CN108132309B - Analysis method for determining residual quantity of thiediazole copper in dendrobium officinale - Google Patents
Analysis method for determining residual quantity of thiediazole copper in dendrobium officinale Download PDFInfo
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Abstract
The invention provides a method for determining residual quantity of thiediazole copper in dendrobium officinale, which comprises the steps of adding a sodium sulfide solution into a dendrobium officinale sample, deriving and converting thiediazole copper into a metabolite thiadiazole, extracting acetonitrile, adding an acid to adjust the pH value, adding ethyl acetate for liquid-liquid distribution, concentrating an organic phase to dryness by using a rotary evaporator, removing interfering substances in an extracting solution by using a solid-phase extraction method, and finally detecting by using an ultra-performance liquid chromatography-mass spectrometer/mass spectrometer. The method can effectively avoid the matrix interference of the sample and obtain good effect. The method has the advantages of high accuracy, precision, sensitivity, high recovery rate and small impurity interference, and can effectively determine the content of the thiediazole copper in the dendrobium officinale.
Description
Technical Field
The invention belongs to the technical field of pesticide residue determination, and particularly relates to an analysis method for the residual quantity of thiediazole copper in dendrobium officinale.
Background
Thiacloprid is a patent product developed by chemical Limited company of Longwan of Zhejiang, has the chemical name of 2-amino-5-mercapto-1, 3 and 4-thiadiazole copper complex, and the main metabolite is thiadiazole, so that the thiadiazol copper complex is an efficient and broad-spectrum systemic bactericide. The bactericidal mechanism is unique, the thiazole group has unique prevention effect on bacteria, and the copper ions have prevention and treatment effects on fungi and bacteria, and can be widely used for preventing and treating more than 20 kinds of crops with more than 60 kinds of bacteria and fungal diseases. At present, the pesticide composition is applied to the prevention and treatment of diseases such as soft rot, leaf spot, bacterial blight and the like on crops such as Chinese cabbages, tomatoes, oranges, cucumbers, rice, watermelons, tobaccos and the like. The pesticide has high efficiency, low toxicity and safety, has high efficiency in preventing and treating bacterial and fungal diseases of crops, and has obvious effect in preventing and treating soft rot of dendrobium officinale.
At present, no corresponding national and industrial standards exist for a method for detecting the residual Thiodiazole copper. In recent years, domestic literature reports that the high performance liquid chromatography is adopted to measure the residual quantity of Thiobacillus copper in watermelon, soil and tobacco. Because the matrix of the dendrobium officinale is complex, the high performance liquid chromatography method is adopted for detection, the purification effect is not ideal, the matrix interference is serious, the sensitivity is low, the residual quantity of the thiediazole copper in the dendrobium officinale cannot be accurately measured by using the liquid phase method, and a more effective detection method needs to be developed.
Disclosure of Invention
In order to evaluate the safety of the thiediazole copper in the dendrobium officinale, the invention establishes a method for determining the residual quantity of the thiediazole copper in the dendrobium officinale by using an ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry (UPLC/MS/MS) method. Adding a sodium sulfide solution into a dendrobium officinale sample, deriving and converting thiodiazole copper into a metabolite thiadiazole, extracting acetonitrile, adding acid to adjust the pH value, adding ethyl acetate for liquid-liquid distribution, taking an organic phase, concentrating the organic phase to dryness by using a rotary evaporator, removing interfering substances in an extracting solution by using a solid phase extraction method, and finally detecting by using an ultra performance liquid chromatography-mass spectrometry/mass spectrometry (UPLC/MS/MS). The results show that: the linear range of the method is 0.05-5.0 mg/L, the lowest detection concentration is 0.050 mg/kg, and the average recovery rate is 92-96%. The invention provides the following technical scheme:
an analysis method for determining the residual quantity of thiediazole copper in dendrobium officinale, which is characterized by comprising the following steps:
(1) derivatization: weighing 5-10g of sample, placing the sample in a conical flask with a plug, adding 20-60 mL of 0.1mol/L sodium sulfide solution, heating to 30-60 ℃, and oscillating for 30 minutes;
(2) extraction: adding 20-60 mL of acetonitrile, oscillating at room temperature for 1-2 hours, filtering after oscillation is finished, and using 1mol/L H as filtrate2SO4Adjusting the pH to 4-5;
(3) and (3) extraction: transferring the solution to a separating funnel, adding 50-100 mL ethyl acetate for extraction, taking an upper organic phase, drying with anhydrous sodium sulfate, filtering, concentrating the filtrate under reduced pressure in a constant-temperature water bath at 40 ℃ until the filtrate is nearly dry, adding 2.0 mL petroleum ether and acetone (1: 1, v: v) for dissolution, and waiting for purification;
(4) purifying: taking a Florisil solid phase column, activating with petroleum ether, sampling the extractive solution to be purified, eluting with petroleum ether and acetone (1: 1, v: v), collecting eluate, concentrating under reduced pressure to dry, blowing with nitrogen, diluting with methanol to desired volume, and filtering with filter membrane;
(5) and (3) determination: and detecting by using an ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry combination instrument.
The specific method for determining the residual quantity of thiediazole copper in the dendrobium officinale comprises the following steps:
1. test materials
Reagents and materials: sodium sulfide, dimethylformamide, ethyl acetate, acetone, petroleum ether were all analytical, methanol (chromatographic purity, Merck, Germany), pure water (Millipore Co., Ltd.), Flori silica solid phase column (Beijing vibrato science and technology Co., Ltd.)
And (3) standard substance: thiacloprid standard (purity 99.1%, provided by Longwan chemical Co., Ltd., Zhejiang)
The instrument comprises the following steps: shimadzu LCMS8050 high performance liquid chromatography tandem mass spectrometer; shanghai Shensheng R-201 type rotary evaporator; shanghai Shensheng W201B model digital control constant temperature bath kettle; model SHZ-d (iii) circulating water vacuum pump; an SPS202F model electronic balance; one ten thousandth day of METTLER TOLEDO, switzerland.
2. Test method
Derivative extraction: weighing 5.0g of dendrobium officinale sample, placing the dendrobium officinale sample in a conical flask with a plug, adding 20 mL of 0.1mol/L sodium sulfide solution, heating to 30 ℃, oscillating for 30 minutes, adding 20.0 mL of acetonitrile, continuing oscillating for 1 hour, performing suction filtration after oscillation is finished, performing suction filtration, and using 1mol/L H as filtrate2SO4Adjusting pH to 4-5, transferring the above solution to a separating funnel, adding 50 mL ethyl acetate for extraction, collecting upper organic phase, drying with anhydrous sodium sulfate, filtering, concentrating the filtrate under reduced pressure in 40 deg.C constant temperature water bath to near dry, adding 2.0 mL petroleum ether and acetone (1:)1, v: v) dissolving, and purifying.
Purifying: taking a Florisil solid phase column, activating with petroleum ether, sampling the extractive solution to be purified, eluting with petroleum ether and acetone (1: 1, v: v), collecting eluate, concentrating under reduced pressure in a constant temperature water bath at 40 deg.C until dry, blowing with nitrogen, diluting with chromatographic methanol to desired volume, and filtering with 0.22 μm filter membrane.
3. Conditions of instrumental analysis
3.1 liquid phase conditions
A chromatographic column: waters acquity UPLCTM BEH C18（1.7µm，2.1×100 mm）；
Column temperature: 40 ℃;
flow rate: 0.20 mL/min;
mobile phase: acetonitrile: 0.1% aqueous formic acid =20:80 (v/v)
Sample introduction amount: 1 mu L;
quantification by external standard method.
3.2 Mass Spectrometry conditions
Mass spectrometer conditions: capillary voltage is 4.0 kV, DL temperature is 250 ℃, atomizing gas flow is 3.0L/min, Interface temperature is 300 ℃, heater flow is 10L/min, ionization mode: ESI+The detection mode is multi-reaction monitoring scan mode (MRM), see table 1.
TABLE 1 Mass Spectrometry conditions
| Parent ion | Daughter ions | Q1 Pre Bias(V) | CE(V) | Q3 Pre Bias(V) |
| 133.90 | 75.00 | -14 | -17 | -16 |
| 133.90 | 42.95 | -24 | -31 | -17 |
4. Linear relation of method
And dissolving the standard sample by using dimethylformamide to prepare a 100 mg/L standard stock solution of the thiediazole copper. Diluting with dimethylformamide to obtain the standard working solutions of Thiobacillus copper series with concentrations of 0.05, 0.10, 0.20, 0.50, 1.0, 2.0 and 5.0 mg/L. Adding a series of working solutions with the sample injection concentration of 0.05, 0.10, 0.20, 0.50, 1.0, 2.0 and 5.0 mg/L into blank water, injecting according to the processing steps and instrument conditions of the method, drawing a standard curve of the thiediazole copper by using concentration-peak area, wherein the regression equation is y = 287604x-5164, R = 0.9995, wherein y is the area of the thiediazole copper peak, and x is the concentration of the standard solution.
5. Method recovery and relative standard deviation
In the blank dendrobium officinale samples, 3 levels of concentration (0.050, 0.50 and 10 mg/kg) of thiediazole copper standard solutions are respectively added, each level is repeated for 5 times, meanwhile, the 3 levels of concentration of thiediazole copper standard solutions are added into the blank aqueous solution to be used as standard solution for treatment, sample injection is carried out according to the treatment steps and the instrument method, the recovery rate is measured, the result is shown in table 2, and the recovery rate curve is shown in fig. 2. Experiments show that the recovery rate meets the detection requirement of pesticide residue, and the method is proved to have better recovery rate and repeatability.
TABLE 2 Thiodiazole copper addition recovery test
6. Minimum detected concentration of the method
By applying the method, the minimum addition concentration of the thiediazole copper in the dendrobium officinale is 0.050 mg/kg, and the response values of samples on the instrument are all larger than 3 times of the signal-to-noise ratio of the instrument, so that the following results are obtained: the lowest detection concentration of the thiediazole copper in the dendrobium officinale is 0.050 mg/kg.
7. Minimum detected amount
Under the above analysis conditions, the minimum detection amount of Thiodiazole copper by the instrument is 5.0X 10-11g. Taking the 3 times signal-to-noise ratio of the instrument as the detection limit of the instrument, and taking the minimum detection amount (g) = detection limit (mg/L) × sample injection volume (muL) × 10-9。
The analysis method for determining the residual quantity of the thiediazole copper in the dendrobium officinale provided by the invention has the positive effects that: the method can effectively avoid the matrix interference of the sample and obtain good effect. The method has the advantages of high accuracy, precision, sensitivity, high recovery rate and small impurity interference, and can effectively determine the content of the thiediazole copper in the dendrobium officinale.
Drawings
FIG. 1 is a chromatogram of a blank Dendrobium officinale sample without Thiodiazole copper.
FIG. 2 is a chromatogram of a blank Dendrobium officinale sample added with 0.50 mg/kg Thiodiazole copper.
Detailed Description
To more fully explain the implementation of the present invention, an example of an analysis method for the residual amount of thiediazole copper in dendrobium officinale is provided. These examples are merely illustrative and do not limit the scope of the invention. All of which are commercially available.
Example 1
(1) Derivatization: weighing 5g of dendrobium officinale sample, placing the dendrobium officinale sample in a conical flask with a plug, adding 20 mL of 0.1mol/L sodium sulfide solution, heating to 30 ℃, and oscillating for 30 minutes;
(2) extraction: then 20 mL of acetonitrile is added, the mixture is shaken for 1 hour at room temperature, after shaking, the mixture is filtered, and the filtrate is used at the concentration of 1mol/L H2SO4Adjusting the pH to 4-5;
(3) and (3) extraction: transferring the solution to a separating funnel, adding 50 mL of ethyl acetate for extraction, taking an upper organic phase, drying by using anhydrous sodium sulfate, filtering, concentrating the filtrate under reduced pressure in a constant-temperature water bath at 40 ℃ until the filtrate is nearly dry, adding 2.0 mL of petroleum ether and acetone (1: 1, v: v) for dissolution, and waiting for purification;
(4) purifying: taking a Florisil solid phase column, activating with petroleum ether, sampling the extractive solution to be purified, eluting with petroleum ether and acetone (1: 1, v: v), collecting eluate, concentrating under reduced pressure to dry, blowing with nitrogen, diluting with methanol to desired volume, and filtering with filter membrane;
(5) and (3) determination: detecting by using an ultra-high performance liquid chromatography-mass spectrum/mass spectrum combined instrument;
(6) and (3) measuring results: the content of the thiediazole copper in the dendrobium officinale is determined to be lower than 0.050 mg/kg through the steps.
Example 2
(1) Derivatization: weighing 10g of dendrobium officinale sample, placing the dendrobium officinale sample in a conical flask with a plug, adding 60 mL of 0.1mol/L sodium sulfide solution, heating to 60 ℃, and oscillating for 30 minutes;
(2) extraction: adding 60 mL of acetonitrile, shaking at room temperature for 2 hours, filtering after shaking is finished, and using 1mol/L H as filtrate2SO4Adjusting the pH to 4-5;
(3) and (3) extraction: transferring the solution to a separating funnel, adding 100 mL of ethyl acetate for extraction, taking an upper organic phase, drying by using anhydrous sodium sulfate, filtering, concentrating the filtrate under reduced pressure in a constant-temperature water bath at 40 ℃ until the filtrate is nearly dry, adding 2.0 mL of petroleum ether and acetone (1: 1, v: v) for dissolution, and waiting for purification;
(4) purifying: taking a Florisil solid phase column, activating with petroleum ether, sampling the extractive solution to be purified, eluting with petroleum ether and acetone (1: 1, v: v), collecting eluate, concentrating under reduced pressure to dry, blowing with nitrogen, diluting with methanol to desired volume, and filtering with filter membrane;
(5) and (3) determination: detecting by using an ultra-high performance liquid chromatography-mass spectrum/mass spectrum combined instrument;
(6) and (3) measuring results: the content of the thiediazole copper in the dendrobium officinale is determined to be 0.081 mg/kg through the steps.
Example 3
(1) Derivatization: weighing 7.5 g of dendrobium officinale sample, placing the dendrobium officinale sample in a conical flask with a plug, adding 20-60 mL of 0.1mol/L sodium sulfide solution, heating to 40 ℃, and oscillating for 30 minutes;
(2) extraction: then 40 mL of acetonitrile is added, the mixture is shaken at room temperature for 1.5 hours, after shaking, the mixture is filtered, and the filtrate is used at the concentration of 1mol/L H2SO4Adjusting the pH to 4-5;
(3) and (3) extraction: transferring the solution to a separating funnel, adding 70 mL of ethyl acetate for extraction, taking an upper organic phase, drying by using anhydrous sodium sulfate, filtering, concentrating the filtrate under reduced pressure in a constant-temperature water bath at 40 ℃ until the filtrate is nearly dry, adding 2.0 mL of petroleum ether and acetone (1: 1, v: v) for dissolution, and waiting for purification;
(4) purifying: taking a Florisil solid phase column, activating with petroleum ether, sampling the extractive solution to be purified, eluting with petroleum ether and acetone (1: 1, v: v), collecting eluate, concentrating under reduced pressure to dry, blowing with nitrogen, diluting with methanol to desired volume, and filtering with filter membrane;
(5) and (3) determination: detecting by using an ultra-high performance liquid chromatography-mass spectrum/mass spectrum combined instrument;
(6) and (3) measuring results: the content of the thiediazole copper in the dendrobium officinale is determined to be lower than 0.050 mg/kg through the steps.
It will be apparent to those skilled in the art that various changes and modifications can be made in the above embodiments without departing from the scope and spirit of the invention, and it is intended that all such changes and modifications as fall within the true spirit and scope of the invention be interpreted in accordance with the principles of the invention. And the invention is not limited by the example embodiments set forth in the description.
Claims (1)
1. An analysis method for determining residual quantity of thiediazole copper in dendrobium officinale, which is characterized by comprising the following steps:
(1) derivatization: weighing 5-10g of dendrobium officinale sample, placing the dendrobium officinale sample in a conical flask with a plug, adding 20-60 mL of 0.1mol/L sodium sulfide solution, heating to 30-60 ℃, and oscillating for 30 min;
(2) extraction: adding 20-60 mL of acetonitrile, oscillating at room temperature for 1-2 hours, filtering after oscillation is finished, and using 1mol/L H as filtrate2SO4Adjusting the pH to 4-5;
(3) and (3) extraction: and (2) transferring the solution to a separating funnel, adding 50-100 mL of ethyl acetate for extraction, taking an upper organic phase, drying by using anhydrous sodium sulfate, filtering, concentrating the filtrate at a constant temperature of 40 ℃ under reduced pressure until the filtrate is nearly dry, and adding 2.0 mL of petroleum ether: acetone, v: v = 1: 1, dissolved, ready to be purified;
(4) purifying: taking a Florisil solid phase column, activating petroleum ether, taking the extract to be purified, and sampling the extract, namely petroleum ether, acetone, v: v = 1: 1, eluting, collecting eluate, concentrating under reduced pressure to dry, blowing dry with nitrogen, diluting to constant volume with methanol, and filtering with filter membrane;
(5) and (3) determination: detecting by adopting a liquid chromatography-mass spectrometer, wherein the determination conditions are as follows: a chromatographic column: waters acquity UPLCTM BEH C18, 1.7 μm, 2.1 × 100 mm; column temperature: 40 ℃; flow rate: 0.20 mL/min; mobile phase: acetonitrile: 0.1% aqueous formic acid =20:80, v/v; sample introduction amount: 1 mu L; quantifying by an external standard method; mass spectrum conditions: the capillary voltage is 4.0 kV, the DL temperature is 250 ℃, the atomizing gas flow is 3.0L/min, the Interface temperature is 300 ℃, and the heater flow is 10L/min; an ionization mode: ESI+The detection mode is a multi-reaction monitoring scanning mode, and the quantitative and qualitative ion pair is 133.90>75.00, quant Q1-17V; CE-17V; Q3-16V, 133.90>42.95, qualitative Q1-24V; CE-31V; Q3-17V.
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