L-566.58 ug/L, the linear equation y is 2447.66x-3454.87, and the correlation coefficient R is2Method three is the most preferred method, 0.9997.
1.2.2 comparison of detection Limit with quantification Limit
| Serial number | Experiment of | Detection limit | Limit of |
| 1 | Method one (comparison example) | 0.089mg/L | 0.400mg/ |
| 2 | Method two (comparative example) | 0.037mg/L | 0.1430mg/ |
| 3 | Method III (invention) | 0.050μg/L | 0.165μg/L |
And (4) conclusion: the first method and the second method are comparative experiments, and the detection limit of the first method is 0.089mg/L, the quantification limit is 0.400mg/L, the detection limit of the second method is 0.037mg/L, and the quantification limit is 0.1430mg/L, which are higher than the detection limit of the third method of the preferred method of the invention, namely 0.050 mug/L and 0.165 mug/L.
To summarize: the invention has good linear relation in the lower concentration range of the oxine-copper, namely 4.53 ug/L-566.58 ug/L, while the concentration range of the method using the comparison file is higher, specifically 0.01 mg/L-2.0 mg/L; the detection limit of the invention can reach 0.050 mug/L, the quantification limit reaches 0.165 mug/L, while the detection limit of the method using the comparison document is 0.089mg/L, and the quantification limit is 0.400mg/L, which are superior to the comparison document; the preparation process of the test sample is simple to operate, the test sample solution is relatively stable within 48 hours, the precision of the instrument is high, the repeatability of the reference substance is good, the RSD% value is 0.96%, and the method can effectively detect the low-content oxine-copper in water.
While the invention has been described in detail in the foregoing by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that certain changes and modifications may be made therein based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (4)
1. A method for detecting oxine-copper in water by using a UPLC-MS/MS method is characterized by comprising the following steps:
preparation of a test solution: weighing 0.0396g of 36% Chunlei quinoline copper suspending agent sample in a 100mL volumetric flask, adding aerated water to dilute to a scale, putting 10.0mL in a 2000mL beaker, diluting with aerated water to 2000mL to obtain a quinoline copper aqueous solution with the concentration of 653.40 mug/L, namely the quinoline copper aqueous solution to be detected, adding 0.1-0.5% sulfuric acid aqueous solution into the quinoline copper aqueous solution to be detected according to the volume ratio of 1: 1-1: 3, carrying out vortex mixing for 5-20 min, carrying out ultrasonic treatment for 5-20 min after full reaction, filtering with a 0.45um filter membrane to obtain the derivative quinoline copper aqueous solution, and determining by UPLC-MS/MS;
(2) preparation of control solutions: weighing 0.0114g of oxine-copper standard sample, placing the weighed sample in a 100.00mL volumetric flask, treating the sample with 0.1-0.5% sulfuric acid aqueous solution, carrying out vortex mixing for 5-20 min, carrying out ultrasonic treatment for 5-20 min after full reaction, filtering the sample with a 0.45um filter membrane to obtain a standard sample stock solution with the concentration of the derived oxine-copper of 113.32mg/L, sucking a proper stock solution, diluting the stock solution with 0.1-0.5% sulfuric acid aqueous solution to prepare a series of standard working solutions with the gradient concentrations of 4.53 mu g/L, 9.07 mu g/L, 22.66 mu g/L, 45.33 mu g/L, 113.32 mu g/L, 226.63 mu g/L and 566.58 mu g/L, and determining the standard working solutions by UPLC-MS/MS;
(3) measurement and calculation of results: setting instrument parameters, and performing UPLC-MS/MS measurement on the reference solution and the test solution after the instrument is stable:
the UPLC operating conditions were: 1) sample introduction amount: 2.0 mu L; 2) column temperature: 40 ℃; 3) flow rate: 0.3 mL/min; 4) a chromatographic column: agilent Hilic Plus RRHD, Specification: 2.1X 50mm, 1.8 μm; 5) elution solvent and procedure: eluting solvent: mobile phase A, methanol, mobile phase B: 0.1% formic acid water; the elution procedure was:
The MS/MS operation conditions are as follows: 1) and (3) monitoring mode: MRM; 2) detection mode: negative poleAn ionic mode; 3) ion source parameters: drying gas: n is a radical of2(ii) a Temperature of the drying gas: 300 ℃; flow rate of drying gas: 5L/min; sheath gas: n is a radical of2(ii) a Temperature of sheath gas: 350 ℃; flow rate of sheath gas: 11L/min; atomizer pressure: 45 psi; nozzle voltage: 500V; capillary voltage: 3500V, EMV gain: 0V;
the MRM ion acquisition parameters are as follows: monitoring for 0-3.5 min; the name of the target compound is 8-hydroxyquinoline; 145.1 parent ions, 128.1 daughter ion quantitative ions, 150V fragment voltage, 104eV collision energy and 26V cell acceleration voltage; the parent ion 145.1, the daughter ion 118.1, the Fragmentor voltage 150V, the collision energy 104eV, the cell acceleration voltage 24V,
recording a chromatogram, taking the content of the 8-hydroxyquinoline as the content of the oxine-copper, and calculating according to an external standard method.
2. The method for detecting oxine-copper in water by using the UPLC-MS/MS method according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
(1) preparation of a test solution: weighing 0.0396g of a 36% Chunlei quinoline copper suspending agent sample in a 100mL volumetric flask, adding aerated water to dilute the sample to a scale, putting 10.0mL in a 2000mL beaker, diluting the sample to 2000mL with aerated water to obtain a quinoline copper aqueous solution with the concentration of 653.40 mug/L, namely the quinoline copper aqueous solution to be detected, adding 0.2-0.4% sulfuric acid aqueous solution into the quinoline copper aqueous solution to be detected according to the volume ratio of 1:2, carrying out vortex mixing for 5-10 min, carrying out ultrasonic treatment for 5-10 min after full reaction, filtering the solution with a 0.45um filter membrane to obtain a derivative quinoline copper aqueous solution, and detecting the derivative quinoline copper aqueous solution by UPLC-MS/MS;
(2) preparation of control solutions: weighing 0.0114g of oxine-copper standard sample, placing the weighed sample in a 100.00mL volumetric flask, treating the sample with 0.2-0.4% sulfuric acid aqueous solution, carrying out vortex mixing for 5-10 min, carrying out ultrasonic treatment for 5-10 min after full reaction, filtering the sample with a 0.45um filter membrane to obtain a standard sample stock solution with the concentration of the derived oxine-copper of 113.32mg/L, sucking a proper stock solution, diluting the stock solution with 0.2-0.4% sulfuric acid aqueous solution to prepare a series of standard working solutions with the gradient concentrations of 4.53 mu g/L, 9.07 mu g/L, 22.66 mu g/L, 45.33 mu g/L, 113.32 mu g/L, 226.63 mu g/L and 566.58 mu g/L, and determining the standard working solutions by UPLC-MS/MS;
(3) measurement and calculation of results: setting instrument parameters, performing UPLC-MS/MS determination on the reference solution and the test solution after the instrument is stabilized, recording a chromatogram, and calculating according to an external standard method by taking the content of 8-hydroxyquinoline as the content of oxine-copper.
3. The method for detecting oxine-copper in water by using the UPLC-MS/MS method according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
(1) preparation of a test solution: weighing 0.0396g of 36% Chunlei quinoline copper suspending agent sample in a 100mL volumetric flask, adding aerated water to dilute to a scale, putting 10.0mL in a 2000mL beaker, diluting with aerated water to 2000mL to obtain a quinoline copper aqueous solution with the concentration of 653.40 mug/L, namely the quinoline copper aqueous solution to be detected, taking the quinoline copper aqueous solution to be detected, adding 0.3% sulfuric acid aqueous solution according to the volume ratio of 1:1, carrying out vortex mixing for 5min, carrying out ultrasonic treatment for 5min after full reaction, filtering with a 0.45um filter membrane to obtain the derivative quinoline copper aqueous solution, and detecting by UPLC-MS/MS;
(2) preparation of control solutions: weighing 0.0114g of oxine-copper standard sample, placing the weighed sample in a 100.00mL volumetric flask, treating the sample with 0.3% sulfuric acid aqueous solution, vortex mixing for 5min, carrying out ultrasonic treatment for 5min after full reaction, filtering the sample with a 0.45um filter membrane to obtain a standard sample stock solution with the concentration of the derived oxine-copper of 113.32mg/L, sucking a proper stock solution, diluting the standard sample stock solution with 0.3% sulfuric acid aqueous solution to prepare a series of standard working solutions with the gradient concentrations of 4.53 mu g/L, 9.07 mu g/L, 22.66 mu g/L, 45.33 mu g/L, 113.32 mu g/L, 226.63 mu g/L and 566.58 mu g/L, and determining the standard working solutions by UPLC-MS/MS;
(3) measurement and calculation of results: setting instrument parameters, performing UPLC-MS/MS determination on the reference solution and the test solution after the instrument is stabilized, recording a chromatogram, and calculating by taking the content of the 8-hydroxyquinoline as the content of the oxine-copper.
4. The method for detecting oxine-copper in water by using the UPLC-MS/MS method according to claim 1, wherein the method comprises the following steps: the method has the detection limit LOD of 0.050 mu g/L and the quantification limit LOQ of 0.165 mu g/L for the oxine-copper.
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