CN104459002B - A kind of method measuring zinc thiazole residue in vegetables and fruit - Google Patents
A kind of method measuring zinc thiazole residue in vegetables and fruit Download PDFInfo
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- CN104459002B CN104459002B CN201410856739.2A CN201410856739A CN104459002B CN 104459002 B CN104459002 B CN 104459002B CN 201410856739 A CN201410856739 A CN 201410856739A CN 104459002 B CN104459002 B CN 104459002B
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Abstract
The invention belongs to technical field of analytical chemistry, specifically a kind of method measuring zinc thiazole residue in vegetables and fruit, its determination step is, 1) process of sample: get edibility sample part, smash with food masher, mixing; 2) extract: with the ultrasonic extraction of 2% aqueous formic acid; 3) purify: purify with HLB solid-phase extraction column, methanol-eluted fractions; 4) liquid chromatography tandom mass spectrometry determination step 3 is adopted) meoh eluate of gained; 5) according to step 4) amount of the zinc thiazole of gained, the content of zinc thiazole in calculation sample.The present invention is after a kind of sample extracts under acidic aqueous conditions and uses Solid-Phase Extraction column purification, with the method for measuring of liquid chromatography-tandem mass spectrometry instrument, not only assay method fast, simply, and the Accurate Determining of zinc thiazole residuals content in vegetables and fruit can be realized, detection limit is lower than GB2763-2014 limit standard.
Description
[technical field]
The invention belongs to technical field of analytical chemistry, specifically a kind of method measuring zinc thiazole residue in vegetables and fruit.
[background technology]
The Pesticide Residue of various agricultural byproducts is more and more outstanding in recent years, brings direct or indirect impact to health.The different Pesticide Residue of degree is all deposited in countries in the world, and particularly developed country pays much attention to Pesticide Residue, all define more and more stricter limit standard to various agricultural byproducts Pesticide Residues.Many countries take Pesticide Residue as technology barriers, and the import of restriction agricultural product, this directly affects the agricultural byproducts international trade of China.Just start the Pesticide Residue with reference to developed countries from 1981 Nian Qi China, progressively release China's Pesticide Residue standard." Pesticide maximum residue limit " (GB2763-2014) that within 2014, newly issue has increased 60 Multiple Pesticides residue limits indexs newly, wherein also includes some novel agrochemicals.
Zinc thiazole (amino-5 sulfydryls-1 of 2-, 3,4-thiadiazoles zinc, cas number 1202750-31-9) be a kind of newly developed can for the germifuge class agricultural chemicals of multiple fungal disease, good preventive and therapeutic effect is had to the bacterial conditions such as black spot, anthracnose, powdery mildew, angular leaf spot, scarce zinc yellow leaf disease of the crops such as Chinese cabbage, peanut, paddy rice, cucumber, tomato, the defense response of energy activated plant self simultaneously, improves plant to the resistivity of the bad condition such as low temperature, arid.
Zinc thiazole is a kind of organic zinc compound being different from copper agent completely, is widely used in vegetables, paddy rice and part fruit tree kind at present, shows excellent effect.Owing to being a kind of product newly developed, the material secure data of zinc thiazole is also incomplete, and the suction of its residue or feed, the ill symptomses such as human skin stimulation, respiratory tract, stomach stimulation, vomiting, diarrhoea can be caused, infringement health.Therefore zinc thiazole is also put in GB2763-2014 Pesticide maximum residue limit standard.
At home and abroad there is no the detection method of zinc thiazole residue in vegetables and fruit at present in, and zinc thiazole has been listed in limit standard by GB2763-2014, the detection method therefore setting up a zinc thiazole residue is extremely urgent.
[summary of the invention]
Although have maximum residue limit(MRL) requirement for the zinc thiazole newly added in GB2763-2014, but the problem of corresponding method of detection is not had, the invention provides a kind of extraction, purification and Liquid Chromatography-Tandem Mass Spectrometry and detect the method that in vegetable and fruit, zinc thiazole is residual, not only assay method fast, simply, and can realize the Accurate Determining of zinc thiazole content in vegetables and fruit.
Design for achieving the above object and a kind ofly measure the residual method of zinc thiazole in vegetables and fruit, comprise the following steps:
1) sample pretreatment: sample thief, smashes sample, mixes, and loads in glass container for subsequent use;
2) extraction of sample: take appropriate step 1) gained sample, with the ultrasonic extraction of 2% aqueous formic acid;
3) purification of sample extracting solution: get step 2) gained extract, activated good HLB Solid-Phase Extraction column purification, by methanol-eluted fractions;
4) adopt Liquid Chromatography-Tandem Mass Spectrometry instrument to measure the amount of zinc thiazole residue in extract, the condition determination of this Liquid Chromatography-Tandem Mass Spectrometry instrument is:
(1) liquid-phase chromatographic column adopts HALOC18 post, and specification is column length 10 centimetres, column internal diameter 4.6 millimeters, particle diameter 2.7 microns;
(2) liquid chromatography column temperature is set as 25 DEG C;
(3) sample size: 5uL;
(4) flow velocity: 0.3mL/min;
(5) eluent gradient sees the following form:
(6) mass spectrometry parameters sees the following form:
5) last, according to step 4) amount of the zinc thiazole residue of gained, the content of zinc thiazole in calculation sample.
Step 1) in, edibility part got by sample, smashes with food masher, preserves at the sample loaded in glass container is placed in 4 DEG C.
Step 2) in, again mix sample by stirring rod before sampling, then take sample in centrifuge tube, add the aqueous formic acid of 2%, vortex mixing sample, with ultrasonic extractor water bath sonicator 30 minutes, centrifugal 10 minutes in 8000 revs/min, supernatant liquor was filtered in volumetric flask, residue divides secondary extraction of ocean eddies 1min with 2% aqueous formic acid again, be filtered in volumetric flask, finally with 2% aqueous formic acid constant volume to scale, mixing.
Step 3) in, HLB solid-phase extraction column is first successively with methyl alcohol, 2% aqueous formic acid activation, get step 2) in sample extracting solution cross column purification, with 2% aqueous formic acid drip washing pillar, drain pillar, discard all effluxes, by methanol-eluted fractions, drain pillar, collect all extraction solution, in this purification process flow velocity all control 2-3 drip/minute, finally getting this solution appropriate, to cross 0.22 μm of PTFE organic phase pin type filter membrane for subsequent use in LC sample introduction bottle.
Step 5) in, be converted to the amount of zinc thiazole in sample by the amount of zinc thiazole residue in extract, according to matrix calibration curve, adopt quantified by external standard method.
Beneficial effect of the present invention is: the present invention is the method for zinc thiazole in a kind of sample extraction, purification, use liquid chromatography-tandem mass spectrometry instrument mensuration vegetables and fruit, assay method not only fast, simply, and the Accurate Determining of zinc thiazole content in vegetables and fruit can be realized, its detection limit is lower than the maximum residue limit of GB2763-2014, solve in GB2763-2014 the problem only having limit standard not have corresponding method of detection, meet the requirement to zinc thiazole Residue Monitoring in vegetables and fruit completely.
[accompanying drawing explanation]
Fig. 1 is the liquid chromatogram of zinc thiazole in embodiment 2;
Fig. 2 is the multiple-reaction monitoring ion massspectrum figure of zinc thiazole in embodiment 2.
[embodiment]
The invention belongs to the mensuration to zinc thiazole residue in vegetables and fruit in analytical chemistry field, its principle is: extracted by the zinc thiazole aqueous formic acid in sample, use Solid-Phase Extraction column purification, then by the amount of zinc thiazole in liquid chromatography-tandem mass spectrometry instrument working sample.
The method that in mensuration vegetables of the present invention and fruit, zinc thiazole is residual, comprises the following steps:
1) sample pretreatment: sample thief, smashes sample, mixes, and loads in glass container for subsequent use;
2) extraction of sample: take appropriate step 1) gained sample, with the ultrasonic extraction of 2% aqueous formic acid;
3) purification of sample extracting solution: get step 2) gained extract, activated good HLB Solid-Phase Extraction column purification, by methanol-eluted fractions;
4) Liquid Chromatography-Tandem Mass Spectrometry instrument is adopted to measure the amount of zinc thiazole residue in extract;
5) last, according to step 4) amount of the zinc thiazole residue of gained, the content of zinc thiazole in calculation sample.
Wherein, step 1) in, edibility part got by sample, smashes with food masher, preserves at the sample loaded in glass container is placed in 4 DEG C.Step 2) in, again mix sample by stirring rod before sampling, then take sample in centrifuge tube, add the aqueous formic acid of 2%, vortex mixing sample, with ultrasonic extractor water bath sonicator 30 minutes, centrifugal 10 minutes in 8000 revs/min, supernatant liquor was filtered in volumetric flask, residue divides secondary extraction of ocean eddies 1min with 2% aqueous formic acid again, be filtered in volumetric flask, finally with 2% aqueous formic acid constant volume to scale, mixing.Step 3) in, HLB solid-phase extraction column is first successively with methyl alcohol, 2% aqueous formic acid activation, get step 2) in sample extracting solution cross column purification, with 2% aqueous formic acid drip washing pillar, drain pillar, discard all effluxes, by methanol-eluted fractions, drain pillar, collect all extraction solution, in this purification process flow velocity all control 2-3 drip/minute, finally getting this solution appropriate, to cross 0.22 μm of PTFE organic phase pin type filter membrane for subsequent use in LC sample introduction bottle.Step 5) in, be converted to the amount of zinc thiazole in sample by the amount of zinc thiazole residue in extract, according to matrix calibration curve, adopt quantified by external standard method.
Below in conjunction with specific embodiment, following further illustrating is done to the present invention:
Embodiment 1: the mensuration of zinc thiazole residual quantity in oranges and tangerines
1. the preparation of sample solution:
By oranges and tangerines peeling, and remove seed, smash with food masher, mixing, add a cover for subsequent use in loading glass container.Take 5 grams of samples in 50mL centrifuge tube, add the aqueous formic acid of 10mL2%, vortex mixing sample, with ultrasonic extractor water bath sonicator 30 minutes, centrifugal 10 minutes in 8000 revs/min, supernatant liquor Buchner funnel suction filtration enters in Erlenmeyer flask, and residue divides secondary extraction of ocean eddies 1 minute with 5mL2% aqueous formic acid again, and suction filtration enters in Erlenmeyer flask, be transferred in 20mL volumetric flask completely, finally use 2% aqueous formic acid constant volume to 2 scales, mixing, for subsequent use.HLB solid-phase extraction column (200mg/6cc) is first successively with 3mL methyl alcohol, the activation of 3mL2% aqueous formic acid, get the above-mentioned sample extracting solution of 10mL and cross post, with 3mL2% aqueous formic acid drip washing pillar, pillar is drained under slightly high pressure, discard all effluxes, use 5mL methanol-eluted fractions, drain pillar, collect all extraction solution.In purification process, flow velocity all controls at 2 ~ 3 droplets/minute.Getting this solution appropriate, to cross 0.22 μm of PTFE organic phase pin type filter membrane for subsequent use in LC sample introduction bottle.
2. set instrument parameter:
1) liquid-phase chromatographic column adopts HALOC18 post, and specification is column length 10 centimetres, column internal diameter 4.6 millimeters, particle diameter 2.7 microns;
2) liquid chromatography column temperature is set as 25 DEG C;
3) sample size: 5uL
4) flow velocity: 0.3mL/min
5) eluent gradient sees the following form:
6) mass spectrometry parameters sees the following form:
3. quantitative and qualitative analysis
1) qualitative
Retention time through sample peak with standard items peak is compared, and sample peak mass spectrogram is compared with standard substance mass spectrogram, determines whether detect determinand in sample.
2) quantitative
Adopt matrix calibration curve quantified by external standard method
4. calculate
The content of zinc thiazole in solution per sample, the content of zinc thiazole in calculation sample.
Embodiment 2: thiazole Direct spectrophotometry in Chinese cabbage
1. the preparation of sample:
Chinese cabbage removes root, smashes with food masher, mixing, adds a cover for subsequent use in loading glass container.Take 5 grams of samples in 50mL centrifuge tube, add the aqueous formic acid of 10mL2%, vortex mixing sample, with ultrasonic extractor water bath sonicator 30 minutes, centrifugal 10 minutes in 8000 revs/min, supernatant liquor is with being filtered in 20mL volumetric flask, residue divides secondary extraction of ocean eddies 1 minute with 5mL2% aqueous formic acid again, is filtered in 20mL volumetric flask, finally with 2% aqueous formic acid constant volume to scale, mixing, for subsequent use.HLB solid-phase extraction column (200mg/6cc) is first successively with 3mL methyl alcohol, the activation of 3mL2% aqueous formic acid, get the above-mentioned sample extracting solution of 10mL and cross post, with 3mL2% aqueous formic acid drip washing pillar, pillar is drained under slightly high pressure, discard all effluxes, use 5mL methanol-eluted fractions, drain pillar, collect all extraction solution.In purification process, flow velocity all controls at 2 ~ 3 droplets/minute.Getting this solution appropriate, to cross 0.22 μm of PTFE organic phase pin type filter membrane for subsequent use in LC sample introduction bottle.
2. set instrument parameter:
1) liquid-phase chromatographic column adopts HALOC18 post, and specification is column length 10 centimetres, column internal diameter 4.6 millimeters, particle diameter 2.7 microns;
2) liquid chromatography column temperature is set as 25 DEG C;
3) sample size: 5uL
4) flow velocity: 0.3mL/min
5) eluent gradient sees the following form:
6) mass spectrometry parameters sees the following form:
3. quantitative and qualitative analysis
1) qualitative
Retention time through sample peak with standard items peak is compared, and sample peak mass spectrogram is compared with standard substance mass spectrogram, determines whether detect determinand in sample.
2) quantitative
Adopt matrix calibration curve quantified by external standard method
4. calculate
The content of zinc thiazole in solution per sample, the content of zinc thiazole in calculation sample.
As shown in Figures 1 and 2, the liquid chromatography of zinc thiazole, mass spectrogram is respectively.
Claims (5)
1. measure a method for zinc thiazole residue in vegetables and fruit, it is characterized in that, comprise the following steps:
1) sample pretreatment: sample thief, smashes sample, mixes, and loads in glass container for subsequent use;
2) extraction of sample: take appropriate step 1) gained sample, with the ultrasonic extraction of 2% aqueous formic acid;
3) purification of sample extracting solution: get step 2) gained extract, activated good HLB Solid-Phase Extraction column purification, by methanol-eluted fractions;
4) adopt Liquid Chromatography-Tandem Mass Spectrometry instrument to measure the amount of zinc thiazole residue in extract, the condition determination of this Liquid Chromatography-Tandem Mass Spectrometry instrument is:
(1) liquid-phase chromatographic column adopts HALOC18 post, and specification is column length 10 centimetres, column internal diameter 4.6 millimeters, particle diameter 2.7 microns;
(2) liquid chromatography column temperature is set as 25 DEG C;
(3) sample size: 5uL;
(4) flow velocity: 0.3mL/min;
(5) eluent gradient sees the following form:
(6) mass spectrometry parameters sees the following form:
5) last, according to step 4) amount of the zinc thiazole residue of gained, the content of zinc thiazole in calculation sample.
2. the method for claim 1, is characterized in that: step 1) in, edibility part got by sample, smashes with food masher, preserves at the sample loaded in glass container is placed in 4 DEG C.
3. the method for claim 1, is characterized in that: step 2) in, again mix sample by stirring rod before sampling, then sample is taken in centrifuge tube, add the aqueous formic acid of 2%, vortex mixing sample, with ultrasonic extractor water bath sonicator 30 minutes, centrifugal 10 minutes in 8000 revs/min, supernatant liquor is filtered in volumetric flask, and residue divides secondary extraction of ocean eddies 1min with 2% aqueous formic acid again, is filtered in volumetric flask, finally with 2% aqueous formic acid constant volume to scale, mixing.
4. the method for claim 1, it is characterized in that, step 3) in, HLB solid-phase extraction column is first successively with methyl alcohol, 2% aqueous formic acid activation, get step 2) in sample extracting solution cross column purification, with 2% aqueous formic acid drip washing pillar, drain pillar, discard all effluxes, by methanol-eluted fractions, drain pillar, collect all extraction solution, in this purification process flow velocity all control 2-3 drip/minute, finally getting this solution appropriate, to cross 0.22 μm of PTFE organic phase pin type filter membrane for subsequent use in LC sample introduction bottle.
5. the method for claim 1, is characterized in that: step 5) in, be converted to the amount of zinc thiazole in sample by the amount of zinc thiazole residue in extract, according to matrix calibration curve, adopt quantified by external standard method.
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| CN101194611A (en) * | 2007-06-08 | 2008-06-11 | 浙江新农化工股份有限公司 | Thiazole zincium suspension agent and method for producing the same |
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| CN101194611A (en) * | 2007-06-08 | 2008-06-11 | 浙江新农化工股份有限公司 | Thiazole zincium suspension agent and method for producing the same |
Non-Patent Citations (5)
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| 20%噻唑锌悬浮剂的高效液相色谱分析;魏晓林 等;《现代农药》;20141031;第13卷(第5期);23-24,27 * |
| Activity of a novel bactericide, zinc thiazole against Xanthomonas oryzae pv. oryzae in Anhui Province of China;Y.Chen 等;《Ann. Appl. Biol.》;20141027;第166卷;129-135 * |
| Complexes of thiazoles. I. Zinc(II), cobalt(II), copper(II), nickel(II), and platinum(II) derivatives of alkyl-substituted thiazoles;John A. Weaver 等;《Inorganic Chemislry》;19700228;第9卷(第2期);268-273 * |
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