CN107462646B - Method for detecting residual quantity of cyanamide in fruit - Google Patents
Method for detecting residual quantity of cyanamide in fruit Download PDFInfo
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- CN107462646B CN107462646B CN201710648571.XA CN201710648571A CN107462646B CN 107462646 B CN107462646 B CN 107462646B CN 201710648571 A CN201710648571 A CN 201710648571A CN 107462646 B CN107462646 B CN 107462646B
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G01N30/12—Preparation by evaporation
Abstract
The invention relates to a method for detecting residual quantity of cyanamide in fruits. The method comprises the following specific steps: (1) drawing a standard curve; (2) sample extraction; (3) deriving from the concentrated solution; (4) measuring the recovery rate; (5) measuring the content of the cyanamide in the sample; according to the method for detecting the residual quantity of cyanamide in the fruit, anhydrous sodium sulfate is used for removing water, ethyl acetate is used for extracting, an extracting solution is concentrated, purification is not needed, the extracting solution can be directly derived from dansyl chloride, and the test operation is simple and convenient. The liquid chromatogram tandem mass spectrum multi-reaction monitoring mode is adopted, so that the selectivity and the sensitivity are high, the impurity interference can be effectively reduced, the accuracy and the precision are high, and the technical support is provided for further perfecting and supplementing the dietary intake and risk data of cyanamide of residents and formulating the maximum residual limit.
Description
Technical Field
The invention relates to the technical field of trace analysis, in particular to a method for detecting residual quantity of cyanamide in fruits.
Background
The cyanamide is not only a plant growth regulator, but also can be used as an insecticide and a fertilizer, and is widely applied in agriculture. However, the current standard detection method for detecting the residual quantity of cyanamide in China only stipulates the temporary limit of the cyanamide on the grapes in the national standard GB 2763-2016 food safety standard. The main reason is that cyanamide has a small molecular weight, is very soluble in water and is volatile, and is difficult to extract and concentrate by common solvents. In addition, the cyanamide has no chromophoric group, is unstable under heat, acid and alkali, and has great difficulty in directly detecting the residual quantity of the cyanamide without derivation. In order to understand and find out the dietary intake level and risk of the cyanamide in domestic residents, the maximum residual limit value of the cyanamide in agricultural products is specified, and a simple, quick and effective residual analysis method of the cyanamide in the agricultural products is required to be established as the premise. The invention provides such a detection method.
Disclosure of Invention
The invention aims to solve the defects that the standard detection method for the residual quantity of cyanamide in the field of cyanamide in the prior art is blank, the dietary intake and risk data of the cyanamide of residents are incomplete, and the maximum residual limit value of the cyanamide on food is not specified, and provides a quick, simple, convenient and accurate detection method for the residual quantity of the cyanamide in agricultural products.
The invention is realized by the following technical scheme:
a method for detecting the residual quantity of cyanamide in fruits is characterized by comprising the following specific steps:
(1) drawing of standard curve
Weighing cyanamide solid and diluting with acetonitrile to obtain 10mg/kg and 1.0mg/kg cyanamide solutions, taking 10mg/kg and 1.0mg/kg cyanamide solutions with different volumes, and adding 0.5mL of water, 0.05g of sodium bicarbonate and 0.5mL of 0.5% dansyl chloride acetone solution into each solution with different volumes;
carrying out water bath at the temperature of 50 ℃ and oscillation reaction, then cooling to room temperature, fixing the volume to 2 mL to obtain standard solutions of cyanamide of 0.01mg/kg, 0.05mg/kg, 0.10mg/kg, 0.50mg/kg and 1.0mg/kg, filtering through a filter membrane of 0.45 mu m, and carrying out liquid chromatography tandem mass spectrometry on the cyanamide;
performing regression by taking the concentration as a horizontal coordinate and the peak area as a vertical coordinate to obtain a standard curve of the cyanamide;
(2) sample extraction
Weighing a sample to be detected after homogenate by a wall breaking machine, adding ethyl acetate, performing vortex operation, then adding anhydrous sodium sulfate, performing vortex operation continuously, filtering by filter paper, washing for 2 times by using ethyl acetate, performing rotary evaporation on filtrate, performing water bath at the temperature of 30 ℃, performing reduced pressure rotary evaporation and concentration, adding acetone to a constant volume of 1mL, and obtaining a concentrated solution to be derived;
(3) derivative of concentrated solution
Taking 0.5mL of a to-be-derivatized concentrated solution, adding 0.5mL of water, 0.05g of sodium bicarbonate and 0.5mL of 0.5% dansyl chloride acetone solution, carrying out water bath at the temperature of 50 ℃ and carrying out oscillation reaction to obtain a derivatization solution, and detecting by using a liquid chromatography-tandem mass spectrometer;
(4) determination of recovery
Weighing 15 blank samples homogenized by a wall breaking machine, adding cyanamide standard solutions according to three addition concentrations of 0.01mg/kg, 0.1 mg/kg and 1.0mg/kg, repeating the step (2) and the step (3) for 5 times to obtain a derivative solution to be detected, performing liquid chromatography tandem mass spectrometry, comparing with the cyanamide standard curve in the step (1), calculating to obtain a measured value of cyanamide, and calculating the recovery rate.
(5) Determination of the content of cyanamide in the sample
And (4) comparing the content of the cyanamide detected in the step (3) with the standard curve of the cyanamide in the step (1), and calculating to obtain the actual content of the cyanamide in the sample to be detected.
Preferably, in the step (1), different volumes of the 10mg/kg and 1.0mg/kg cyanamide solution are extracted as follows: 20. mu.L and 100. mu.L of 1.0mg/kg cyanamide solution were pipetted into 2 stoppered tubes, and then 20. mu.L, 100. mu.L and 200. mu.L of 10mg/kg cyanamide solution were pipetted into 3 stoppered tubes, 0.5mL of water, 0.05g of sodium bicarbonate and 0.5mL of 0.5% dansyl chloride in acetone were added to each tube.
Further, in the step (1), the cyanamide standard curve y =3077670X-18185.1, and the correlation coefficient r = 0.9996;
preferably, in the steps (1) and (3), the reaction time is 50-60min by water bath and oscillation.
Preferably, in the step (2), the ratio of the sample to the ethyl acetate and the anhydrous sodium sulfate is 10ml of ethyl acetate and 7g of anhydrous sodium sulfate for every 1g of sample.
Preferably, in the steps (1) and (4), the liquid chromatography conditions are that the chromatographic column: shim-pack XR-ODS 2.0X 75 mm X1.6 μm; the column temperature is 40 ℃; fluidity A: 0.05% formic acid +2 mmol/L ammonium acetate, flowability B: methanol; the fluidity gradient is 0.01 min 10% B, 0.2min 10% B, 0.9min50% B, 3.0min70% B, 3.1min 95% B, 3.6min95% B, 4.0min 10% B; the flow rate is 0.4 mL/min; the sample volume is 1 mu L;
the mass spectrum condition is a positive ion point spray ionization mode; the temperature of the DL pipe is 250 ℃; heating the module at 400 ℃; the flow rate of the drying gas is 15L/min, and the pressure of the collision gas is 230 kPa; the scanning mode is multi-reaction monitoring;
ion pair of target compound: 276.0/156.1 quantitative ion pair, 276.0/171.1 qualitative ion pair.
According to the method for detecting the residual quantity of cyanamide in the fruit, anhydrous sodium sulfate is used for removing water, ethyl acetate is used for extracting, an extracting solution is concentrated, purification is not needed, the extracting solution can be directly derived from dansyl chloride, and the test operation is simple and convenient. The liquid chromatogram tandem mass spectrum multi-reaction monitoring mode is adopted, so that the selectivity and the sensitivity are high, the impurity interference can be effectively reduced, the accuracy and the precision are high, and the technical support is provided for further perfecting and supplementing the dietary intake and risk data of cyanamide of residents and formulating the maximum residual limit.
Drawings
FIG. 1: the reaction scheme of the cyanamide and the dansyl chloride is shown in the invention;
FIG. 2: the standard curve of cyanamide of the invention;
FIG. 3: in the embodiment of the invention, the sample is added with 0.1 mg/kg of cyanamide standard solution to obtain the high performance liquid chromatography tandem mass spectrometry (MRM) chromatogram.
Detailed Description
The following description will be given of specific embodiments of the present invention with reference to the accompanying drawings for further explanation of the detection method of the present invention.
Example 1
1. Main instrumentation and materials
Shimadzu LC/MS 8040; a Guohua SHA-B constant temperature oscillator; shanghai Yangrong RE-52AA rotary evaporator (with Beijing Bo Yi kang HX-1050 type constant temperature circulator); a quick blending device.
Methanol, acetone, ammonium acetate and formic acid are all chromatographically pure.
2. Measurement method
(1) Drawing of standard curve
The cyanamide solid was weighed and diluted with acetonitrile to give 10mg/kg and 1.0mg/kg cyanamide solutions, and a pipette pipettor pipetted 20. mu.L and 100. mu.L of 1.0mg/kg cyanamide solution respectively in 2 stoppered test tubes, and then 20. mu.L, 100. mu.L and 200. mu.L of 10mg/kg cyanamide solution respectively in 3 stoppered test tubes, to each of which was added 0.5mL of water, 0.05g of sodium bicarbonate and 0.5mL of 0.5% dansylchloride acetone solution.
Carrying out water bath at the temperature of 50 ℃ and carrying out oscillation reaction for 50-60min, then cooling to room temperature, fixing the volume to 2 mL to obtain standard solutions of cyanamide of 0.01mg/kg, 0.05mg/kg, 0.10mg/kg, 0.50mg/kg and 1.0mg/kg, filtering through a 0.45 mu m filter membrane, and carrying out liquid chromatography and mass spectrometry analysis and detection on the cyanamide.
And (3) performing regression by taking the concentration as an abscissa and the peak area as an ordinate to obtain a cyanamide standard curve y =3077670X-18185.1 and a correlation coefficient r = 0.9996.
(2) Sample extraction
Weighing 2.0g of large cherry sample homogenized by a wall breaking machine, adding 20mL of ethyl acetate, performing vortex operation for 1min, adding 14g of anhydrous sodium sulfate, performing vortex operation for 1min, filtering by using filter paper, washing by using 10mL of ethyl acetate for 2 times, performing reduced pressure rotary concentration on filtrate by using a rotary evaporator in a water bath at 30 ℃ until the filtrate reaches the size of soybeans, and adding acetone to fix the volume to 1mL to obtain a concentrated solution to be derived;
(3) derivative of concentrated solution
Taking 0.5mL of a to-be-derivatized concentrated solution, adding 0.5mL of water, 0.05g of sodium bicarbonate and 0.5mL of 0.5% dansyl chloride acetone solution, carrying out water bath and oscillation reaction for 50-60min at the temperature of 50 ℃ to obtain a derivatized solution, and determining the content of cyanamide in a sample to be detected by using a liquid chromatography tandem mass spectrometer;
(4) determination of recovery
Weighing 15 parts of 2.0g of large cherry blank sample homogenized by a wall breaking machine, repeating the step (2) and the step (3) according to the addition concentrations of the cyanamide of 0.01mg/kg, 0.1 mg/kg and 1.0mg/kg respectively, repeating each addition concentration for 5 times to obtain a solution to be detected for derivatization, performing liquid chromatography tandem mass spectrometry to obtain a measured value of the cyanamide, and calculating the recovery rate, wherein the data are shown in table 1.
(5) Determination of the content of cyanamide in the sample
And (4) comparing the content of the cyanamide detected in the step (3) with the standard curve of the cyanamide detected in the step (1), and calculating to obtain the actual residual content of the cyanamide in the sample to be detected.
Wherein, the conditions of the liquid chromatogram tandem mass spectrometer are set as follows:
liquid chromatography conditions: a chromatographic column: shim-pack XR-ODS 2.0X 75 mm X1.6 μm; the column temperature is 40 ℃; fluidity A: 0.05% formic acid +2 mmol/L ammonium acetate, flowability B: methanol; the fluidity gradient is 0.01 min 10% B, 0.2min 10% B, 0.9min50% B, 3.0min70% B, 3.1min 95% B, 3.6min95% B, 4.0min 10% B; the flow rate is 0.4 mL/min; the sample size was 1. mu.L.
Mass spectrum conditions: a positive ion point spray ionization mode; the temperature of the DL pipe is 250 ℃; heating the module at 400 ℃; the flow rate of the drying gas is 15L/min, and the pressure of the collision gas is 230 kPa; the scanning mode is multi-reaction monitoring.
Ion pair of target compound: 276.0/156.1 quantitative ion pair, 276.0/171.1 qualitative ion pair.
And (3) carrying out single cyanamide residual quantity detection analysis on 20 random cherry samples (facility cultivation) in the Fushan area of the tobacco terrace according to the detection steps, wherein single cyanamide residual quantity is detected in 4 samples, and the residual quantity is 0.005mg/kg-0.018 mg/kg.
Example 2
1. Main equipment (same as embodiment 1)
2. Measurement method
(1) Standard curve plotting (same as example 1)
(2) Sample extraction
Weighing 1.0g of grape sample homogenized by a wall breaking machine, adding 10mL of ethyl acetate, performing vortex operation for 1min, adding 7g of anhydrous sodium sulfate, performing vortex operation for 1min, filtering by using filter paper, washing by using 10mL of ethyl acetate for 2 times, performing reduced pressure rotary evaporation on the filtrate by using a rotary evaporator in a water bath at 30 ℃ to obtain a near-dry solution, and performing volume fixing on acetone to 1mL to obtain a concentrated solution to be derived;
(3) derivative of concentrated solution
Taking 0.5mL of a to-be-derivatized concentrated solution, adding 0.5mL of water, 0.05g of sodium bicarbonate and 0.5mL of 0.5% dansyl chloride acetone solution, carrying out water bath and oscillation reaction for 60min at the temperature of 50 ℃ to obtain a derivatized solution, and determining the content of cyanamide in a to-be-detected sample by using a liquid chromatography tandem mass spectrometer;
(4) determination of recovery
Weighing 15 parts of 1.0g of grape blank sample homogenized by a wall breaking machine, repeating the step (2) and the step (3) according to the addition concentrations of the cyanamide of 0.01mg/kg, 0.1 mg/kg and 1.0mg/kg respectively, repeating each addition concentration for 5 times to obtain a derivative solution to be detected, performing liquid chromatography tandem mass spectrometry to obtain a measured value of the cyanamide, and calculating the recovery rate, wherein the data is shown in table 2.
(5) Determination of the content of cyanamide in the sample
And (4) comparing the content of the cyanamide detected in the step (3) with the standard curve of the cyanamide detected in the step (1), and calculating to obtain the actual residual content of the cyanamide in the sample to be detected.
The conditions of the liquid chromatography tandem mass spectrometry instrument were the same as in example 1.
And (3) carrying out single cyanamide residue detection analysis on 20 random grape samples of the Futai Penglai according to the detection steps, wherein no single cyanamide residue is detected from any sample.
Example 3
1. Main equipment (same as embodiment 1)
2. Measurement method
(1) Standard curve plotting (same as example 1)
(2) Sample extraction
Weighing 5.0g of pear sample homogenized by a wall breaking machine, adding 50mL of ethyl acetate, performing vortex operation for 1min, then adding 35g of anhydrous sodium sulfate, performing vortex operation for 1min continuously, filtering by using filter paper, washing by using 10mL of ethyl acetate for 2 times, performing reduced pressure rotary concentration on filtrate by using a rotary evaporator in a water bath at 30 ℃ until the filtrate reaches the size of soybean grains, and adding acetone to fix the volume to 1mL to obtain a concentrated solution to be derived;
(3) derivative of concentrated solution
Taking 0.5mL of concentrated solution, adding 0.5mL of water, 0.05g of sodium bicarbonate and 0.5mL of 0.5% dansyl chloride acetone solution, carrying out water bath at the temperature of 50 ℃ and carrying out oscillation reaction for 50-60min to obtain a derivative solution, and measuring the content of cyanamide in a sample to be measured by using a liquid chromatography tandem mass spectrometer;
(4) determination of recovery
Weighing 15 parts of 5.0g of pear blank sample homogenized by a wall breaking machine, repeating the step (2) and the step (3) according to the addition concentrations of cyanamide of 0.01mg/kg, 0.1 mg/kg and 1.0mg/kg respectively, repeating each addition concentration for 5 times to obtain a derivative solution to be detected, performing liquid chromatography tandem mass spectrometry to obtain a measured value of the cyanamide, and calculating the recovery rate.
(5) Determination of the content of cyanamide in the sample
And (4) comparing the content of the cyanamide detected in the step (3) with the standard curve of the cyanamide detected in the step (1), and calculating to obtain the actual residual content of the cyanamide in the sample to be detected.
The conditions of the liquid chromatography tandem mass spectrometry instrument were the same as in example 1.
And (3) performing single cyanamide residual quantity detection analysis on 20 random pear samples of the Tai Laiyang tobacco according to the detection steps, and detecting no single cyanamide residual quantity in the samples.
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (5)
1. A method for detecting the residual quantity of cyanamide in fruits is characterized by comprising the following specific steps:
(1) drawing of standard curve
Weighing cyanamide solid and diluting with acetonitrile to obtain 10mg/kg and 1.0mg/kg cyanamide solutions, taking 10mg/kg and 1.0mg/kg cyanamide solutions with different volumes, and adding 0.5mL of water, 0.05g of sodium bicarbonate and 0.5mL of 0.5% dansyl chloride acetone solution into each solution with different volumes;
carrying out water bath at the temperature of 50 ℃ and oscillation reaction, then cooling to room temperature, fixing the volume to 2 mL to obtain standard solutions of cyanamide of 0.01mg/kg, 0.05mg/kg, 0.10mg/kg, 0.50mg/kg and 1.0mg/kg, filtering through a filter membrane of 0.45 mu m, and carrying out liquid chromatography tandem mass spectrometry on the cyanamide;
performing regression by taking the concentration as a horizontal coordinate and the peak area as a vertical coordinate to obtain a standard curve of the cyanamide;
(2) sample extraction
Weighing a sample to be detected after homogenate by a wall breaking machine, adding ethyl acetate, performing vortex operation, then adding anhydrous sodium sulfate, performing vortex operation continuously, filtering by filter paper, washing for 2 times by using ethyl acetate, performing rotary evaporation on filtrate, performing water bath at the temperature of 30 ℃, performing reduced pressure rotary evaporation and concentration, adding acetone to a constant volume of 1mL, and obtaining a concentrated solution to be derived; the adding ratio of the sample to the ethyl acetate and the anhydrous sodium sulfate is as follows: 10mL of ethyl acetate and 7g of anhydrous sodium sulfate are added to each 1g of sample;
(3) derivative of concentrated solution
Taking 0.5mL of a to-be-derivatized concentrated solution, adding 0.5mL of water, 0.05g of sodium bicarbonate and 0.5mL of 0.5% dansyl chloride acetone solution, carrying out water bath at the temperature of 50 ℃ and carrying out oscillation reaction to obtain a derivatization solution, and carrying out on a machine for determination;
(4) determination of recovery
Weighing a blank sample homogenized by a wall breaking machine, adding a cyanamide standard solution according to the addition amounts of 0.01mg/kg, 0.1 mg/kg and 1.0mg/kg, repeating the step (2) and the step (3) to obtain a solution to be detected for derivatization, performing liquid chromatography tandem mass spectrometry, comparing with the cyanamide standard curve in the step (1), calculating to obtain a measured value of the cyanamide, and calculating the recovery rate.
2. The method for detecting the residual quantity of cyanamide in the fruit as claimed in claim 1, wherein: further comprises the step (5) of measuring the content of the cyanamide in the sample
And (4) comparing the content of the cyanamide detected in the step (3) with the standard curve of the cyanamide in the step (1), and calculating to obtain the actual content of the cyanamide in the sample to be detected.
3. The method for detecting the residual quantity of cyanamide in the fruit as claimed in claim 1, wherein: in the step (1), different volumes of 10mg/kg and 1.0mg/kg of cyanamide solution are extracted as follows: 20. mu.L and 100. mu.L of 1.0mg/kg cyanamide solution were pipetted into 2 stoppered tubes, and then 20. mu.L, 100. mu.L and 200. mu.L of 10mg/kg cyanamide solution were pipetted into 3 stoppered tubes, 0.5mL of water, 0.05g of sodium bicarbonate and 0.5mL of 0.5% dansyl chloride in acetone were added to each tube.
4. The method for detecting the residual quantity of cyanamide in the fruit as claimed in claim 1, wherein: in the step (1), the standard curve y =3077670X-18185.1 of cyanamide and the correlation coefficient r = 0.9996;
in the steps (1) and (3), water bath and oscillation are carried out for 50-60 min.
5. The method for detecting the residual quantity of cyanamide in the fruit as claimed in claim 1, wherein: in the steps (1) and (4), the liquid chromatography conditions are that a chromatographic column: shim-pack XR-ODS 2.0X 75 mm X1.6 μm; the column temperature is 40 ℃; fluidity A: 0.05% formic acid +2 mmol/L ammonium acetate, flowability B: methanol; the fluidity gradient is 0.01 min 10% B, 0.2min 10% B, 0.9min50% B, 3.0min70% B, 3.1min 95% B, 3.6min95% B, 4.0min 10% B; the flow rate is 0.4 mL/min; the sample volume is 1 mu L;
the mass spectrum condition is a positive ion point spray ionization mode; the temperature of the DL pipe is 250 ℃; heating the module at 400 ℃; the flow rate of the drying gas is 15L/min, and the pressure of the collision gas is 230 kPa; the scanning mode is multi-reaction monitoring;
ion pair of target compound: 276.0/156.1 quantitative ion pair, 276.0/171.1 qualitative ion pair.
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| CN113466377A (en) * | 2021-07-16 | 2021-10-01 | 广州国标检验检测有限公司 | Method for detecting cyanamide impurities in medicine |
| CN114235991A (en) * | 2021-11-27 | 2022-03-25 | 山东省烟台市农业科学研究院 | High performance liquid chromatography for determining sec-butylamine content |
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| CN101793881B (en) * | 2009-12-17 | 2012-10-24 | 东北农业大学 | Method for detecting biogenic amine in food |
| CN103822998A (en) * | 2012-11-19 | 2014-05-28 | 中国科学院大连化学物理研究所 | Method for analyzing amine substances in dansyl chloride derived-plasma based on liquid chromatography mass spectrometry |
| CN104502473B (en) * | 2014-12-10 | 2016-07-20 | 黄河三角洲京博化工研究院有限公司 | A kind of quantitative approach utilizing HPLC method detection cyanamide |
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